Industrial Edition

RHI Bulletin >2>2013

The Journal of Refractory Innovations

Sulphur Recovery Unit

Chrome Corundum
New Thrust Lock System for Applications in Glass Novel Gas Purging System
Rotary Cement Kilns Melting Furnaces for Copper Anode Furnaces
 RHI Bulletin >2 > 2013
The Journal of Refractory Innovations

RHI Bulletin 2/2013

Industrial Edition

Published by: RHI AG, Vienna, Austria

Chief Editor: Bernd Buchberger
Executive Editor: Markus Dietrich, Alfred Spanring
Technical Writer: Clare McFarlane
Proofreaders: Bernd Buchberger, Clare McFarlane
Project Manager: Ulla Kuttner
Photography, Graphics
and Production: Markus Kohlbacher, Christoph Brandner
Design and Typesetting: Universal Druckerei GmbH, Leoben, Austria
Printers: Universal Druckerei GmbH, Leoben, Austria

Contact: Ulla Kuttner

RHI AG, Technology Center
Magnesitstrasse 2
8700 Leoben, Austria
E-mail: ulla.kuttner@rhi-ag.com
Tel: +43 (0) 502 13-5323
Fax: +43 (0) 502 13-5237
www.rhi-ag.com

The products, processes, technologies, or tradenames in the
RHI Bulletin may be the subject of intellectual property rights
held by RHI AG or other companies.

2<
RHI worldwide
Refractories Simply
Explained in the New RHI
Animation Video
Austria >> A new RHI video, titled
What are Refractory Products? pro-
vides a short animated explanation of
the importance, application, and produc-
tion of refractories. Available in both
English and German on the RHI website
(www.rhi-ag.com), it is designed to be
informative for nonexperts and high-
lights the indispensibility of refractories
for everyday life.
New Transport and Storage
Brochures Available
Austria >> Following frequent customer
requests, RHI created new bilingual
(German/English and English/Russian)
brochures concerning transport and stor-
age issues, with additional languages
planned. Containing state of the art three-
dimensional illustrations, they highlight
the main packaging types, labels, and
storage advice. Furthermore, an insight
into the undesirable hydration process is
provided, along with possible on-site
tests.
Due to different customer requirements,
the new brochures are available in Steel
and Industrial versions, both of which are
available on request from RHI Sales and
Technical Marketing personnel.
TUNFLOWThe RHI Tundish
Flow Modifier
Since its market launch in 2010, RHIs
impact pot and flow modifier for the
tundish has successfully entered 19 coun-
tries all over the world. Experienced
researchers and the use of CFD and water
modelling simulations are the basis for
RHIs customer-orientated approach with
this product, enabling steel plants to make
the best of their existing conditions, such
as tundish geometry, by using the opti-
mum tailored flow modifier concept.
Under the brand name TUNFLOW, RHI
sold over 4000 pieces in 2012 and expects
total sales of more than 6000 pieces in
2013, with an ongoing trend for further
growth in the next years.
RHI Attends UNITECR 2013
Canada >> The 13th Biennial Worldwide Congress on Refractories,
UNITECR13, was held from September 1013, 2013, in Victoria,
British Columbia.
More than 600 international participants were present, including
refractory producers, raw material suppliers, customers from vari-
ous industry segments, and academia. Considered the most impor-
tant refractory conference worldwide, it provides the opportunity
to discuss the latest trends in the sector of high-temperature mate-
rials.
RHI participated in various sessions, presenting topics including
zirconia characterization methods, the challenges for Western mag-
nesia-carbon brick manufacturers, and investigation of thermal
shock in lower slide gate plates. Additional papers focused on dif-
ferent destructive and nondistructive methods to characterize mag-
nesia and magnesia-chromite bricks, improved physical properties
of alumina-silica bricks using sol impregnation, and the perfor-
mance advantages provided by hybrid spinel technology in basic
bricks for cement rotary kiln applications. The latter topic is also
included in the first paper of this Bulletin (page 10).
INTERSTOP Awarded Delivery of Stopper
Control System for the New Baosteel Steel
Plant in Zhanjiang
China >> Baosteel Group Corporation is one of the largest steel
producers in the world, with an installed capacity totalling 45 mil-
lion tonnes per annum. Currently, Baosteel is building a completely
new basic oxygen furnace plant in Zhanjiang (China), as part of a
strategy to concentrate production units and operate process tech-
nology that meets market requirements.
The steel plant will operate three BOFs with a nominal capacity
of 350 tonnes. As highly sophisticated steel grades (e.g., silicon
steels) are scheduled to be produced, converter slide gates for slag
retainment are foreseen. Furthermore, one ladle furnace and two
RH degassers are planned.
In the initial phase, with startup scheduled for the fourth quarter
of 2015, 2 x 2 strand slab casters from Siemens VAI Metals Tech-
nologies will be installed with an annual steel output of 6 million
tonnes. In the next stage, the existing 2 x 1 strand Danieli continu-
ous casting machines (CCMs) from Baosteel Luojing will be relo-
cated and revamped to a 1 x 2 strand CCM at Zhanjiang. After all
three CCMs are operational, the total output will reach 8.75 million
tonnes per annum in 2016.
Baosteel invited international bids for the entire stopper
control system to be installed initial on the 2 x 2 strand slab cast-
ers. The scope of equipment offered by RHI included stopper rods,
electrically actuated stopper drives, the newest generation of VUHZ
mould level sensors, an advanced argon management system
including data storage, and the process control system. A team
from INTERSTOP in Switzerland and Shanghai worked jointly on
the bid, convincing Baosteel of the technology leadership in this
field of flow control. As a result, on October 18, 2013, Stopinc AG
(Switzerland) was informed it had been awarded the contract.
Delivery of the equipment is scheduled for the third quarter of
2014.
>
> 33
 RHI worldwide
RHI Clasil Receives IRMA
Award for Excellence
India >> At the Indian Refractory Mak-
ers Associations (IRMA) 52nd annual
general meeting, held on August 17,
2013, the IRMA Awards for Excellence in
20122013 were announced. RHI Clasil
Ltd., (India) received the accolade Over-
all Excellence in Export Performance for
20122013 in the large scale sector. This
is the second consecutive year RHI Clasil
has been honoured with this award.
The IRMA was established in 1958 and
is the national organization representing
companies designing, engineering, and
installing refractories in India. Currently,
more that 70 refractory manufacturing
companies are members of the IRMA.
RHI Commissions Three
BOF Taphole Changing Units
at Tata Steel Jamshedpur
India >> Tata Steel is one of the largest
steel producers in India with an installed
capacity of 10 million tonnes per annum.
The plant has three BOF steel melting
shops designated LD#1 (2 x 165 tonnes),
LD#2 (3 x 165 tonnes), and LD#3 (2 x 165
tonnes). Whereas LD#1 and LD#2 have
been operating for a long time, LD#3
was only commissioned in 20112012.
In LD#1 and LD#3, the two vessel BOF
operation requires a high-efficiency tap-
hole exchange mechanism to ensure
maximum productivity is achieved. RHI
was approached by Tata Steel to assist
in this regard and after a detailed techni-
cal discussion it was finalized that RHIs
Taphole Breakout Device (TBD) along
with ISOJET C type tapholes would be
the best possible solution to achieve the
desired taphole exchange time. As a
result, RHI received an order for three
TBD machines and the ISOJET C taphole
requirement for both shops.
RHI worked closely with Tata Steel and
within a period of 12 months all four
BOFs in LD#1 and LD#3 were converted
to the ISOJET C taphole system and the
three TBD machines were successfully
commissioned. The taphole exchange
time frame as well as the taphole life
achieved so far is in line with the cus-
tomers expectations.
4<
4 <
TMS Annual Meeting in February 2014
USA >> The 143rd TMS Annual Meeting and Exhibition will take
place at the San Diego Convention Center, California. More than
4000 of the worlds business leaders, engineers, scientists, and
other professionals in the materials field are expected at this event,
which is scheduled from February 1620, 2014, and provides the
opportunity for an outstanding exchange of technical knowledge.
RHI will be presenting technical papers during the prestigious
EPD Symposium in honour of David G.C. RobertsonCelebrating
the Megascaleincluding a paper titled Modelling and Compari-
son of Refractory Corrosion at RHIs Technology Center. RHI will
also participate in the 5th International Symposium on High-Tem-
perature Metallurgical Processing. RHI personnel from numerous
departments look forward to seeing you at booth No. 229 to dis-
cuss any point of interest relating to the presented topics and other
refractory-related areas.
New Casting Sequence Record for RHI at
Outokumpu Stainless Alabama
USA >> Outokumpu Stainless USA (Calvert, Alabama) is a green-
field steel plant that produced its first heat on November 16, 2012.
Currently, RHI has a supply contract for 100% of the isostatically
pressed continuous casting refractory requirements.
On September 12, 2013, the first 8 heat sequence was success
fully cast with a RHI submerged entry nozzle (SEN), surpassing the
previous 6 heats. This achievement was recognized and celebrated
by the Outokumpu casting personnel, along with RHI.
The stainless steel grade was 304, in a mould width of 1260 mm,
with a total casting time of 499 minutes. The SEN (DELTEK
HX10Z98WX08), along with the ladle shroud (DELTEK A100) and
stopper rod (DELTEK A100D99N) were produced at the RHI Say-
brook plant (Ohio, USA).
An enormous amount of effort from the RHI and Outokumpu
team members contributed to this achievement, and additional
improvements are still possible.
56th International Colloquium on Refractories
2013
Germany >> The 56th International Colloquium on Refractories,
held in Aachen from September 2526, 2013, provided an impor-
tant opportunity to present current research topics as well as
develop and recruit the next generation of refractory engineers and
scientists. Diverse new ideas, with the focus on industrial applica-
tions, were introduced by European and international industries
and research institutes. RHI presented papers regarding basic
refractory wear in the nonferrous metals industry; an investigation
and verification of ultrasonic and resonant frequency measurement
methods for fired refractory products; and the importance, organi-
zation, and evaluation of interlaboratory tests.
Once again RHI had a booth in the exhibition area, providing a
meeting place for creative brainstorming and knowledge exchange.
Since a considerable number of delegates came from outside
Europe, this networking platform had an international character.
Nucor Steel Texas Awards
Contract for INTERSTOP
Automatic Mould Level
System
USA >> Nucor Steel Texas, part of the
Bar Mill Group, recently awarded RHI a
contract for the INTERSTOP 13QC Auto-
matic Mould Level System. Five tundishes
will be converted along with twenty gates
for production of 350000 short tons of
round billets annually, and a possible
expansion to 1.1 million tons. Commis-
sioning is scheduled for the second quar-
ter of 2014.
SIEMENS VAI Honours RHI
as a Highly Innovative
Supplier
Austria >> During an award ceremony in
Linz on November 6, 2013, plant manufac-
turer Siemens VAI honoured the perfor-
mances of its outstanding suppliers. RHI
was among seven finalists selected from
numerous international companies. The
Supplier Star was awarded for innovation
regarding the delivery and selection of
refractory materials for FAST, an opti-
mized and patented tapping system that
is integral in SIMETAL EAF Quantum.
The awards are presented on a biennial
basis to recognize its most outstanding
suppliers, since SIEMENS VAI considers
it essential to have strong and reliable
partners in order to be successful on the
global market.
This is the second occasion RHI has
won a Supplier Star award and underlines
the good cooperation between S iemens
VAI and RHI as well as confirms RHIs
position as a competent and innovative
supplier of refractory materials.
50th Anniversary of
ANKERHARTH Mixes
Austria >> In the last 50 years, ANKER-
HARTH has become the No. 1 hearth ram-
ming mix for electric arc furnaces on the
global market. To celebrate this success
story, all ANKERHARTH big bags from the
Breitenau and Hochfilzen plants will have
anniversary stickers in the coming
months. Further information regarding the
ANKERHARTH product range can be
found in the RHI Bulletin > 1 > 2013Steel
Edition.
South America Hosts the Copper 2013
International Conference
Chile >> The 8th Copper/Cobre 2013 conference took place from
December 14, 2013, at the CasaPiedra Convention Center in San-
tiago de Chile. More than 1000 delegates from 160 companies and
organizations participated at this very important meeting, which
has taken place every three years since 1987. RHI had a booth at
the exhibition and also presented five technical papers at the con-
ferencethe worlds largest nonferrous metal meeting, with the
main focus on copper.
The presented papers focused on material characterization of
basic refractories, corrosion testing methods, and a scientific
journey through the area of wear mechanisms in the nonferrous
metal industry. The two additional topics: Novel gas purging tech-
nology for stationary and tilting copper anode furnaces (page 50)
and thermal shock resistant alumina-chromia brands (page 54) are
included in this edition of the Bulletin. For further information
regarding any of the presentations, please contact
nfm-marketing@rhi-ag.com
RHI Achieves a Record Casting Sequence
at SDI Butler
USA >> Steel Dynamics, Inc., in Butler (Indiana) have operated
two thin slab casters since 1998, each with an annual capacity of
1.5 million tonnes. From this time, a major competitor had been
the sole supplier of submerged entry nozzles (SENs) to the plant.
As part of RHIs ISO growth strategy, the Saybrook plant (Ohio,
USA) targeted SENs and stoppers at this customer. After extensive
trials, RHI won a share of the SEN supply in 2012. It had been rec-
ognized by SDI for some time that the SEN slag band wear rate
was better than the long-term supplier. Therefore, on August 18,
2013, SDI personnel had the confidence to run an RHI SEN on
boron grades for 18.5 hours, achieving 3.5 hours beyond the nor-
mal casting time. These grades are the sternest test of thin slab
SENs.
Application Instructions for Basic Mixes
Austria >> Following close collaboration between various
epartments at RHI, the application instructions have been revised
d
and standardized for all grades in the current basic mix product
portfolio.
In contrast to shaped products that are delivered ready for instal-
lation, the correct processing of unshaped products at the custom-
er is an essential and often crucial step in order to achieve the
requested performance level. Therefore, for each grade all the
quality-relevant processing steps, from the right storage conditions
through to installation, are now described in tailor-made operating
instructions. These descriptions are as comprehensive as neces-
sary, while being as simple as possible. Additionally, pictograms
are included in all instructions, which highlight the most important
characteristics and provide hints for proper mix application. In the
future these pictograms should also enable users with reading dif-
ficulties to understand the main content of the instructions and
ensure correct utilization. As part of the project, the operating
instructions for nonbasic and basic mixes have also been
standardized.
>5
Total dedication throughout the year
RHI personnel provide a range
of refractory solutions
 Seasons greetings
from staff at the
Technology Center Leoben

www.rhi-ag.com
 ANKRAL Q-Series
Pure innovation
setting the pace

hybrid spinel technology by RHI

RHI AGRefractory competence for the cement industry

Sophisticated refractory products

Excellence
www.rhi-ag.com

in Refractories
Editorial Contents
A decade ago we launched the RHI Bulletin and over 200 articles 10 Hybrid Spinel Technology Provides
have been published describing innovative products and services Performance Advances for Basic Cement
from RHI as well as broader refractory-related topics. Available in
Rotary Kiln Bricks
both printed and digital format, it regularly communicates how
We lead the Industry. Everywhere. Anytime. 13 New Sol-Bonded Product Members
Gunning Experiences and Shotcasting
This edition contains a wide range of papers, principally focusing Applications
on the cement, glass, and nonferrous metal industries. The first
17 RHI Thrust Lock System for Cement
paper describes how hybrid spinel technology in the ANKRAL
Rotary Kilns
Q-series incorporates brick flexibility into magnesia bricks, which is
not only essential for lining mechanically critical areas but is highly 20 Safety in the Mining IndustryA Value
advantageous in the case of alkali salt infiltration. This is followed by 25 Low Carbon Economy Roadmap for the
a description of the new sol-bonded monolithics that have been
Ceramic Industry
developed for shotcasting and shotcreting applications, enabling
rapid and efficient installation of large amounts of material. Addition- 27 Chrome Corundum: An Alternative to
ally, the extended production programme to facilitate global access Isostatically Pressed Products
to the sol-bonded products is highlighted. A newly designed retain- 31 Postmortem Studies of Standard Silica,
ing system for the outlet zone in rotary kilns is the subject of the next No-Lime Silica, and Fused Cast AZS from
paper, illustrating how the RHI Thrust Lock System will significantly
Oxy-Fuel Fired Soda-Lime Glass Melting
improve refractory service life in this highly stressed kiln section.
Furnaces
Advances described for the glass industry include an economic 36 Microstructural Analysis of Magnesia
alternative to isostatically pressed chrome-containing material for Bricks Operating Under Altered Conditions
areas in glass furnaces that require high corrosion resistance. The in the Regenerator Condensation Zone of
bonded alumina-chrome developed by RHI provides an additional Glass Melting Furnaces
benefit of superior thermal shock resistance. Two further papers
describe postmortem studies that demonstrate the STELLA GNL
40 RHI US Ltd Provides Value-Added Services
no-lime silica brand is advantageous for crown applications in oxy- to Environmental, Energy, and Chemical
fuel fired glass furnaces and microstructural analysis of magnesia Sectors in the USA
bricks operating under altered conditions in the regenerator conden- 42 American Petroleum Institute Refractory
sation zone. Installation Certification Programme
An innovative gas purging system for stationary and tilting copper 44 Determining Resistance to Abrasion at
anode furnaces is introduced in the nonferrous section, as well as Ambient TemperatureImproving
thermal shock resistant alumina-chromia products for the copper Comparability Between Laboratories
industry, and FEA modelling of a lead rotary furnace that resulted in 50 New Innovative Gas Purging System for
a modified lining design and improved furnace lifetime. Stationary and Tilting Copper Anode
Furnaces
Additional papers in this edition describe the full service capability
now offered by RHI US Ltd., the American Petroleum Institute refrac- 54 Thermal Shock Resistant Alumina-Chromia
tory installation programme that has been developed to improve Products for the Copper Industry
refractory reliability and service life, and an approach to increase the 59 Thermomechanical Finite Element
reproducibility of material abrasion testing results. Furthermore, an
Simulation of Heat-Up Processes in a
article regarding safety in the mining industry provides an insight
Lead Rotary Furnace
into this critical issue and the low carbon economy roadmap for the
ceramic industry is summarized in a paper that also includes the first
PRE results providing an average European carbon footprint for a
range of refractory products. Subscription Service
In closing I extend my gratitude to all the authors who kindly contrib-
and Contributions
uted to this edition and the editorial team for their dedication to this
We encourage you, our customers and inter-
publication, many of whom have been involved from its inception. ested readers, to relay your comments, feed-
back, and suggestions to improve the publica-
tion quality using the contact details below.
Yours sincerely Furthermore, to receive the RHI Bulletin free of
charge please e-mail or fax your details to the
Bernd Buchberger Subscription Service using the form on the
Corporate Research and Development back page.
RHI AG
E-mail: ulla.kuttner@rhi-ag.com
Phone: +43 (0) 502 13-5323
Fax: +43 (0) 502 13-5237
>9
 RHI Bulletin > 2 > 2013, pp. 1012

Gerald Gelbmann, Roland Krischanitz and Susanne Jrg

Hybrid Spinel Technology Provides Performance

Advances for Basic Cement Rotary Kiln Bricks
Basic refractories used in cement rotary kiln applications are exposed to a complex mix of
simultaneously acting thermal, mechanical, and chemical stresses. This paper demonstrates
that incorporating brick flexibility into magnesia-based bricks is not only crucial for lining
mechanically critical areas, but it is also highly beneficial in the case of chemical attack
caused by alkali salt infiltration. The second issue is relevant in view of the steadily increasing
amount of alternative fuels fired in rotary kilns. Through the development of a new flexibiliz-
ing technology, this property has been significantly improved compared to magnesia spinel
bricks containing conventional magnesia-alumina spinel (MA spinel, MgAl2O4) for flexibiliza-
tion. The new approach based on a hybrid spinel technology has been implemented in the
Q-series brick brands: ANKRAL QF, ANKRAL Q1, ANKRAL Q2, and ANKRAL QE. With the
ANKRAL Q-series, RHI is able to offer solutions with outstanding thermomechanical behav-
iour even if significant alkali salt densification occurs.

Introduction
Cement rotary kiln refractories are exposed to severe
stresses originating from thermal, mechanical, and chemi-
cal loads. In particular, kiln rotation places basic refractory
materials under critical stresses because magnesia-based
bricks are comparatively brittle. Therefore, special additives
are used, so-called flexibilizing additives, to reduce the brit-
tleness in order to fulfil the high thermomechanical require-
ments in cement rotary kilns.
In addition to the thermomechanical stresses present in
rotary kilns, chemical load must also be considered, espe-
cially in view of the steadily increasing use of alternative
fuels. The infiltration of volatile components like K2O, SO3 ,
and Cl leads to two effects: Corrosion of the ceramic brick
bonding and thereby degeneration of the brick structure,
and a second no less critical effect, densification of the brick
structure by alkali salts that results in loss of thermome-
chanical flexibility.
While in the past chrome ore was used as a standard flexi-
bilizing concept, nowadays spinel group (AB2X4) minerals
are state of the art. These minerals have a lower thermal
expansion than magnesia, and the greater the thermal mis-
match compared to magnesia, the more effective the reduc-
tion in brittleness. The most commonly used minerals are
magnesia-alumina spinel, MgAl2O4 (MA spinel); iron-alu-
mina spinel, FeAl2O4 (hercynite); and manganese-alumina
spinel, MnAl2O4 (galaxite). The main focus of the research
performed was to develop, through the systematic use of
different spinels, high-performance bricks for cement rotary
kilns able to withstand high mechanical loads in combina-
tion with chemical stresses. An additional aim was to
reduce the loss of flexibility once the brick structure is den-
sified by alkali salts.
Spinel-Containing Magnesia Bricks
Two different brick types based on sintered synthetic high-
purity magnesia (MgO > 98 wt.%) and one type based on
sintered natural magnesia (MgO > 97 wt.%) were produced
on a pilot scale for the analyses. Type A was a magnesia
spinel brick, while types B and C were based on hybrid spi-
nels and different sintered magnesia grades (Table I). All the
brick types were fired at the same temperature.
Dynamic Youngs Modulus
Initially the dynamic Youngs modulus of all three materials
was determined to characterize the thermomechanical
behaviour. This investigation was performed by measuring
the ultrasonic velocity as a sample was heated from room
temperature to 1400 C and as it cooled back to room tem-
perature [1].
The Youngs modulus or modulus of elasticity describes the
amount of stress required to create a defined, reversible
deformation in a material. It is also a characteristic of the
amount of stored elastic energy at this defined deformation
(i.e., a high Youngs modulus indicates a high amount of
stored elastic energy). The higher this value, the higher the
brittleness and the lower the thermal shock resistance of
the material. When the dynamic Youngs modulus of a pure
magnesia brick sample without flexiblizer was determined,
it showed a very brittle behaviour that slightly reduced with
increasing temperature and then increased back to the orig-
inal value as the sample cooled to room temperature (Fig-
ure 1). In comparison, the Youngs modulus was signifi-
cantly lower when MA spinel flexibilizer was present. Fur-
thermore, the temperature-dependent change of the
Youngs modulus was significantly different for the magne-
sia MA spinel sample compared to the pure magnesia
A B C
MgO 88.0 87.2 86.1
CaO 0.7 0.7 1.6
SiO2 0.3 0.3 0.8
Al2O3 10.5 9.1 9.0
Fe2O3 0.5 2.7 2.5
Table I. Chemical composition (wt.%) of the magnesia-based
brick types containing different spinel concepts.

10 <
 RHI Bulletin > 2 > 2013

refractory (see Figure 1). At room temperature the Youngs
modulus was low, slightly increasing as the sample was
heated up. Upon cooling the Youngs modulus significantly
increased until it reached a maximum at approximately
10001100 C. With further cooling the Youngs modulus
returned to the original value at ambient temperature. The
increase during cooling down was caused by the thermal
misfit between magnesia and flexibilizer.
The type B material containing hybrid spinel showed a
lower overall dynamic Youngs modulus compared to the
conventional magnesia MA spinel brick sample (type A)
(Figure 2), as did type C. In addition, not only was the
Youngs modulus at a lower level during the entire heat-up
procedure, which would lead to a lower risk of spalling at
the hot face during heat-up in a cement rotary kiln, the
increase during cooling was also much less. Since the brick
type B did not show such a significant increase in brittle-
ness during cooling down, the danger of spalling at the hot
face during kiln cooling would be considerably reduced.
load/displacement curve during stable crack propagation
and indicates a materials ability to absorb thermomechani-
cal stress. To provide a more detailed understanding of the
different brick types thermomechanical properties, wedge
splitting tests were performed at 1100 C, the temperature at
which the most brittle behaviour was determined from the
dynamic Youngs modulus. Brick type B showed a signifi-
cantly higher Gf (area under the graph) than brick type A
(Figure 3). The maximum vertical force occurred at a higher
displacement compared to the brick type A and after passing
the maximum, the vertical force remained at a higher level,
which indicates a higher resistance against crack propaga-
tion. Brick type C showed similar results to brick type B.
In summary, both brick types containing hybrid spinels
showed a significantly lower dynamic Youngs modulus and
a very high resistance against crack propagation compared
to the magnesia MA spinel brick. These thermomechanical
properties are advantageous in high mechanically loaded
rotary kilns.

Thermomechanical Properties of
Wedge Splitting Test
Infiltrated Bricks
The wedge splitting test enables the mechanical fracture
In order to examine the thermomechanical behaviour under
behaviour of refractory materials to be examined and can
chemical load, further laboratory investigations were per-
be performed at temperatures up to 1500 C [2]. The spe-
formed. Crucibles were prepared from the three different
cific fracture energy, Gf , is determined by evaluating the
brick types. The crucibles were filled with KHSO4, heated to
950 C, and held for 24 hours. The dynamic Youngs modulus
800 of the crucible material was measured ultrasonically before
and after the materials had been subject to chemical loading.
700 Pure magnesia brickbrittle
Dynamic Youngs modulus [GPa]

600
As expected the noninfiltrated crucibles with hybrid spinel
technology showed a lower Youngs modulus compared to
500 noninfiltrated magnesia MA material (Table II). However, the
400
Type mass (%) E0 (%) E1 (%)
300
A 5.7 100 118
200 B 5 65 97
100 C 5.9 64 95
Magnesia brick with flexibilizerlow brittleness
0
Table II. Mass increase (mass) and relative Youngs modulus of
0 500 1000 1500
the three brick types before and after chemical loading. E0 is the
Temperature [C] relative Youngs modulus prior to chemical loading compared to
a noninfiltrated magnesia MA spinel sample and E1 denotes the
Figure 1. Dynamic Youngs modulus of brittle (pure magnesia) relative Youngs modulus after chemical loading compared to a
and flexible (magnesia MA spinel) brick samples. noninfiltrated magnesia MA spinel sample.

800 900
n A n A
700 n B n B

600
Youngs modulus [GPa]

600
Vertical force [N]

500

400

300
300
200

100

0 0
0 500 1000 1500 0 1 2 3 4 5 6 7 8 9 10
Temperature [C] Displacement [mm]

Figure 2. Dynamic Youngs modulus of magnesia MA spinel (A) Figure 3. Wedge splitting test performed on magnesia MA spinel
and magnesia hybrid spinel (B) brick samples. and magnesia hybrid spinel brick samples at 1100 C.

> 11
 RHI Bulletin > 2 > 2013

heavily infiltrated crucibles with hybrid spinel technology Established several years ago, the first member of the
also had a lower Youngs modulus than the nonchemically Q-series, ANKRAL QF, is the top grade in the series. It has
loaded magnesia MA spinel material (Figure 4). This result demonstrated outstanding performance in critical kiln areas,
justifies the expectation that magnesia hybrid spinel bricks for example tyre sections subjected to alkali salt attack [3].
with outstanding thermomechanical properties provide In many cases the lifetime of previous installations has
excellent service lifetimes in high chemically loaded cement been increased significantly, in some cases even more than
rotary kilns. Since magnesia hybrid spinel bricks strongly doubled. The experience gained from in service results with
infiltrated with alkali salts are not as brittle as noninfiltrated ANKRAL QF was the starting point for further product
standard magnesia MA spinel bricks, the sensitivity of den- developments. For example, the hybrid spinel technology
sified bricks containing the hybrid spinel technology to ther- was adapted for use with RHIs own sintered magnesia
mal shock and thereby spalling at the hot face is signifi- resources. The result was ANKRAL Q2, a product with an
cantly reduced. unparalleled price/performance ratio. This RHI brand also
has a long list of successful references [4]. As installation
The Q-SeriesA Complete Product Range results have shown, ANKRAL Q2 is able to successfully
compete with high cost competitor products and also offers
Based on research results and experience gained from suc-
solutions for highly loaded transition zones in alternative
cessful installations and brick performances, the product
fuel fired kilns.
range containing the hybrid spinel technology has been
extended and a comprehensive new product line is avail
ANKRAL Q1 has been operational in various kilns since the
ablethe Q-series.
beginning of 2013 and supplements the high-grade Q-series
product range, also focusing on highly loaded transition
zones in alternative fuel fired kilns.
125
n A
115 n B Additionally, the Q-series offers a solution for the sintering
n C zone. With ANKRAL QE RHI has developed a hybrid spinel
Relative Youngs modulus [%]

105 brick based on iron-rich sintered magnesia. This brand pro-

motes the superior coating adherence desired for applica-
95 tions in the central burning zone with the outstanding flexi-
bility of the Q-series. ANKRAL QE comprises an additional
85
novel technology enabling excellent refractoriness under
75
load (i.e., T0.5 = 1660 C). Accordingly, ANKRAL QE can be
recommended not only for severely stressed central burn-
65 ing zones but also for transition zones.

55 With the various different brands currently available in the

0.0 2.0 4.0 6.0 8.0
Q-series, the most appropriate brick for a particular applica-
Relative mass increase during corroision test [%]
tion and operating conditions can be selected. This provides
cement customers with outstanding refractory performance
Figure 4. Comparison of the relative Youngs modulus of
noninfiltrated and chemically loaded magnesia MA spinel for the range of conditions in the basic lining zone at a low
samples and magnesia hybrid spinel samples. investment cost.

References
[1] Triessnig, A., Studnicka, H. and Prietl, T. Determination of Thermo-Mechanical Properties at the RHI Refractories Technology Center Leoben.
RHI Bulletin. 2006, No.1, 3337.
[2] Tschegg, E., Fendt, K., Manhart, C. and Harmuth, H. Fracture Properties of Refractory Materials Under Uniaxial and Biaxial Loading. RHI Bulletin.
2010, No. 1, 4047.
[3] Jrg, S., Gelbmann, G., Krischanitz, R. and Fritsch, P. ANKRAL QFA New Brick to Combat Tyre Stresses. RHI Bulletin. 2010, No. 1, 812.
[4] Jrg, S., Gelbmann, G. and Krischanitz, R. ANKRAL Q2An Innovative Solution for Transition Zones. RHI Bulletin. 2012, No. 2, 811.

Authors
Gerald Gelbmann, RHI AG, Technology Center, Leoben, Austria.
Roland Krischanitz, RHI AG, Industrial Division, Vienna, Austria.
Susanne Jrg, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Roland Krischanitz, roland.krischanitz@rhi-ag.com

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RHI Bulletin > 2 > 2013, pp. 1316

Ren von der Heyde, Roland Krischanitz and Milo Blajs

New Sol-Bonded Product MembersGunning

Experiences and Shotcasting Applications
Very different types of sol-bonded monolithic refractories have been introduced and described
in past Industrial [13] and Steel [4,5] RHI Bulletins. These articles highlighted the diverse
application methods, industries, and customer-orientated research and development activities
at RHI regarding the sol-bonded product range. Particularly in the cement industry, these prod-
ucts have earned a very good reputation in the last years [6]. This paper presents, along with
impressive service performances of existing products, new application techniques available
using shotcasting (pumping) and shotcreting (wet gunning), which were developed in close
cooperation with an installation company and customers. Shotcasting is highly sophisticated
and enables very large amounts of material to be installed in a very short time frame with low
manpower. The first recent application using this technique to install more than 100 tonnes of
material at a Swiss cement plant is described as well as a smaller installation in Germany.

Introduction for example COMPAC SOL F53G-6. The chemical composi-

The sol-bonded castables have been previously described
in detail in the RHI Bulletin [15]. The key features are easy
installation, no predrying, rapid and simple heat-up, high
application temperatures, and superior physical and chemi-
cal properties throughout the complete product group. After
very good results with old stored material, the recom-
mended shelf life of COMPAC SOL and CARSIT SOL prod-
ucts was recently increased to 18 months (previously 12
months), which provides customers, particularly in the case
of long-term planning, more possibilities regarding project
stock management. Currently, the sol-bonded materials
have a shelf life of more than 200% compared to common
low-cement castables and a very impressive 400% longer
storage life in comparison to other quick drying monolithics
available on the market.
Driven by continued increasing sales in the cement and
lime, steel, and environmental, energy, and chemical indus-
tries, the volume of sol-bonded alumina monolithic prod-
ucts sold, for the core brands COMPAC SOL, CARSIT SOL,
and COMPAC ROX, has risen by almost 170% compared to
2012 [3]. This continuous trend places these materials
among the fastest developing product group for RHI.
With sales and applications growing in all industries, not
only the actual tonnage sold is evolving fast, the product
portfolio is also rapidly developing. With more and more
customers experiencing the wide range of advantages pro-
vided by these products, including installation ease, drying
out and performance advantages, the pressure on competi-
tors in the market is rising. RHI is committed to retaining
this leading role and further extending market share
through new research and development activities, for
example the gunning advances described in this paper.
Sol-Gunning Experiences
Particularly the dry gunning products have had a very posi-
tive market impact. Comparing the period from Q3/2011
Q2/2012 with Q3/2012Q2/2013, sales of COMPAC SOL and
CARSIT SOL gunning mixes grew by more than 300%. The
gunning mixes are indicated in the brand nomenclature by G,
tion and material properties of the current sol-bonded gun-
ning and shotcreting product range are detailed in Table I.
To date, no competitor can offer fast drying materials for
gunning applications. In the past 12 months, sol-bonded
dry gunning materials were installed for example in Ger-
many, France, Ireland, Italy, the United Kingdom, Switzer-
land, India, and Luxembourg, mainly in the cement and
lime industries.
The first sol-bonded dry gunning material installations were
carried out at the beginning of 2011 and were described in
detail in the last Industrial RHI Bulletin [3]. An installation in
the roof and sidewall of a cooler in Germany provides a
very good example of the extraordinary performance dem-
onstrated by sol-bonded gunning materials. During the
installation one roof field was installed with a competitor
cement-bonded gunning material. The two different cast
ables can be easily distinguished by their colour in Figures
14, since the competitor cement-bonded gunning castable
appears more orange in colour. After one year (March 2012)
there was no major difference in the appearance of the two
materials (see Figures 1 and 2). However, after the second
year in service (February 2013), significant wear was
observed with the cement-bonded gunning castable (see
Figures 3 and 4), whereas CARSIT SOL F10G-6 was still in
very good condition. This result is even more convincing if
it is taken into account that the sol-bonded material was
based on fireclay whereas the conventional gunning mate-
rial had a mullitic raw material base. Both monolithics con-
tained approximately 10 wt.% silicon carbide.
Sol-Bonded Shotcreting
Dry gunning (i.e., torcreting or guniting) is a well-known
and commonly used installation method for fast turnaround
repairs. It is very rapid, flexible, and cheap in terms of
machinery demand. However, there are further gunning
methods that exist for installing large amounts of monolith-
ics that can now also be used for sol-bonded products,
namely shotcasting and shotcreting. Whilst torcreting
enables 12 tonnes of monolithic to be installed per hour,
using shotcasting 10 tonnes per hour can be achieved

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 RHI Bulletin > 2 > 2013

Brand Al2O3 SiO2 Fe2O3 SiC CCS (N/mm2) LTE ATL SL Raw materials Additional information
(wt.%) (wt.%) (wt.%) (wt.%) 110 C 1000 C 1000 C (C) (months)
(%)
COMPAC SOL F53G-6 50.0 47.0 0.7 - 45 45 0.55 1570 18 Dense fire clay, low iron
COMPAC SOL M64G-6 61.0 34.0 0.7 - 55 65 0.55 1670 18 Mullite
COMPAC SOL S64G-6 63.0 36.0 0.5 - 55 60 0.55 1670 18 Andalusite
COMPAC SOL FS99-3 1.5 98.0 0.2 - 20 30 0.00 1600 18 Fused silica
COMPAC SHOT FS99-3 0.2 99.5 0.1 - 12 25 0.00 1650 18 Fused silica Shotcreting, hot repair
CARSIT SHOT F30SB-6 39.0 30.0 0.6 30 63 75 0.55 1550 18 Dense fire clay, low iron/SiC Shotcreting
CARSIT SHOT M10SB-6 58.0 28.0 0.9 10 55 65 0.55 1650 18 Mullite/SiC Shotcreting
CARSIT SOL F10G-6 45.0 42.0 0.7 10 45 50 0.55 1550 18 Dense fire clay, low iron/SiC
CARSIT SOL F30G-6 38.0 31.0 0.7 30 45 45 0.55 1550 18 Dense fire clay, low iron/SiC
CARSIT SOL M10G-6 57.0 30.0 0.7 10 55 65 0.55 1650 18 Mullite/SiC
CARSIT SOL M30G-6 44.0 20.0 0.7 30 65 75 0.55 1580 18 Mullite/SiC
CARSIT SOL S10G-6 60.0 23.0 0.7 10 55 55 0.55 1650 18 Andalusite/SiC
CARSIT SOL S30G-6 44.0 22.0 0.7 30 55 55 0.55 1580 18 Andalusite/SiC

Table I. Product range of sol-bonded gunning and shotcreting mixes for the cement industry. Abbreviations include cold crushing
strength (CCS), linear thermal expansion (LTE), application temperature limit (ATL), and shelf life (SL).

Figure 1. Cooler roof in a German cement plant 1 year after Figure 3. Cooler roof section in Figure 1 after 2 years in opera-
installation. The darker orange field in the background was lined tion. The orange coloured cement-bonded material in the back-
with a competitors conventional cement-bonded gunning mate- ground showed heavy wear.
rial. The other areas were lined with CARSIT SOL F10G-6.

Figure 2. Reverse view of the cooler roof section in Figure 1. Figure 4. Cooler roof section in Figure 2 after 2 years. The
Both gunned materials looked very similar in terms of wear after anchoring was completely exposed in the orange coloured
1 year and the performance was considered equal by the cus- cement-bonded material in the foreground and material loss had
tomer at this time. occurred due to significant crack formation.

14 <
 RHI Bulletin > 2 > 2013
easily. Shotcasting is a wet gunning method using adapted
vibration castables. It involves mixing the monolithic with
the required amount of liquid in a paddle or compulsory
mixer, pumping the wet material via double piston pumps to
the application area, and finally gunning with the use of a
small amount of compressed air and an accelerating liquid.
For shotcasting applications, the well-known RHI sol-bonded
vibration castables were slightly adapted to improve their
pumping propertiesmainly to reduce friction in the pipes
and hoses. In addition, it was necessary to develop a com-
pletely new accelerating liquid, since the sodium silicate
solution (DIKASIL K) commonly used for cement-bonded
materials does not work with the cement-free bonding sys-
tem. As it is very effective, only a few litres of the newly
developed DIMASIL SB-LIQUID accelerator are needed per
tonne of shotcasting mix.
To fulfil the very tight development schedule, ensure optimal
workability, and to profit from the experience of an installa-
tion company, RHI worked closely together with Moeller
Feuerfesttechnik GmbH & Co. KG (Germany). Moeller was
very interested in this project because it sees great potential
in the sol-bonding features, particularly the short heat-up
period. The trials included tests with different pumps, a real-
istic gunning environment, including overhead gunning and
anchoring, as well as sample preparation to examine the
physical properties after installation (Figures 5 and 6).
Development during the 4 trial days at Lemgo (Moeller main
yard) and the RHI Urmitz plant is a very good example of the
successful collaboration between a refractory producer and
an experienced installation company to create a new
Figure 5. Machinery and setup for a shotcreting trial with the
German installation company Moeller Feuerfesttechnik in 2013
at their main yard in Lemgo.
Figure 6. Shotcreting trial at Lemgo showing overhead gunned
panels. The lower left section generated a gunned sample for
further testing.
product. In fact two products were created containing silicon
carbide, CARSIT SHOT M10SB-6 and CARSIT SHOT F30SB-6.
The acronym SB in the brand name indicates sol-bonded and
distinguishes these products from the conventional cement-
bonded brands.
Initially the cooperation with Moeller resulted in the installa-
tion of more than 100 tonnes of CARSIT SHOT M10SB-6 and
CARSIT SHOT F30SB-6 for a Swiss cement plant repair (i.e.,
cooler, kiln hood, nose zone, and inlet chamber area) in spring
2013 (Figure 7). A few weeks later a further cooler repair was
carried out in a German cement plant (Figure 8) by Moeller.
Sol NewsRecent Developments
In the last years, the focus for sol-bonded castables was
mostly on Europe, with a more recent extension of the
demand worldwide. Therefore, whilst virtually all sol-bonded
castables were originally produced in Urmitz (Germany),
RHIs largest alumina monolithic production plant, now a
selection of sol-bonded products are also available from RHI
production sites in India, Canada as well as Mexico, facilitat-
ing access to these sophisticated products for customers
globally.
North and South America
After the first excellent results with sol-bonded materials in
North and South America delivered from Europe, production
of selected castables from the sol-bonded product range was
extended to the RHI plants in Tlalnepantla (Mexico) and Burl-
ington (Canada). In addition, products for torcreting applica-
tions are in preparation (Figures 9 and 10) and will be avail
able by the end of 2013.
Figure 7. Kiln hood (roof) gunned with CARSIT SHOT M10SB-6
at a Swiss cement plant in spring 2013.
Figure 8. Shotcreting application of CARSIT SHOT M10SB-6 in a
cooler area at a German cement plant in spring 2013.
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 RHI Bulletin > 2 > 2013

Figure 9. First sol-bonded gunning trial at the RHI Tlalnepantla Figure 10. Gunning equipment at the RHI Tlalnepantla plant
plant (Mexico) in April 2013. (Mexico), including an Allentown pressure vessel gunning
machine.

Asia-Pacific also show excellent performance and doubtless meet cus-

For the last two years, sol-bonded materials for casting
applications have been available from the RHI joint venture
Clasil plant in Visakhapatnam (India), mainly serving the
Asia-Pacific market. As a result of the reported excellent
performances of CARSIT SOL M10-5 V from cement cus-
tomers in Taiwan (i.e., nose zone) and New Zealand (i.e.,
burner pipe), in which the service life of various units was
increased significantly, demand for such innovative solu-
tions has risen. Therefore, the development of gunning
materials to be produced at Clasil is currently underway
and the first products will be available by the end of 2013.
Conclusions and Outlook
The first dry gunning sol-bonded installations and initial
results were presented a year ago [3]. Now longer term
results are available that further demonstrate the advan-
tages of these gunning mixes that no other refractory sup-
plier can currently offer. Not only regarding installation, but
also in terms of performance, they show significant advan-
tages and more and more customers are benefiting from
these types of materials.
The very successful sol-bonded monolithics were recently
adapted for application using shotcreting technology and
the initial installations have been very successful. If past
experiences are taken as a guide, these applications will
tomer expectations.
Trials with sol-bonded monolithics started only a number
of years ago with a few tonnes of cast material installed in
German cement plants. Since this time sol-bonded cast
ables have virtually developed into the standard lining
materials at numerous cement plants, not only in areas that
are difficult to dry and heat-up, but also for applications
with severe operating conditions in terms of alkali attack,
mechanical and thermal load, as well as thermal shock.
Since it is only a relatively short period of time since the
market introduction of the sol-bonded products it is difficult
to determine their eventual success; however, indications
are they will way exceed initial expectations in the future.
The sol-bonding technology is still under development,
with further improvements ongoing and the next promis-
ing technology already in sight. The so-called mullite-
bonded castables [5], which are also cement-free cast
ables, represent a further advance in the sol-bonded
mixes. The unique matrix design enables outstanding
material properties to be realized. The first products have
already proven very successful for electric arc furnace
roofs in the steel industry. In view of the high application
temperatures, this is also a promising product for the most
severe operating conditions in the cement industry, for
example the burner tip.

References
[1] Blajs, M., von der Heyde, R., Fritsch, P. and Krischanitz, R. COMPAC SOLThe New Generation of Easy, Safe, and Fast Heat-Up No Cement
Castables. RHI Bulletin. 2010, No. 1, 1317.
[2] Fritsch, P., von der Heyde, R. and Krischanitz, R. COMPAC SOLOperational Experiences With the Easy, Fast Heat-Up No Cement Castable.
RHI Bulletin. 2011, No. 2, 4245.
[3] von der Heyde, R., Krischanitz, R., Hall, D. and Zingraf, E. COMPAC SOLThe Success Story Continues With Gunning Mixes and New Product
Developments. RHI Bulletin. 2012, No. 2, 1216.
[4] Schtz, J., Maranitsch, A. and Blajs, M. New Oxycarbide Refractory Products Demonstrate Outstanding PropertiesFirst Practical Results.
RHI Bulletin. 2012, No 1, 1619.
[5] Hochegger, M., Blajs, M., Nonnen, B. and Zottler, P. First Practical Results With COMPAC SOL A100S-15A High-End Sol-Bonded Castable
Designed for EAF Deltas. RHI Bulletin. 2013, No. 1, 1419.
[6] von der Heyde, R., Taha, H. and Sadek, W. The Keys to Improvement. World Cement. 2013, 44, No. 8, 7376.

Authors
Ren von der Heyde, RHI AG, Industrial Division, Mlheim-Krlich, Germany.
Roland Krischanitz, RHI AG, Industrial Division, Vienna, Austria.
Milo Blajs, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Roland Krischanitz, roland.krischanitz@rhi-ag.com

16 <
RHI Bulletin > 2 > 2013, pp. 1719

Andreas Wiry and Hans Ulrich Marshall

RHI Thrust Lock System for Cement Rotary Kilns

The permanent refractory lining problems in the outlet zone of many rotary kilns need to be
tackled with the highest priority. Therefore, a specific project was initiated by RHI to evaluate
prevailing wear mechanisms as well as the strengths and limitations of existing designs. The
outcome of this project is a newly designed retaining concept, called the RHI Thrust Lock
System, which will significantly improve the refractory lining service life in this highly
stressed kiln section. The design differences and targeted advantages compared to existing
concepts are highlighted in this paper.

Introduction The Veitscher-Magotteaux system [2] (Figure 3) was the

The specific topic of excessive thermomechanical stresses
at the rotary kiln outlet was the focus of a previous RHI Bul-
letin article [1]. Despite numerous different lining designs
and refractory materials installed and tested in the past
(e.g., magnesia and SiC bricks, castables, and preshaped
blocks), until now no comprehensive solution has been
available to solve all the severe lining problems that occur
in the kiln outlet zone (Figure 1).
Due to the excessive axial lining thrust of modern high-per-
formance kilns and the resulting thermomechanically over-
stressed lining, conventional designs, namely brick and/or
castable lining combined with rectangular retaining rings
(Figure 2), often do not achieve an acceptable service life or
stop the axial lining thrust entirely.
first, but also the latest design, offering considerable
improvements. However, under excessive stress and unfa-
vourable conditions even this conical multistep retaining
ring system sometimes does not perform satisfactorily.
The central limitation of this design is the relatively small
inclination angle of the metallic retaining segments, which
is only 20. Due to the prevailing high temperatures, lim-
ited heat resistance, and low mechanical strength of the
metallic honeycomb segments at higher temperatures,
the height of these metallic segments is restricted to about
70 mm. As a result of various operating conditions, for
example frequent shutdowns, ovality, and kiln shell defor-
mation, the special bricks installed at the segments can
override (Figure 4) causing force transmission to the outlet
segments.

Figure 1. Destroyed brick lining at the retaining ring of a rotary kiln. Figure 3. Veitscher-Magotteaux system (four steps).

Figure 2. Rectangular retaining ring design. Figure 4. Veitscher-Magotteaux system showing a 40 mm brick
override (arrows) in the direction of the kiln outlet.

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 RHI Bulletin > 2 > 2013

RHI Thrust Lock System brand termed ANKRAL TLS was created for this special
application. Moreover, due to the raw material basis com-
The challenging target was to design a new system that
prising the purest sintered synthetic magnesia and a special
would provide additional benefits compared to already
spinel concept, ANKRAL TLS offers excellent resistance
existing concepts as well as the possibility to upgrade cur-
against corrosion and clinker melt infiltration. Depending
rent retaining designs. Instead of the common brick and
on the installation position and working conditions, high-
rectangular retaining ring design, a special skew brick set is
alumina bricks or SiC bricks can also be used.
used in the RHI Thrust Lock System (Figure 5). Due to the
skew brick inclination (>> 20), the contact face between
Continuing the basic RHI Thrust Lock System idea, a slightly
retaining elements and brick lining is much higher and modified skew brick set (Figure 7) can be installed mid-kiln,
therefore the resulting contact pressure is considerably directly in front of an outlet segment, or additionally as part
reduced. In addition, the axial lining thrust is diverted into of an existing Veitsch-Magotteaux system.
radial and circumferential forces and consequently mechan-
ical stress in the bricks is further reduced.

Using the Abaqus, Version 6.12, finite element method

(FEM) program, three-dimensional models were created to
compare the load profiles and stress centres generated with
the Veitsch-Magottaeux system (20), a common rectangu-
lar retaining ring design, and the new RHI Thrust Lock Sys-
tem (Figure 6).

The simulated brick movement and load distribution with

the Veitsch-Magotteaux system, under excessive load con-
ditions, are shown in Figure 6a. The other models demon-
strate that while the mechanical stress generated with the
common brick and rectangular retaining ring design (Figure
6b) can easily exceed the brick crushing strength and cause
the well-known brick damage (e.g., crack formation and (a)
crushed bricks) associated with this system, the maximum
axial stress level with the Thrust Lock System is reduced by
at least 30%. An inclination of 40 was selected for the RHI
Thrust Lock System. In the model a homogeneous load dis-
tribution over the entire contact face of bricks was visible
(Figure 6c). The slight brick override can be compensated
with an expansion joint.

In spite of the favourable load reduction with this new sys-

tem, the thrust bearing bricks are highly stressed and there-
fore particular material characteristics are required to with-
stand the complex thermomechanical load conditions.
Based on the knowledge gained during development of the
unique ANKRAL Q-series technology, focused on outstand-
ing structural flexibility combined with high mechanical
(b)
strength at high temperatures (see page 10), a new top

(c)

Figure 5. New RHI Thrust Lock System installed at a retaining
ring, comprising special skew brick sets (cream and brown) and
an expansion joint (white).
Figure 6. Three-dimensional FEM models of the (a) Veitsch-
Magotteaux system (one step 20), (b) common brick and rectan-
gular retaining ring design, and (c) RHI Thrust Lock System
(skew brick 40). Dark green indicates tensile stresses and light
green to dark red depicts the increasing compressive stresses.

18 <
 RHI Bulletin > 2 > 2013
Figure 7. New RHI Thrust Lock System installed mid-kiln.
Conclusion
After decades of struggling to cope with lining problems in
the outlet zone, RHI is able to provide a promising concept
applicable for all rotary kilns.
References
[1] Marschall, H.U. and Wiry, A. Computer-Aided Thermo-Mechanical Stress Modelling of Different Rotary Kiln Outlet Designs. RHI Bulletin. 2004,
No. 2, 1216.
[2] Landthaler, A. Drehrohrofen. German Patent DE 2643412 C3, 1987.
Authors
Andreas Wiry, RHI AG, Industrial Division, Vienna, Austria.
Hans Ulrich Marschall, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Andreas Wiry, andreas.wiry@rhi-ag.com
The new RHI Thrust Lock System offers the following
advantages:
>> Lower mechanical stress in load bearing bricks, retain-
ing rings, and outlet segments.
>> Modifiable inclination angle (2080) of the skew brick
set.
>> High heat resistance (>> 1000 C).
>> Universally applicable at the outlet and mid-kiln region.
>> Installation as a single or multistep concept.
>> Easily combined with all existing retaining designs.
>> Considerable cost savings for the refractory lining.
>> Higher kiln availability.
>> Easy installation procedure.
>> Shorter downtime in the case of relining.
The first trials are planned for the second half of 2013. Tech-
nical support, investigation of current wear mechanisms,
process analysis, and installation supervision will be pro-
vided by RHIs experts.
A patent application for the new RHI Thrust Lock System
has been filed.
> 19
 RHI Bulletin > 2 > 2013, pp. 2024
Thomas Drnek
Safety in the Mining IndustryA Value
Introduction
Safety is a value and must be handled as such in the mining
industry. It is also the most important issue in the mining
business. However, this sector has an image problem
because mining is considered to be very dangerous by the
general public. To examine the actual situation and recent
developments, data published regarding mining safety was
analysed and the current status assessed. In addition, this
enabled the question of what future provisions can be made
to improve the situation to be considered. The safety data
available for large mining companies was collected and ana-
lysed as well as reporting practices and the situation in dif-
ferent mining countries and regions. Since experience and
technological advances are paramount to improve safety, the
current training and education opportunities available for
mining personnel in Austria were also examined.
Injuries and Fatalities in Large Mining
Companies
The safety situation was analysed for the large mining com-
panies Rio Tinto, Anglo American, and BHP Billiton. The
information was obtained from both annual reports and sus-
tainability reports published by these corporations [1]. The
figures presented are the lost time injury frequency rate
(LTIFR) (i.e., lost time injuries per 2 x 105 hours) (Figure 1)
and absolute number of fatalities (Figure 2). In general, the
data and reports were easily accessible (via the internet)
and show that these companies are working very hard to
improve safety issues. For example, analysis of the trends
revealed not only very low LTIFR values (i.e., 0.41.1 LTIFR/
2 x 105 working hours) for these three mining corporations,
but also a continuous improvement in this area.
The data regarding fatalities does not indicate such a strin-
gent development for all three companies. While the
improvement at Anglo American shows a very significant
two-thirds reduction over 5 years, decreasing from close to 45
to around 15 fatalities, the values for Rio Tinto peaked in 2008
due to a helicopter crash in which 10 exploration crew died.
2.0
1.8
Lost time injuries/2 x 105 working hours
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
2006 2007 2008
Year
Figure 1. Annual injury frequency rates for three large mining
companies [1].
20 <
Excluding this accident, the figures for Rio Tinto and BHP Bil-
liton are in the region of 5 fatalities per year.
The large mining companies examined in the analysis have a
very good reporting standard, as proposed by the Interna-
tional Council on Mining and Metals (ICMM), London. In the
last years, these companies achieved significant improve-
ments regarding the injury frequency rates, and in the case
of Anglo American the number of fatalities also decreased.
The question that arises from these figures is what has
caused this trend? The simple answer is that safety has
become the most important job for board members; they
have taken personal responsibility for the issue. In addition,
policies have been established and executed, for example
the Occupational Health and Safety Advisory Services
(OHSAS) standard 18001, which provides a very useful way
to monitor, measure, and improve safety and health in the
workplace.
Safety in a Major Mining Country: Republic
of South Africa
The situation in the Republic of South Africas mining sector
is very well highlighted in the 2011 and 2012 annual reports
published by the Chamber of Mines of South Africa [2,3],
where an entire chapter is dedicated to this topic. Particularly
remarkable is the significant reduction in fatalities over the
last 10 years (Figure 3). One reason for this trend is that the
Chamber together with mining companiesfor example
Anglo American is a major player in the South African min-
ing industryhas set target values for the reduction of fatali-
ties, as well as other milestones regarding health and safety
in the South African mining sector.
In summary, the significant improvements realized in South
Africa are due to the Chamber of Mines of South Africa being
very active in the area of safety, with the mining industry acting
as the most important supporting factor. In recent years multi-
ple aims have been defined, very positive progress has been
achieved, and results are reported on a regular basis [2,3].
50
n BHP Billiton n BHP Billiton
45
n Rio Tinto n Rio Tinto
n Anglo American 40 n Anglo American
35
Absolute numbers
30
25
20
15
10
5
0
2009 2010 2011 2005 2006 2007 2008 2009 2010 2011
Year
Figure 2. Annual fatalities in three large mining companies [1].
 RHI Bulletin > 2 > 2013

Safety in an Another Major Mining Country: Mining Education in the USA

USA
When the situation in the USA was examined, the first sig-
nificant observation was the excellent availability of statis-
tics on the Mine Safety and Health Administration (MSHA)
homepage [4]. The data is updated on a daily basis, and
each accident is documented and analysed. Table I provides
an example of the detailed information available on this
website: The daily fatality report for the coal mining indus-
try [5]. Additional statistics that can be accessed include the
actual number of mining-related fatalities in the USA
between 20012011 (Figure 4). ous in underground operations and checking the roof (rock)
When the trends and injury reasons in the USA were ana-
lysed, no clear patterns appeared immediately evident. One
article summarized the situation with the statement: Since
2006, a series of disastrous mining accidents with multiple
casualties has shocked the US American mining industry
[6]. However, closer inspection revealed that the large min-
ing accidents in the USA were mainly caused by two rea-
sons: Methane gas explosions and massive roof failures.
This then raised the question: Why did these accidents hap-
pen when methane is widely known to be extremely danger-

Fatalities chargeable to the 2007 2008 2009 2010 2011

coal mining industry UG S UG S UG S UG S UG S
Electrical 0 0 1 1 0 0 0 0 0 1
Exploding vessels under pressure 0 0 0 0 0 0 0 0 0 0
Explosive and breaking agents 0 1 0 0 0 0 0 0 0 0
Fall/slide material 1 0 0 0 0 0 0 0 1 0
Fall of face/rib/high wall 9 2 0 1 1 0 3 0 2 3
Fall off roof or back 3 0 4 0 2 0 3 0 1 0
Fire 0 0 0 0 0 0 0 0 0 0
Handling material 1 0 0 0 0 1 0 0 0 0
Hand tools 0 0 0 0 0 0 0 0 0 0
Nonpowered haulage 0 0 0 0 0 0 0 0 0 0
Powered haulage 1 3 7 3 1 7 4 5 3 1
Hoisting 0 0 0 0 1 1 0 0 0 0
Ignition/explosion of gas/dust 0 0 0 0 0 0 29 1 0 0
Inundation 0 0 0 0 0 0 0 0 0 0
Machinery 2 2 3 7 0 1 2 1 2 6
Slip/fall of person 0 8 0 1 1 1 0 0 0 1
Step/kneel on object 1 0 0 0 0 0 0 0 0 0
Striking or bumping 0 0 0 0 0 0 0 0 0 0
Others 0 0 0 2 1 0 0 0 0 0
Year to date totals 18 16 15 15 7 11 41 7 9 12
Combined year to date totals 34 30 18 48 21
End of year total 34 30 18 48 21

Table I. MSHA coal mining industry daily fatality report on July 5, 2012, for the USA. Abbreviations include underground (UG) and
surface (S) mining [5].

0.35 80

0.30 70
Fatalities/1 x 106 worked hours

60
0.25
Absolute number

50
0.20
40
0.15
30
0.10
20

0.05 10

0.00 0
2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2001 2003 2005 2007 2009 2011
Year Year

Figure 3. Annual mining-related fatality rates in South Africa [2]. Figure 4. MSHA annual mining-related fatalities in the USA [4].

> 21
 RHI Bulletin > 2 > 2013
conditions in mines is a primary task for all miners? Having
identified these two factors, it appears the underlying causes
are both related to the following education issues:
>> Miners not having enough experience.
>> Mining engineers being insufficiently educated.
The reason for an overall decrease in experience amongst
US miners is that the average age has increased from 35
years old in 1980 to 47 in 2008 [6]. As a result of retirement,
the experience gained by senior miners is gradually being
lost, and safe behavioural practices are no longer being
transferred from experienced miners to inexperienced
young miners. In addition, after only six months new miners
can now take an exam and upon successful completion are
considered sufficiently experienced to work on their own
anywhere in a mine.
Regarding the second issue, due to high salaries offered by
the industry to graduates with a bachelors degree as well
as high tuition costs at US universities, fewer young engi-
neers are willing to study for masters and doctoral degrees.
This has resulted in excessive aging of university staff, in
addition to mining authorities and research institutions fac-
ing a shortage of postgraduate employees.
CONSOL EnergyAbsolute ZERO Value System
A positive example in the USA of a mining company that
has been very effective in creating a safe working environ-
ment is CONSOL Energy [7], where 97% of the more than
7500 employees worked in 2007 without a single accident
occurring. The company lists three principal factors that are
required to achieve such figures [6]:
>> Strict compliance with all safety regulations. Although,
these provisions alone are generally not sufficient and
effective.
>> Application of all available technologies even beyond the
mandatory legal requirements, including mine gas moni-
toring and wireless communication systems.
>> A corporate culture where the top priority is safe,
accident-free behaviour in the workplace. Employees
assume a central role in this culture and are responsible
for their own safety and health. The employees are not
only authorized, but explicitly required to immediately
correct any and all unsafe working conditions and if
necessary stop the production process in order to rectify
any defects. Regular training sessions and formal evalua-
tions of the safety behaviour also contribute towards
creating an active zero accident culture among all
employees [7].
CORESafety
In 2012, the US National Mining Association started the
CORESafety initiative: 20 steps until 2015 [8,9]: The following
modules, from a total of 20, are included in this programme:
>> Leadership development.
>> Responsibility and accountability.
>> Management system coordination.
>> Fatality prevention and risk management.
>> Training and competence.
>> Emergency management.
>> Culture enhancement.
>> Collaboration and communication.
22 <
The aim of CORESafety is to reduce fatalities to zero and
decrease the injury rate by 50% within 5 years.
In addition to these initiatives, the US Assistant Secretary
of Labor for Mine Safety and Health, Mr. Joe Main, called
for the creation of incentives so operators improve safety
practices as well as stronger civil and criminal penalties
to act as a powerful deterrent against mine operators
knowingly or persistently putting the lives of miners at
risk [10].
Safety in Europe
When the situation in Europe was examined, it showed
that the number of accidents and fatalities in the mining
sector is very low compared to other industries (Figure 5).
Unfortunately, these are the only overall European mining
statistics available; however, they do reveal the severity of
the accidents that have occurred in the mining sector,
since the percentage of fatalities is fivefold higher than
that of injuries [11].
Sweden and Austria
To provide a more in-depth assessment of the situation,
Sweden and Austria were examined individually, since
they both have a vital mining industry and very good sta-
tistics are available [12,13]. In both countries the lost day
injury frequency rate (LTIFR) (i.e., number of occupational
injuries per 1 x 106 working hours) shows a general decline
for both countries (Figures 6), namely in the last decade
the rate of 25 injuries per 1 million worked hours
decreased to 7.7 and 12 in Sweden and Austria, respec-
tively. Furthermore, the LTIFR in Austria reduced signifi-
cantly from 70 injuries per 1 million worked hours in 1970
to approximately 25 in 2000. The reason for this trend was
better equipment, stricter legislation, good education, and
a general improvement in public health. The number of
fatalities is in the range of 0 to 1 per year, with Austria
having 1 in 2010 and 2011, and Sweden having 1 in 2002,
2007, and 2009. In both countries there were zero fatalities
in the other years.
Mining Education in Austria
In part, the relatively low number of injuries and fatalities
in Austria can be attributed to the training and education
opportunities available for mining personnel in this coun-
try, which are divided into:
>> Miner.
>> Foreman.
>> Mine manager.
The training for a miner consists of a minimum of two
years working in a mine as a junior miner, during which
time the apprentice is not allowed to work alone and must
be accompanied by a well-experienced miner. After this
practical training (including several safety training ses-
sions) a mining course must be taken that consists of 120
lectures (each 50 minutes in duration). It covers all relevant
mining issues and ends with an exam [14].
Several years experience in the mining industry is required
before embarking on the foreman education programme.
The initial training consists of a 10 week basic course (39
hours per week), culminating in a written and oral exam.
 RHI Bulletin > 2 > 2013

After the basic course has been completed, one or more spe- University level education is subdivided into bachelors and
cial courses can be taken that focus on different topics (e.g., masters degree programmes. In addition, doctoral studies
open pit, underground, and mineral processing). The special can be performed. Most students in Austria graduate with
courses comprise the same number of lessons as the basic a masters degree. A bachelor programme (7 semesters) is
course [15]. In Autumn 2013, the Berg- und Httenschule HTL offered at the University of Leoben under the title: Mineral
in Leoben also started to offer a 5 year course focused on raw Resources Engineering. After completing this B.Sc., a mas-
materials for pupils typically aged 1519 years old [16]. ters programme (3 semesters) can be undertaken.

Mining and quarrying

Construction

Manufacturing

Transportation and storage

Wholesale and retail trade

Agriculture, forestry, and fishing

Administrative and support service activities

Human health and social work activities

Accommodation and food service activities

Public administration and defence

Water supply; sewerage, waste management

Professional, scientific, and technical activities

Education

Arts, entertainment, and recreation

Other service activities

Information and communication

Financial and insurance activities

Electricity, gas, steam, and air conditioning supply

Real estate activities

Activities of extraterritorial organisations and bodies n Serious accidents

n Fatal accidents
Activities of households as employers

0 5 10 15 20 25 30

Figure 5. Percentage of serious and fatal accidents at work in Europe, according to economic activity (total cases: 3942999, fatalities:
4898) [11].

30 80

70
No. of injuries/1 x 106 working hours

No. of injuries/1 x 106 working hours

25
60
20
50

15 40

30
10
20
5
10

0 0
2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 1970 1973 1987 1996 2000 2002 2004 2006 2008 2010 2011
(a) Year
(b) Year

Figure 6. Annual lost day injury frequency rates in the (a) Swedish [12] and (b) Austrian mining industry [13].

> 23
 RHI Bulletin > 2 > 2013

This is more focused and there are two areas available:
Mining and Tunnelling, and Raw Materials Engineering [17].
Safety in China
Currently, no statistical data is available regarding mining
safety in China. The only information is from media reports
(e.g., Xinhua) and the Government website [18]. The official
number of fatalities reported in coal mines for 2010 was
1920 (2436 in 2009); however, it is assumed that the number
of unreported cases is considerably higher, since a Chinese
miner is 100 times more likely to die in an accident than a
US miner [19].
The Chinese government is committed to improving the sit-
uation and a safety tax was imposed in 2012. This equates
to ~ US$4.8/tonne of coal and funds are planned to be used
to improve the safety of facilities, increase safety education,
set up health damage prevention programmes, build under-
ground shelters, and monitor equipment that is a major
danger source. The results of these measures have not
been published to date, but the impact could be enormous
because of the huge revenue available from such a taxation
scheme.
Summary and Recommendations
The analysis of mining safety data revealed there are no
comprehensive global statistics available. While the Interna-
tional Labour Organization (ILO), a United Nations agency,
provides some information, the data regarding injuries and
fatalities is incomplete. Large mining companies have very
good data and show very positive progress with their aims
to achieve zero injuries in the workplace. In contrast, analy-
sis of the available government data revealed a mixed situ-
ation, with some governments providing access to very
good data and others that do not have or want to publish
such statistics. However, in general from the large mining
company and specific country statistics there appears to be
a positive trend in the area of safety. One key factor influ-
encing safety is good training and education for all person-
nel working in the mining industrystarting with miners
and ending at executive management level.
In conclusion, the mining community must pay even more
attention to safety issues, and also promote more detailed
training and education opportunities for all mining person-
nel. Additionally, the International Organizing Committee of
the World Mining Congresses needs to place far more
attention on safety issues. Therefore, it was very positive to
see several sessions at the 23rd World Mining Congress
(Montreal, Canada), in August 2013, were focused entirely
on safety.

References
[1] Annual reports and Sustainability reports for Rio Tinto, BHP, and Anglo American (20072011).
[2] http://www.bullion.org.za/documents/ar_2011-small.pdf
[3] http://www.bullion.org.za/documents/AR_2012_web_Final.pdf
[4] www.msha.gov
[5] http://www.msha.gov/stats/charts/coaldaily.asp
[6] Brune, J. Occupational Safety and Health in US American Mines Problems and Potential Solutions. World of Mining - Surface and Underground.
2012, 64, No. 6, 382389.
[7] http://www.consolenergy.com/about-us/corporate-responsibility/safety.aspx
[8] www.nma.org
[9] http://www.coresafety.org/index.html
[10] http://www.dol.gov/ocia/congressionaltestimony/20100520_JMain.htm
[11]http://epp.eurostat.ec.europa.eu/statistics_explained/index.php/Health_and_safety_at_work_statistics
[12] http://www.svemin.se/MediaBinaryLoader.axd?MediaArchive_FileID=f4416fc2-1c6a-4276-bf1f-1cfc1245459f&FileName=%C3%85rsrapport+201
1engelsk.pdf
[13]http://www.bmwfj.gv.at/EnergieUndBergbau/SicherheitImBergbau/Documents/Sp%C3%B6rker,%20Unfallstatistik.pdf
[14] http://www.htl-leoben.at/files/spezialkursprogramm2013_1_1.pdf
[15] http://www.htl-leoben.at/index.php?article_id=69
[16] http://www.htl-leoben.at/index.php?article_id=162
[17]http://starter.unileoben.ac.at/fileadmin/shares/starter/docs/Studienbrosch%C3%BCre_13_Web.pdf
[18] www.gov.cn
[19] http://www.bbc.co.uk/news/business-11497070

Author
Thomas Drnek, RHI AG, Raw Materials Division, Breitenau, Austria.
Corresponding author: Thomas Drnek, thomas.drnek@rhi-ag.com

24 <
RHI Bulletin > 2 > 2013, pp. 2526
Franz Maier and Clare McFarlane
Low Carbon Economy Roadmap for the Ceramic
Industry
Introduction
The European Commission is looking at cost-efficient ways
to make the European economy more climate friendly and
less energy consuming because if global warming is to be
held below 2 C compared to the temperature in preindus-
trial times it considers all major economies will need to
make deep emission reductions [1]. Therefore, in July 2009,
leaders of the European Union (EU) and the G8 announced
an objective to reduce greenhouse gas emissions by at least
80% below 1990 levels by 2050, and in October 2009 the
European Council set the appropriate abatement objective
for Europe and other developed economies at 8095% below
1990 levels by 2050 [2]. Additionally, the Commission esti-
mated the European industry has a technological and eco-
nomical potential to reduce the greenhouse gas (GHG) emis-
sions in the order of 8387% by 2050 [3]. As far as industrial
sectors are concerned, the European Commission is calling
on them to develop individual roadmaps to address these
targets, as solutions will be highly sector specific.
To show the potentials of the ceramic industry, Cerame-
Unie, the trade industry association representing the eight
sectors of the European ceramic industry (i.e., refractories,
technical ceramics, brick and roof tiles, wall and floor tiles,
table and ornamentalware, sanitaryware, clay pipes, and
abrasives), across 25 EU member states, launched a
Ceramic Roadmap to 2050 for a low carbon economy [4,5].
As a member of the European Refractories Producers Feder-
ation (PRE), a representative organization of the European
refractory industry closely affiliated with Cerame-Unie, RHI
contributed to the refractory section of this roadmap.
Political Background
Europe 2020 is the EUs growth strategy for the coming
decade [6]. It lays downs targets in the fields of:
>> Employment.
>> Innovation.
>> Climate and energy.
>> Education.
>> Social inclusion.
To support a successful realization of these targets, the EU
developed seven flagship initiatives contributing to smart,
sustainable, and inclusive growth [7]. Three of these initia-
tives are of particular relevance to the ceramic industry,
namely the Innovation Union, resource efficient Europe, and
an industrial policy for a globalization era.
As a consequence of the Europe 2020 strategy develop-
ment, the Commission also designed several roadmaps
(i.e., low carbon economy, resource efficiency, energy,
transport, and agriculture). All these roadmaps are interre-
lated and aim at the same objective of a competitive but
extremely green economy (e.g., resource utilization, CO2
emissions, and energy efficient) by 2050.
The Ceramic Roadmap to 2050
Following the Commissions request to develop applicable
roadmaps for a low carbon economy [3], in 2012 Cerame-
Unie published the ceramic industry roadmap: Paving the
Way to 2050 [4,5]. This representative assessment was
made for the refractory, brick and roof tile, and wall and
floor tile sectors, since they account for 90% of the entire
ceramic industrys emissions (Figure 1).
The emissions reduction model was developed with the
following assumptions:
>> Constant production from 2010 to 2050.
>> High degree of kiln capacity utilization.
>> 95% decarbonization of the electricity supply by 2050
(compared to 1990 levels).
Furthermore, future key technologies were considered even
if they require significant development, such as heat recov-
ery from the kiln stack or new kiln design, or they are break-
through technologies like carbon capture and storage (CCS),
on-site syngas or biogas production, and low temperature
heat recovery.
The potential for a 65% emission reduction by 2050 was
predicted with the model where syngas/biogas technology
is developed to replace fossil fuels and a sustainable and
affordable feedstock is secured. However, it also requires
the sector attains sufficient financial support for break-
through research and development and that a stable regula-
tory framework is implemented so the industry can com-
pete with manufacturers outside Europe.
Theoretically, a reduction potential of 7578% could be real-
ized with a model that includes 50% electrification of the
ceramic kilns to replace fuel firing, assuming a 95% decar-
bonization of electricity production. However, such an elec-
trification programme would be completely uneconomical
because it would require an investment of 90 billion.
Electricity
18%
Process
emissions
16%
Fuel
66%
Figure 1. Sources of 90% of the entire ceramic industrys CO2
emissions in 2010 [5].
> 25
 RHI Bulletin > 2 > 2013

Furthermore, the write-off and lost production costs would
account for an additional 40 billion and it would result in
absolutely unprofitable running costs.
Therefore, while the refractory industry will significantly
contribute to resource and energy efficiency, it is not feasi-
ble to the extent outlined in the EU 2050 roadmap. Since
refractories will continue to be indispensible for down-
stream users in the future and enable resource and energy
efficient production in other sectors, a regulatory framework
that enhances European competitiveness, supports sustain-
able growth, and avoids the risk of carbon and job leakage
must be considered the primary target.
The study showed the product carbon footprint directly cor-
related with the energy intensity, which mainly depended
on the kiln load. It also revealed that environmental require-
ments, such as mandatory post process waste gas combus-
tion, can increase the energy intensity by up to 30%.
The European refractory industry is committed to continu-
ing this exercise since it provides the possibility to reveal
emission-related trends. In addition to increasing the num-
ber of product groups covered by the analysis, future aims
include the use of national rather than European conversion
factors.

European Carbon Footprint for Refractory 0.7

Products

Tonne CO2 equvalent/tonne of product

0.6
To provide its members and their downstream customers
with information about the refractory industrys carbon foot- 0.5
print, in September 2013 PRE published the first results of
the refractory product carbon footprint exercise [8,9]. The 0.4
data was collected from 40 sites and represents over 40% of
the total annual turnover represented by PRE membership 0.3
(i.e., approximately 1.7 million tonnes). It provides the aver-
age European carbon footprint for a range of different 0.2
refractory products and includes values obtained for eight
0.1
process steps typically involved in refractory manufacture
(Figure 2). The carbon footprint associated with raw materi-
0.0
als and product transport was excluded. Not only does this Total Total Precast Basic Unshaped
data enable the European refractory industry to analyse its nonbasic basic unfired
environmental position, it also provides refractory user fired shaped fired shaped shaped
industries with specific figures to calculate a more accurate
carbon footprint for their products. Figure 2. Carbon footprint of different refractory product groups [9].

References
[1] http://ec.europa.eu/clima/policies/roadmap/
[2] http://www.roadmap2050.eu/attachments/files/Volume1_fullreport_PressPack.pdf
[3] A Roadmap for Moving to a Competitive Low Carbon Economy by 2050. Communication From the Commission to the European Parliament,
the Council, the European Economic and Social Committee and the Committee of the Regions. COM(2011) 112 final, Ed.; EU-Commission,
Brussels, 2011.
[4] http://www.cerameunie.eu/en/news/european-ceramic-industry-launches-2050-roadmap-paving-the-way-to-a-better-future
[5] Paving the Way to 2050. The Ceramic Industry Roadmap. Cerame-Unie, Brussels, November 2012.
[6] http://ec.europa.eu/europe2020
[7] http://ec.europa.eu/europe2020/europe-2020-in-a-nutshell/flagship-initiatives/index_en.htm
[8] http://www.pre.eu/
[9] PRE Product Carbon Footprint Report. European Refractories Producers Federation, Brussels, September 2013.

Authors
Franz Maier, RHI AG, Technology Center, Leoben, Austria.
Clare McFarlane, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Franz Maier, franz.maier@rhi-ag.com

26 <
RHI Bulletin > 2 > 2013, pp. 2730
Markus Dietrich and Stefan Postrach
Chrome Corundum: An Alternative to Isostatically
Pressed Products
Introduction
For several years, chrome-containing refractory products
have been installed in critical areas of soda-lime glass fur-
naces. Their high corrosion resistance against glass melts
ensures an extended furnace lifetime and the stability of
important furnace segments like weir walls and throats. In
particular, isostatically pressed products (iso-chrome) with
high chromium content (typically 95 wt.%) have become
more frequently installed for these applications over the last
years. However, besides their advantageous properties,
these products also exhibit the drawback of low thermal
shock resistance as well as a very elevated price. Therefore,
RHI has been focused on alternative materials based on
bonded alumina-chrome and for several years has been
able to offer much more economic solutions for areas with
high wear in all glass melting tanks. These products exhibit
corrosion resistance close to that of isostatically pressed
material in combination with superior thermal shock resis
tance.
Chrome Corundum
Chrome corundum is based on -Al2O3 (corundum) and
Cr2O3 (eskolaite). These two oxides exhibit a very similar
crystal lattice and therefore chrome corundum can exist as
a mixed crystal at any Al2O3 /Cr2O3 ratio. The phase diagram
of the chrome-alumina system in Figure 1 shows this com-
plete miscibility.
Standard chrome corundum products are produced by
mixing and firing pure eskolaite (Cr2O3) and corundum
(Al2O3) raw materials. The mixed crystal phase is generated
during the firing process and later during operation at high
2300
2250
2200
Temperature [C]
2150
2100
2050
2045 5 C
2000
1950
0 20 40 60
Al2O3
Composition [mol.%]
Figure 1. Phase diagram showing the continuous miscibility of
Al2O3-Cr2O3 [1].
temperatures. A higher product homogeneity can be
achieved by using fused chrome corundum raw materials.
This so-called smelt is produced in electric arc furnaces.
During fusion, the process parameters need to be accu-
rately controlled due to the high sensitivity to oxidation-
reduction reactions. The resulting fused chrome corundum
raw material consists of a very homogeneous mixed crystal
with a well-defined Al2O3 /Cr2O3 ratio and therefore uniform
properties. Another advantage of this process is that not
only primary raw materials can be fused but also recyclable
material and production scrap, which further supports RHIs
sustainability targets. Two different fused materials with a
Cr2O3 content of 30 wt.% and 60 wt.% are available. The for-
mulation of RHIs new generation of chrome corundum
products is based on these two well-defined raw materials.
Properties of Chrome Corundum
The most important property of chrome-bearing refractories
is their high corrosion resistance against glass melts. This
property is determined in the laboratory using the static
plate corrosion test. It consists of dipping refractory sam-
ples in glass melt for a defined time at a fixed temperature.
The samples are corroded by the glass melt mainly at the
triple point where the refractory is in contact with both the
glass melt and atmosphere, producing a notch in the sam-
ple. The corrosion resistance is determined by measuring
the notch depth. The test is comparative and a sample of
the most common glass contact material, fused cast AZS, is
used as the standard. Figure 2 shows the results of this cor-
rosion test examining the relative corrosion resistance of
chrome corundum (i.e., SUPRAL brands), iso-chrome, and
fused cast AZS. It was clearly evident that all the chrome-
bearing products were much less corroded than the fused
SUPRAL RK70 ISO-chrome SUPRAL RK50S AZS 40
2275 25 C
80 100 0.9 0.8 0.9 3.6
Cr2O3
Notch depth [cm]
Figure 2. Static plate corrosion test results. RHIs SUPRAL RK50S
and SUPRAL RK70 chrome corundum grades (containing 53 wt.%
and 72.5 wt.% Cr2O3 , respectively) were compared to isostatically
pressed chrome and fused cast AZS material for 144 hours at
1500 C in soda-lime glass.
> 27
 RHI Bulletin > 2 > 2013

cast AZS with 40% ZrO2 , whereas the difference between
the different chrome-containing materials was minor: The
uniaxially pressed chrome corundum grades were nearly as
resistant to corrosion as the isostatically pressed product.
At several positions in glass furnaces, good thermal shock
resistance is essential. This is a weak point of isostatically
pressed high chrome material. Thermal shock resistance is
tested by heating up cylindrical samples to 950 C and then
quenching them in water. Isostatically pressed products
only survive a few such cycles, 2 or 3 in general.
More recently, chrome-bearing material with > 30 wt.%
chromium oxide has been installed in soda-lime glass fur-
naces. The material is only used in zones with high wear
rates, for example the weir wall in container glass furnaces
(Figure 3), doghouse corners, and the throat. Since 2004,
RHI has also supplied uniaxially pressed chrome corundum
grades with a chrome content of 3070 wt.% for about 40
soda-lime glass furnaces worldwide. A closer look at the
weir walls has shown that chrome corundum greatly
extends their lifetime, when compared to the use of fused
cast AZS.

Due to good structural flexibility, chrome corundum mate-
rial exhibits a much better thermal shock resistance. The
addition of small amounts of zirconia-based phases further
improves this characteristic. These grains have a different
thermal expansion behaviour compared to chrome corun-
dum and this creates a zone of microcracks in their vicinity.
The microcracks can stop the growth of larger cracks, which
would otherwise destroy the material. This effect is called
microcrack reinforcement. Results of a thermal shock test
comparing various chrome-containing refractory grades are
listed in Table I. The excellent thermal shock resistance of
chrome corundum enables it to be installed even as hot
repair overcoating tiles behind corroded soldier blocks on
container and float glass tanks.
Weir walls significantly influence the glass melt flow profile,
supporting homogenization. At the same time the wall
retains impurity particles, which could otherwise lead to
glass defects. Thus, chrome corundum weir walls contribute
to longer production periods with high quality glass.
Batch material is fed into the furnace through the dog-
house. Due to the abrasive action of unmelted batch as well
as thermal shock, the doghouse corner blocks are especially
subjected to significant corrosion. When completely worn,
the doghouse corners must be extensively repaired.
Chrome corundum doghouse corners (Figure 4) fulfil the

Practical Experiences
Today, chrome-bearing refractory grades are used when
excellent corrosion resistance is required. For example, fur-
naces for the production of C-glass are entirely lined with
chrome corundum materials, permitting a furnace lifetime
of 4 or more years. Since 1980, RHI has also supplied SUPRAL RK50S
chrome corundum grades to insulation fibre producers and
over the last 12 years about 70 furnaces worldwide have
been equipped entirely or in major sections with these
materials.
SUPRAL RK30S

Grade Cr2O3 content TSR

(%) cycles
DURITAL RK30NP 30 > 30
SUPRAL RK30S 30 25
SUPRAL RK50S 53 20 SUPRAL RK30S
SUPRAL RK70 72 15
Iso-chrome 95 2

Table I. Thermal shock resistance (TSR) of selected chrome- Figure 4. Doghouse corner in a container glass furnace compris-
bearing refractory grades. ing two chrome-bearing refractory grades, SUPRAL RK30S and
SUPRAL RK50S.

Figure 3. Chrome corundum weir wall in a container glass furnace.

28 <

demanding requirements in this difficult application area as
a result of the high corrosion resistance and excellent ther-
mal shock resistance of this material.
Frequently, chrome-bearing refractories are installed at the
throat entrance. In this area corrosion is mainly influenced
by forced convection of the glass melt and block failure is
critical because in many cases hot repairs are difficult to
realize. Therefore, corrosion resistant chrome-bearing mate-
rials have proven advantageous, compared to fused cast
AZS, in achieving long lasting campaigns.
Chrome corundum products can also be used as electrode
blocks for electric boosting. These blocks mainly suffer from
strong glass melt convection around the electrodes. High
chromium oxide containing products (> 70 wt.%) must not
be used in this position due to their low electrical resistivity.
If the resistivity is close to or inferior to that of the glass
melt, a short circuit may occur that can cause significant
damage. Chrome corundum grades (< 50 wt.%) are a good
alternative to standard fused cast AZS for this application
because they exhibit a similar electrical resistivity to AZS
combined with enhanced corrosion resistance (Figure 5).
10000
Electrical resistivity [ohm/cm]
1000
100
10
1
400 600 800 1000
Temperature [C]
Figure 5. Electrical resistivity of DURITAL chrome corundum
grades compared to iso-chrome, fused cast AZS, and soda-lime
glass melt.
(a)
Figure 6. (a) significantly corroded AZS soldier blocks and (b) installation of chrome corundum overcoating tiles providing hot repair.
RHI Bulletin > 2 > 2013
Overcoating Tiles
An additional success story is the repair of tank sidewalls
with chrome corundum overcoating tiles, which are
installed behind corroded soldier blocks in container and
float glass furnaces (Figure 6). As the tiles heat-up very
rapidly during installation, a special thermal shock resistant
chrome corundum grade is used for this application. Since
2004, this approach has been effective for nearly 200 cases
of colour and flint glass furnaces. The direct comparison of
a chrome corundum overcoating tile and an AZS overcoat-
ing tile was performed on a container glass furnace wall,
where both types of material were installed side by side.
Two years after installation, the superior corrosion resist-
ance of the chrome corundum was clearly evident
(Figure 7).
To date, no negative influence of SUPRAL RK blocks and
DURITAL RK30NP overcoating tiles on the colour of flint
glass has been observed. This was confirmed by a cus-
tomer who detected no measurable increase of the chro-
mium concentration in glass products after installation of
overcoating tiles on a flint glass furnace (Figure 8).
n REFEL 1240
n DURITAL RK50S
n DURITAL RK30S
n Chrome 95
n Soda-lime glass
1200 1400 1600
Figure 7. Wear of AZS overcoating tiles (white) in the foreground
and chrome corundum overcoating tiles (black) in the back-
ground, both after 2 years application.
(b)
> 29
 RHI Bulletin > 2 > 2013

25
Installation of the overcoating tiles
20
Cr2O3 [ppm]

15

10

0
6 months 9 months

Figure 8. Chromium concentration in soda-lime glass before and

after installation of chrome corundum overcoating tiles.

Summary
Chrome corundum materials from RHI exhibit excellent
characteristics for different applications in the glass
production process. By using fused raw materials in various
DURITAL and SUPRAL brands (i.e., RK30S and RK50S), the
properties are improved further because the fusion process
ensures homogeneous mixed crystals with a well-defined
Al2O3 /Cr2O3 ratio.

Many years of successful experiences with chrome corun-

dum in C-glass furnaces have demonstrated this material is
appropriate for such a demanding environment. A relatively
new application of chrome corundum products is in soda-
lime glass furnaces. For example SUPRAL RK50S and
SUPRAL RK70 are particularly suitable replacements for iso-
statically pressed products in critical furnace segments such
as the throat, weir wall, and doghouse corner. This is
because a comparable corrosion resistancedespite a
much lower Cr2O3 contentis combined with a significantly
higher thermal shock resistance and a higher electrical
resistivity compared to iso-chrome.

Reference
[1] Bunting, E.N. Phase Equilibrium in the System Cr2O3 -Al2O3. Bur. Standard. J. Research. 1931, 6, 947949.

Authors
Markus Dietrich, RHI AG, Industrial Division, Wiesbaden, Germany.
Stefan Postrach, RHI AG, Industrial Division, Wiesbaden, Germany.
Corresponding author: Markus Dietrich, markus.dietrich@rhi-ag.com

30 <
RHI Bulletin > 2 > 2013, pp. 3135

Rongxing Bei, Klaus Santowski, Christian Majcenovic and Susanne Jrg

Postmortem Studies of Standard Silica, No-Lime

Silica, and Fused Cast AZS from Oxy-Fuel Fired
Soda-Lime Glass Melting Furnaces
Glass melting furnaces with oxy-fuel firing have become popular because of the energy sav-
ings and environmental benefits that can be achieved. However, a problem associated with
this firing technology is the higher NaOH content in the furnace atmosphere that results in
accelerated corrosion of refractories used for the melting furnace crown and superstructure.
In this paper the results of postmortem studies examining standard silica, silica without a
lime-bonded matrix (no-lime silica), and fused cast materials that had been installed in the
crowns of oxy-fuel fired soda-lime glass melting furnaces are reported and demonstrate that
STELLA GNL, a no-lime silica brand, provides considerable advantages for this application.

Introduction primarily in the form of cristobalite and tridymite, which

Since the 1990s, glass melting furnaces with oxy-fuel tech-
nology have been under development because this firing
technology provides the following advantages [13]:
>> Energy savings and an increased melting rate.
>> Environmental benefits, such as reduced NOx emission
levels.
>> Glass quality improvements.
However, disadvantages have also been reported, for exam-
ple higher crown and superstructure refractory corrosion.
This is primarily due to the increased NaOH vapour concen-
tration in the furnace, associated with the elevated water
produced using oxy-fuel firing [4]. As a result, traditional
standard silica is corroded much more rapidly when the fur-
nace is fired with oxygen rather than air [4,5]. To address
this issue glassmakers replaced standard silica with fused
cast AZS or fused cast alumina to achieve longer furnace
lifetimes [6,7]. However, a drawback is these refractories are
more expensive than standard silica. Consequently, the
glass industry has been looking for a material that has high
corrosion resistance when using oxy-fuel technology at a
together comprise ~ 94 wt.%. The additional SiO2 in combi-
nation with CaO forms the wollastonite (CaOSiO2) bonding
phase and accounts for ~ 5 wt.% of the silica brick. During
application in the crown and superstructure these silica
bricks are subject to chemical attack by vapourized com-
pounds from the glass bath, for example alkalis generated
during the soda-lime glass melting process [10].
A phase diagram of the SiO2-CaO-Na2O system (Figure 1) is
provided to explain the chemical reaction processes occur-
ring between alkalis in the furnace atmosphere and silica
bricks. Ignoring any brick impurities, the standard silica
brick composition is represented by the red circle on the
SiO2-CaO line in Figure 1. During application at high tem-
perature, the wollastonite dissolves and forms a first melt
containing SiO2, CaO, and Na2O, with the composition indi-
cated by the orange circle, at 1035 C. Depending on the
CaO
CaSiO3
150
0

reasonable investment price. In response to the market

140

demands, RHI developed a silica brick without lime bonding

0
130

(i.e., STELLA GNL, a no-lime silica brand) for this applica-

0

tion [8,9]. The results of postmortem studies performed on NC2S3 a-CS

standard silica, no-lime silica, and fused cast AZS refracto- NC3S6
ries that had been installed in oxy-fuel fired soda-lime glass
125

1600

Crs
0

melting furnaces are reported in this paper and confirm the

advantages of STELLA GNL for this application. N2CS3
0 2 liquids
120 b-CS

NC2S3
Standard Silica
1400

0 0 NC3S6
1500

110 100
Silica bricks are commonly used by the glass industry. The

Trd
N2CS3 900
good corrosion resistance at temperatures of > 1470 C, a NS2
NS 870
800

low bulk density (approximately 1.8 g/cm3), easy assimila-

Na2O Na2SiO3 60 Na2Si2O5 70 80 90 100

tion into glass, and the relatively low price make silica
refractories indispensable for constructing the crown and
superstructure of glass melting furnaces.
Nowadays, the typical standard silica bricks have 9597
wt.% SiO2 and approximately 2.5 wt.% CaO. The SiO2 exists
wt.% SiO2
Figure 1. Phase diagram of the SiO2-CaO-Na2O system [11].
Standard silica brick composition (red circle) and bulk composi-
tions of silica brick + Na2O (blue triangles) are indicated. The first
wollastonite melt at 1035 C, containing SiO2, CaO, and Na2O, is
indicated (orange circle).

> 31
 RHI Bulletin > 2 > 2013

supplied sodium content, the equilibrium composition of

the bulk system moves along a straight line (green dashed
line) towards the Na2O corner of the ternary system. The
blue triangles at 1400 C, 1500 C, and 1600 C represent the
bulk compositions of silica brick + Na2O, which are fully
molten at the specified temperature.

Two representative silica bricks from near the throat and

doghouse of an oxy-fuel container glass melting furnace
after a 14 year campaign life are shown in Figure 2. Chemi-
cal and mineralogical analyses were performed on samples
taken from the hot face, centre, and cold face of these bricks
(Table I), providing comparative data along the temperature
gradient when the bricks were in operation. The porosity
was also determined for two samples from the brick located
near the throat.

The brick from near the throat had a lower Na2O content at
the hot face (0.4 wt.%) in comparison to the centre and cold
face (1.3 wt.%). This was a result of alkali infiltration from (a) (b)
the hot face towards the cold face. Due to dissolution of
wollastonite, the CaO content at the hot face was low
Figure 2. Silica crown bricks after 14 years application in an oxy-
(0.7 wt.%). Whilst melt containing SiO2 , CaO, and Na2O had fuel fired container glass melting furnace. Brick from (a) near the
dripped down into the glass bath, part of this melt would throat and (b) near the doghouse.
also have migrated towards the cold face, resulting in the
CaO content being even higher in the centre (3.5 wt.%) than
at the cold face (2.5 wt.%) where the CaO content was com-
parable to that of an unused standard silica brick (2.5 wt.%).
Enrichment of CaO in the brick centre has also been
reported in the literature [12]. The main mineral phase in all
samples was cristobalite, which indicates the brick tempera-
ture had become higher than 1470 C during service. The
brick was more porous (24 vol.%) at the hot face than in the
centre (16 vol.%), as a consequence of melt dripping out at
the bricks hot face. Scanning electron microscopy of the
brick hot face clearly revealed sharp edges caused by the
melt dripping off and silica grains surrounded by melt in
the remaining areas (Figure 3).

In the case of the brick from near the doghouse, the Na2O 500 m
content at the hot face was relatively high (2.5 wt.%). Since
the temperature of this brick was lower than the brick from Figure 3. Scanning electron micrograph of the hot face of the sil-
near the throat, the Na2O had not infiltrated further in the ica brick located near the throat.

Brick location Near throat Near doghouse

Sample distance from the hot face (mm) 030 140160 300340 030 140160 300340
(hot face) (centre) (cold face) (hot face) (centre) (cold face)
Chemical analysis1 (wt.%)
Na2O 0.4 1.3 1.3 2.5 0.7 0.3
Al2O3 0.5 0.6 0.4 0.2 0.3 0.4
SiO2 98.1 94.0 95.5 95.9 96.3 96.6
K2O 0.0 0.1 0.1 0.1 0.1 0.1
CaO 0.7 3.5 2.5 1.0 2.4 2.3
Fe2O3 0.1 0.4 0.2 0.2 0.2 0.2
Phase analysis by X-ray diffraction2
Main phase Cristobalite Cristobalite Cristobalite Tridymite Tridymite Tridymite
Apparent porosity (vol.%)
2
24 16

Table I. Chemical composition, phase analysis, and apparent porosity of the silica crown bricks from near the throat and doghouse
after 14 years service in an oxy-fuel fired container glass melting furnace. Determination of the oxides by X-ray fluorescence analysis
after ignition at 1050 C (1) and on the original sample (2).

32 <
 RHI Bulletin > 2 > 2013

direction of the cold face. Consequently the Na2O content in
the centre and at the cold face was low (0.7 wt% and 0.3
wt.%, respectively). At the hot face the CaO level was low
(1.0 wt.%) because the newly formed SiO2 , CaO, and Na2O
containing melt had dripped down into the glass bath. It
was evident that enrichment of CaO in the direction of the
cold face had not occurred, since the CaO content at the
centre and cold face (2.4 wt.% and 2.3 wt.%, respectively)
corresponded to CaO levels in an unused silica brick. Due
to the lower operating temperature in this region, the main
mineral phase in the brick was tridymite.
No-Lime Silica
As described, the corrosion process affecting standard sil-
ica bricks in oxy-fuel fired furnaces is initiated by alkali
vapour causing dissolution of wollastonite in the bonding
matrix [13]. The resulting melt then plays an important role
in the further corrosion of SiO2 . Since a modified bonding
system without wollastonite eliminates this weak point in
silica bricks, a silica brick without limeSTELLA GNLwas
developed by RHI.
In a field trial, standard silica and STELLA GNL bricks were
installed in the superstructure of an oxy-fuel fired container
glass furnace. After 3 months the Na2O diffusion was
measured in these samples. The results showed that Na2O
diffusion into the standard silica was significantly higher
than into STELLA GNL (Figure 4).
Sample 1 represented no-lime silica with 1 wt.% Na2O, cor-
responding to an approximate situation that can occur at
the brick hot face during service (see Figure 4). Sample 2
was standard silica also containing 1 wt.% Na2O, providing
a direct comparison to Sample 1. Sample 3 was standard
silica containing 2 wt.% Na2O, which is a realistic composi-
tion for the hot face of a standard silica brick during ser-
vice (see Figure 4).
The thermodynamic calculations were performed over an
appropriate temperature range and the different phase
amounts (wt.%) were plotted against the specific tempera-
ture (Figure 6). In the case of Sample 1 (STELLA GNL)
there was hardly any CaO, and therefore only SiO2 solid
phases (trydimite up to 1470 C and cristobalite above
1470 C) and melts with two different compositions were
formed. The wollastonite (CaOSiO2 ) that was present in
standard silica dissolved at 1310 C (Sample 2) or 1215 C
(Sample 3).
In Figure 6 the exact amount of each melt is indicated as a
percentage on the curves. For example, at 1400 C Sample 1
(STELLA GNL) had 6.7 wt.% of Melt 1 and 3.1 wt.% of Melt
2, a total melt amount of 9.8 wt.%. However, at the same
temperature (1400 C) the total amount of melt in Sample 2
(standard silica with 1.0 wt.% Na2O) was 16.0 wt.%, and in
Sample 3 (standard silica with 2.0 wt.% Na2O) it was even
higher at 24.2 wt.%. At 1500 C, all the samples had a
higher amount of melt than at 1400 C, but the STELLA GNL

Microscopic analysis of a cross section through the STELLA

GNL brick after the trial (Figure 5) showed an inert struc-
Sample Refractory SiO2 Na2O Al2O3 CaO
ture and no sign of significant attack directly at the hot face
surface. (wt.%) (wt.%) (wt.%) (wt.%)
1 STELLA GNL 98.6 1.0 0.3 0.1
Thermodynamic Calculations 2 Standard silica 95.9 1.0 0.6 2.5
Detailed thermodynamic calculations were performed 3 Standard silica 95.4 2.0 0.6 2.0
using FactSage (Version 6.3) to determine the amount of
melt present in standard silica bricks and STELLA GNL at Table II. Refractory compositions used for the thermodynamic
Na2O concentrations similar to those occuring at the brick calculations presented in Figure 6.
hot face during service in an oxy-fuel fired melting furnace.
The three brick compositions examined are detailed in
Table II.
Hot face

2.5
n Standard silica
n STELLA GNL
2.0
Na2O in silica [wt.%]

1.5

1.0

0.5

0.0
0 10 20 30 40
Distance from hot face [mm] 500 m

Figure 4. Na2O diffusion into standard silica and STELLA GNL Figure 5. Light microscopy of a cut section through the STELLA
bricks after a 3 month field trial in the superstructure of an oxy- GNL brick installed for 3 months in the superstructure of an oxy-
fuel fired container glass furnace. fuel fired container glass furnace. No significant attack at the hot
face was visible.

> 33
 RHI Bulletin > 2 > 2013

(Sample 1) still had the lowest level of melt compared to

standard silica. This clearly demonstrates why STELLA GNL
100 2.0
3.1 has a much higher corrosion resistance than standard silica
Melt 2
Melt 1 if the furnace atmosphere is alkaline.
95 5.7 6.3 5.4
7.0
Phase distribution [wt.%]

6.1
90
6.7 Fused Cast AZS
8.0 When oxy-fuel technology was first introduced, fused cast
85 AZS was used for crown and superstructure applications
because standard silica materials showed increased corro-
80 sion under the operating conditions. However, a technical
SiO2(S4) disadvantage of fused cast AZS is that exudation of the
75 SiO2(S5) glassy phase occurs during operation and is greater in the
case of oxy-fuel firing. This can be clearly observed from
70 the results of a trial that compared fused cast AZS and
1000 1100 1200 1300 1400 1500 1600 STELLA GNL in an oxy-fuel tableware glass furnace. After 3
months in the superstructure the fused cast AZS showed
(a) Temperature [C]
significant exdudation at the hot face while STELLA GNL
Sample 1 Total melt amount had only a slightly wetted surface (Figure 7). Additionally,
No-lime silica STELLA GNL 1400 C: 9.8 wt.% there was higher sodium infiltration into the fused cast AZS
containing 1 wt.% Na2O 1500 C: 13.4 wt.% than into the STELLA GNL (Figure 8). Whilst the risk of exu-
dation can be avoided by using fused cast alumina instead
of fused cast AZS [14,15], STELLA GNL is an economic
100
alternative to fused cast alumina.
Na2Ca3SiO15(S)
95
6.9 Melt 1
Phase distribution [wt.%]

9.2
90 CaSiO3(S) CaSiO3(S2)
13.2
85 16.0

19.3
80
SiO2(S4)
75
SiO2(S5)

70
1000 1100 1200 1300 1400 1500 1600
(b) Temperature [C]
Sample 2 Total melt amount
Standard silica 1400 C: 16.0 wt.%
containing 1 wt.% Na2O 1500 C: 19.3 wt.%
Figure 7. (a) fused cast AZS and (b) STELLA GNL after a 3 month
field trial in the superstructure of an oxy-fuel tableware glass fur-
100 nace.
Melt 2
4.7
95
Na2Ca3SiO15(S)
Phase distribution [wt.%]

8.2
8
90 10.5 Melt 1
n AZS32
7 n STELLA GNL
CaSiO3(S2)
85
Na2O in samples [wt.%]

17.4 6
CaSiO3(S)
80 20.4 5

24.2 4
75 SiO2(S4)

27.7 3
SiO2(S5)
70
2
1000 1100 1200 1300 1400 1500 1600
(c) Temperature [C] 1

Sample 3 Total melt amount 0

Standard silica 1400 C: 24.2 wt.% 0 2 4 6 8 10 12
containing 2 wt.% Na2O 1500 C: 32.4 wt.% Distance from hot face [mm]

Figure 6. Results of the thermodynamic calculations performed Figure 8. Na2O diffusion into fused cast AZS and STELLA GNL
for Samples 13, defined in Table II, using FactSage (Version after a 3 month field trial in the superstructure of an oxy-fuel
6.3). tableware glass furnace.

34 <
 RHI Bulletin > 2 > 2013

Conclusion
Corrosion resistant refractories for crown and superstruc-
ture applications in oxy-fuel fired soda-lime glass melting
furnaces have undergone continuous improvement. The
first generation materialstandard silicawas replaced by
a second generationfused cast products. However, the
new generationno-lime silicacombines the advantages
of standard silica such as the low weight, no exudation, and
economic price with high corrosion resistance.

References
[1] Kobayashi, H. Advances in Oxy-Fuel Fired Glass Melting Technology. Presented at XX International Congress on Glass, Kyoto, Japan. Sept.,
26Oct., 1, 2004.
[2] Gridley, M. Philosophy, Design and Performance of Oxy-Fuel Furnaces. 57th Conference on Glass Problems: Ceram. Eng. Sci. Proc. 1997, 18,
Issue 1, 114.
[3] Ibbotson, A., Hunter, J., Brown, J.T. and McMahon, A.K. The Development of a Large Oxy-Fuel Glass Melter and an Assessment of its
Performance and Potential. Presented at European Seminar on Improved Technologies for the Rational Use of Energy in the Glass Industry,
Wiesbaden, Germany, Feb., 46, 1992.
[4] Faber, A.J. Corrosion of Refractories Under Oxy-Fuel Combustion. Glass Production Technology International. 1997, 6166.
[5] LeBlanc, J. Impact of Silica Attack on Soda Lime Oxy-fuel Furnaces. Presented at Ceramic Industry Manufacturing Conference and Exposition,
Pittsburgh, USA, Oct., 11, 1995.
[6] Godard, H.T., Kotacska, L.H., Wosinski, J.F., Winder, S.M., Gupta, A., Selkregg, K.R. and Gould, S. Refractory Corrosion Behaviour Under Air-Fuel
and Oxy-Fuel Environments. 57th Conference on Glass Problems: Ceram. Eng. Sci. Proc. 1997, 18, Issue 1, 180207.
[7] Duvierre, G., Zanoli, A., Boussant-Roux, Y. and Nelson, M. Selection of Optimum Refractories for the Superstructure of Oxy-Fuel Glass Melting
Furnaces. 57th Conference on Glass Problems: Ceram. Eng. Sci. Proc. 1997, 18, Issue 1, 146163.
[8] RHI Product Information: STELLA GNLA New Silica Brick Without Lime Bonding. Glasstec Exhibition 2006, Dsseldorf, Germany.
[9] Mulch, C., Weichert, T. and Postrach, S. Neuer keramisch gebundener Werkstoff fr den Oberbau von oxy fuel beheizten Glaswannen auf SiO2-
Basis. Presented at Httentechnische Vereinigung der Deutschen Glasindustrie e.V., Meeting, Niederdollendorf, Germany, March 2006.
[10] van Limpt, J.A.C. Modeling of Evaporation Processes in Glass Melting Furnaces, Ph.D., Thesis, Eindhoven University of Technology, Netherlands,
2007.
[11] Morey, G.W. and Bowen, N.L. High SiO2 Corner of System Na2O-CaO-SiO2. J. Soc. Glass Technol. 1925, 9, 232233.
[12] Faber, A.J. and Verheijen, O.S. Refractory Corrosion Under Oxy-Fuel Firing Conditions. 57th Conference on Glass Problems: Ceram. Eng. Sci.
Proc. 1997, 18, Issue 1, 109119.
[13] Beerkens, R., Verheijen, O., van Limpt, H. and Smits, B. Evaporation of Alkali Compounds and Silica Corrosion in Glass Furnaces. Presented at
HVG-NCNG Colloquium on Operation and Modelling of Glass Melting Furnaces, Aachen, Germany, Nov. 8, 2005.
[14] Monofrax Alumina Fused Cast Crowns. Monofrax Report No. 1, 1997.
[15] Winder, S.M., Selkregg, K.R. and Gupta, A. Update on Selection of Refractories for Oxy-Fuel Glass-Melting Service. Ceram. Eng. Sci. Proc., 1999,
20, No. 1, 81105.

Authors
Rongxing Bei, RHI AG, Industrial Division, Wiesbaden, Germany.
Klaus Santowski, RHI AG, Technology Center, Leoben, Austria.
Christian Majcenovic, RHI AG, Technology Center, Leoben, Austria.
Susanne Jrg, RHI AG, Technology Center, Leoben, Austria.
Corresponding author: Rongxing Bei, rongxing.bei@rhi-ag.com

> 35
 RHI Bulletin > 2 > 2013, pp. 3639

Christian Majcenovic, Gerald Gelbmann and Rongxing Bei

Microstructural Analysis of Magnesia Bricks

Operating Under Altered Conditions in the
Regenerator Condensation Zone of Glass Melting
Furnaces
Refractory producers need to offer lining solutions tailored to the different operating condi-
tions occurring in glass melting furnaces [1]. For example, in the regenerator condensation
zone (7001100 C) it is necessary to adapt the lining concept to the specific atmosphere
resulting from the waste gas composition. For oxidizing conditions, forsteritic-bonded magne-
sia-zircon checker bricks are a well-proven lining concept providing satisfactory lining perfor-
mance, while in a reducing atmosphere pure, low-iron magnesia bricks offer the best perfor-
mance in this temperature range. However, the requirement to fulfil environmental regula-
tions by implementing for example NOx reduction measures in addition to severe operating
problems can significantly change the typical regenerator atmosphere. In such cases, the cor-
rosive load on the lining from waste gases is highly intensified. In this paper an insight into
the microstructural changes occurring in brick linings located in the condensation zone when
the atmosphere is drastically changed are discussed with examples from postmortem inves-
tigations and a laboratory trial.

Introduction
Flue gases in oil or gas fired soda-lime glass melting
furnaces consist mainly of fossil fuel combustion prod-
ucts such as SOx (in the case of oil firing), CO, CO2 , HCl,
NOx , O2 , and N2. Additional components in the flue gas
can be SO2 , stemming from the refining agent, and
NaOH, mainly originating from the glass melt [1]. Under
oxidizing operating conditions, volatiles like sodium and
SO3 condense in the so-called condensation zone of
the glass melting tank regenerator, resulting in the final
formation of Na2SO4. This condensation zone occurs
in the temperature range of approximately 7001100 C
(Figure 1). In the case of oxidizing operating conditions
and excess SO3 , aggressive free sulphate is formed
besides sodium sulphate. This resulted in the develop-
ment of forsteritic-bonded magnesia-zircon bricks [2],
which provide the highest corrosion resistance against
sulphate attack.

Since the glass industry is a major combustion source,

in recent years it has had to solve several problems to
reach government environmental regulations, for exam-
ple NOx emission targets. This can be achieved by using
oxy-fuel combustion as well as by operating the furnace
under reducing conditions [3], defined as a CO content
> 1000 ppm (vol) [1]. Reducing conditions can be
reached for instance by decreasing the combustion air
flow to under stoichiometric conditions or by introduc-
ing natural gas into the waste gas stream (i.e., Pilkington Condensation zone
3R process) [4] before it enters the regenerator. Another
possibility is to inject ammonia into the exhaust gas Figure 1. Glass tank regenerator. The condensation zone has a
temperature range of approximately 7001100 C.
stream in the regenerator zone where the temperature
lies within the effective NOx reduction range of between
8701090 C [5].

36 <
 RHI Bulletin > 2 > 2013
The effect of reducing conditions on the waste gas in the
condensation zone is that SO3 is not stable and as a result
sodium sulphate cannot form in the condensation zone. As
a consequence, aggressive sodium remains in the flue gas
[1]. Since sodium has a high reaction potential with SiO2-
rich brick materials, pure, low-iron magnesia bricks are an
appropriate lining recommendation for the regenerator
condensation zone operating under reducing conditions. In
sodium silicate glass melting tanks, particularly in the case
of gas firing where there is a very high load from NaOH in
the flue gas, pure magnesia bricks show the best perfor-
mance.
In summary, depending on the furnace atmosphere, suit
able and well-proven refractory lining recommendations
can be made. However, in cases where during operation
the atmosphere within the regenerator heating phase
changes drastically from the usual oxidizing to reducing
conditions and vice versa, serious chemothermal attack on
the previously well-performing refractory lining can arise.
In extreme cases, the regenerator lining lifetime can
decrease drastically.
The following examples provide a comprehensive view of
the microstructural changes that occurred when bricks
were subjected to a drastically changed atmosphere in the
regenerator. The samples were investigated microscopi-
cally and compared to unused material.
Investigation Procedure
To generate results with the highest possible quality and
accuracy levels, sample investigations were carried out
according to international standard procedures. For exam-
ple calibration was performed using internationally certi-
fied standards. Na was analysed by inductively coupled
plasma optical emission spectrometry (ICP-OES) (ISO
26845), which covers the range from parts per billion to
high wt.%. Sulphur determination (DIN 51085) using LECO
CS 200 covered a range of 030 wt.% sulphur in a refrac-
tory sample with an accuracy of 0.1 wt.%. The
4
1 2
2 1
3 sulphate, Ca-Na-sulphate, Ca-Na-Mg-sulphate, and forsterite
500 m
Figure 2. Magnesia-zircon checker brick after 17 years in service.
At the near surface, up to a maximum of 5 mm from the hot
face, corrosion of magnesia (2) due to the formation of a sul-
phate phase (1) is visible. The forsteritic matrix shows very high
resistance against sulphate attack (3) and pores (4) are indicated.
microscopic investigations were carried out on polished
sections by optical light microscopy and using a JEOL 6400
scanning electron microscope equipped with an energy
dispersive spectrometry (EDS) analysis system to provide
chemical microanalyses.
Results and Discussion
Magnesia-Zircon BricksOxidizing Atmosphere
and High Sulphate Load
Forsteritic-bonded magnesia zircon brick brands like
RUBINAL EZ and RUBINAL VZ are a suitable lining material
for regenerators operating with an oxidizing atmosphere
where there is an excess of sulphate in the flue gas. One
important microscopic feature of this brick type is that ini-
tial magnesia and zircon brick components completely
react during the firing process to form magnesia, forsterite,
and zirconia. Well-selected raw materials that form a dense
microstructure with homogeneously distributed compo-
nents, a strong forsteritic bonding structure in the brick,
and the development of a forsteritic belt protecting the
magnesia provide the microstructural basis for a satisfac-
tory lining life. Due to its acidic character, forsterite does
not react with sulphate. This has been confirmed in several
postmortem studies of samples, not only from the glass
industry, where magnesia with Ca2SiO4 in the interstitial
phase is corroded by sulphate to form merwinite, monticel-
lite, and finally the stable reaction product forsterite [1,6,7].
Figures 2 and 3 provide impressive microstructural exam-
ples of a forsteritic-bonded magnesia-zircon checker brick
that achieved a lining lifetime of 17 years in the condensa-
tion zone despite very high sulphate load. Even in the cen-
tre the SO3 load was 6.77 wt.% with a molar alkali/SO3 ratio
of 0.32. At the immediate surface there was magnesia cor-
rosion due to sulphate attack (see Figure 2) involving the
formation of Na-Mg-sulphate. However, the forsteritic
bonding matrix was stable and almost unaffected. At a
depth of 7 mm there was Na-Mg-sulphate infiltration and
densification of the open pores but no bonding structure
corrosion and only very minor corrosion of the forsterite
protected magnesia grains (see Figure 3).
2
demonstrated with a postmortem sample that had become
affected when the atmosphere was severely changed by the
operating conditions. In this extreme example a 6.8 wt.%
SO3 content with a molar Na2O/SO3 ratio of 0.31 was found
even in the centre of some bricks. Generally, preferential
corrosion of the Ca2SiO4 interstitial phase as well as MgO
2
can occur. Sulphate attack in combination with a certain
amount of sodium and MgO results in the formation of Ca-
(Figure 6). Consequently, there is also corrosion of the MgO
bonding structure. As a result of MgO participating in the
sulphate attack, the formation of idiomorphic, cubic shaped
3 100 m
Figure 3. Microstructural detail 7 mm from the surface of a mag-
nesia-zircon checker brick after 17 years in service. No corrosion
of the forsteritic bonding matrix (1). The forsteritic belt (arrows)
protecting the magnesia grains (2) and Na-Mg-sulphate in the
pores (3) are indicated.
> 37
 RHI Bulletin > 2 > 2013

Magnesia-Zircon BricksReducing Conditions
and Sodium Attack
The following example is a magnesia-zircon brick sample
that was exposed during a laboratory trial to a reducing
atmosphere containing an excess of sodium compared to
sulphur. The temperature was cycled from 800 C to 1100 C
and back to 800 C. Firing during the 30 minute heating
phase was under reducing conditions (35% CO) whilst the
30 minute cooling period was under oxidizing conditions.
A total of 96 cycles were performed. The forsterite reacted
with the supplied sodium to form Na-Mg-silicate (Figure 4).
This resulted in a corroded, softened bonding structure,
especially near the surface. Under strongly reducing condi-
tions the forsteritic bonding structure in magnesia-zircon
bricks is corroded by sodium attack, which increases with
the exposure time and begins at the brick surface. In
extreme cases even ZrO2 can be corroded to form Na-zirco-
nate or Na-Zr-silicate.
demonstrated with a postmortem sample that had become
affected when the atmosphere was severely changed by the
operating conditions. In this extreme example a 6.8 wt.%
SO3 content with a molar Na2O/SO3 ratio of 0.31 was found
even in the centre of some bricks. Generally, preferential
corrosion of the Ca2SiO4 interstitial phase as well as MgO
can occur. Sulphate attack in combination with a certain
amount of sodium and MgO results in the formation of Ca-
sulphate, Ca-Na-sulphate, Ca-Na-Mg-sulphate, and forsterite
(Figure 6). Consequently, there is also corrosion of the MgO
bonding structure. As a result of MgO participating in the
sulphate attack, the formation of idiomorphic, cubic shaped
MgOpericlasecan also occur (Figure 7). This can be
explained by the slight thermal changes and related MgO
saturation limit changes in the salt melt. Higher thermal
load results in an increased ability for MgO to dissolve in
the melt. When this MgO saturated sulphate melt cools,
MgO precipitates, forming idiomorphic, cubic crystals
within the sulphate.

Pure Magnesia BricksReducing Conditions

and Sodium Attack
The usual lining recommendation for the condensation zone
in the case of reducing conditions and the resulting sodium
attack is a pure, low-iron magnesia brick such as ANKER
DG1 or RUBINAL VS [1]. As a basic oxide, MgO has the
highest resistance against basic sodium attack. The typical
microscopic feature of this brick type is a very strong bond-
ing structure between the magnesia grains (Figure 5). In
addition, the magnesia raw material purity, which should
generally have a low Fe-oxide content, is highly important.
The higher the sodium load, the purer the raw material
should be as well as the higher the brick firing temperature.

Pure Magnesia BricksOxidizing Conditions

and Sulphur Attack
Under oxidizing conditions and a resulting molar alkali/sul- 100 m
phate ratio < 1, corrosion of the pure magnesia brick bond-
ing structure can occur. At a lower alkali/sulphate ratio the Figure 5. High fired pure magnesia brick. The fines develop a
corrosion becomes more severe. The effect can be strong bonding matrix.

2
1

2
3 1

100 m 50 m

Figure 4. Magnesia-zircon brick sample that had undergone a
laboratory corrosion test where the heating and cooling phases
were under alternating reducing and oxidizing conditions, respec-
tively. 96 cycles were performed between 800 C and 1100 C.
Mainly sodium attack occurred. Newly formed Na-Mg-silicate
(1) minimal Na-sulphur phases (2), corroded forsteritic matrix
(3) with ZrO2 (white), MgO (4), and pores (black) are indicated.
Figure 6. Pure magnesia brick, approximately 1.5 mm from the
hot face brick, after sulphate attack caused by an oxidizing
atmosphere. Some residual MgO bonding bridges remain.
MgO (1), Na-Mg-(K)-Ca-sulphate (2), Ca-sulphate (3) are indicat-
ed. SEM-EDX analysis of point 2 detected 11.6 wt.% Na2O, 18.7
wt.% MgO, 66.0 wt.% SO3, 1.2 wt.% K2O, and 2.5 wt.% CaO.

38 <
 RHI Bulletin > 2 > 2013

2 densation zone in glass melting furnaces that are selected
1 optimized for the special operational requirements in this
1 1
50 m
Figure 7. Pure magnesia brick after sulphate attack caused by an
oxidizing atmosphere. Precipitation of idiomorphic, cubic shaped
MgO (1) from the sulphate melt (2) is visible.
Conclusion
There are well-proven solutions to line the regenerator con-
according to the operating conditions such as the fuel type
and whether the waste gas atmosphere is oxidizing or
reducing. The microstructure of the various refractories is
critical lining zone. However, when during the heating
phase the usual atmosphere in the regenerator is drastically
changed, the flue gas also significantly changes its corro-
sive potential. Atmosphere changes can occur for instance
in the case of operating problems or due to NOx reduction
measures taken during the life cycle of an existing regener-
ator lining. Therefore, a possible impact on the existing
glass tank regenerator lining and its performance must be
considered. In extreme cases drastically lowered lining per-
formance can occur.

References
[1] Heilemann, G., Schmalenbach, B., Weichert, T., Postrach S., Lynker, A. and Gelbmann, G. New Solutions for Checkers Working Under Oxidizing
and Reducing Conditions. 67th Conference on Glass Problems: Ceram. Eng. Sci. Proc. 2008, 28, Issue 1, 183194.
[2] Weichert, T. and Schmalenbach, B. Use and Further Development of Magnesia-Zircon Bricks in the Glass Industry. 55th Conference on Glass
Problems: Ceram. Eng. Sci. Proc. 1995, 16, Issue 2, 6873.
[3] Kido, N. Recent Problems in Glass Melting from the View Point of Refractory and its Solutions. Advanced Materials Research. 2008, 3940,
593600.
[4] Schmalenbach, B. and Riepl, K. Impact of Reducing Atmosphere on the Corrosion of Refractories in Regenerators of Glass Melting Tanks. Proc.
UNITECR 01, Cancun, Mexico, Nov., 48, 2001; pp. 11351141.
[5] Hughes, D.E. Melting Glass With Reduced NOx Emissions. United States Patent 4,328,020, 1982.
[6] Bartha, P. and Sdje, J. Degradation of Refractories in Cement Rotary Kilns Fired With Waste Fuels. CN Refractories. 2001, 5, 6271.
[7] Jrg, S., Majcenovic, C., Liprandi, F., Mura, R. and Nievoll, J. Outstanding Performance of ANKRAL ZE at the Caravate Plant, Colacem S.p.A., Italy.
RHI Bulletin. 2007, No. 2, 3134.

Authors
Christian Majcenovic, RHI AG, Technology Center, Leoben, Austria.
Gerald Gelbmann, RHI AG, Technology Center, Leoben, Austria.
Rongxing Bei, RHI AG, Industrial Division, Wiesbaden, Germany.
Corresponding author: Christian Majcenovic, christian.majcenovic@rhi-ag.com

> 39
 RHI Bulletin > 2 > 2013, pp. 4041
Joseph Plunkett and Friedrich Schweighofer
RHI US Ltd Provides Value-Added Services to
Environmental, Energy, and Chemical Sectors in
the USA
Introduction
For many years RHI made continual efforts to penetrate the
USA market in the environmental, energy, and chemical
(EEC) sectors. However, it frequently encountered road-
blocks due to established contractor and installer relation-
ships with plant owners and operators, as well as preexist-
ing agreements with refractory manufactures. Therefore,
RHI recently introduced its full service capability in the USA
with RHI US Ltd. Through this strategy, RHI is able to pro-
vide all its services as value added and not just to operate
as a commodity provider. During discussions, both owners
and engineering firms have indicated that this complete ser-
vice is very welcome since it provides multiple advantages
with the Modular Solution System. As a result projects can
be executed very effectively from start to finish. The specific
services included in RHIs Modular Solution System are
detailed in Figure 1.
Complete Service Provider
Recently RHI US Ltd., was approached by Chemetics (USA),
a process technology-based engineering group, to com-
pletely line a sulphur recovery unit (SRU) (Figure 2) at the
Chemtrade facility in Shreveport, Louisiana (USA). The SRU
was failing due to emergency process shutdowns, multiple
hot spots, and structural deterioration of the regeneration
furnace. Continual repairs to this unit had been driven more
by emergency measures than scheduled maintenance. This
resulted in materials being used that were immediately
available and a subsequent high risk of future failure and
low performance reliability.
Engineering
n Basic engineering
n Detailed engineering
nE ngineering plus
(modelling and simulation)
Site Management
n Installation
n Supervision
n Site organization
n Dry out
Figure 1. RHIs Modular Solution System and the value-added services.
40 <
Since the SRU is the heart of the entire plant process, a
long-term solution was essential. While Chemetics offers
excellent process designs, with resources for fabricating the
steel vessel shells, it required refractory lining designs for
the process, material deliveries to meet the scheduled plant
shutdowns, quality controls and assurance during the
installation, and documentation to establish future repair
specifications. RHI was able to meet all these requests, with
RHI DINARIS in Wiesbaden (Germany) providing refractory
designs, comprehensive drawings, and the installation
instructions.
A complete estimate, scheduled timeline, manufactured
specialty shapes, and equipment were provided by RHI Can-
ada Inc., (Boucherville, Quebec), while inventory materials
and manufactured goods were supplied by RHIs Burlington
(Canada) and Tlalnepantla (Mexico) plants. Additional
resources to execute the project were drawn from RHIs
Edmonton branch (Canada) and Wiesbaden. The RHI Con-
struction Manager and supervisors provided on-site direc-
tion and support to locally sourced employees from the
International Union of Bricklayers and Allied Craftworkers.
All the various personnel worked together as a team, being
very instrumental in the project development and plan exe-
cution.
As this was the first project to be run by RHI US Ltd., many
internal systems had to be developed for commercial rea-
sons. For example, Payroll established a system to handle
the various state payrolls, an overall system for order entry,
costs, and invoicing was created in SAP, Purchasing set up
Material
n Production
n Packaging
n Transportation
n Warehousing
Maintenance
n After sales service
n Inspection services including
technical reporting
n Maintenance work
 RHI Bulletin > 2 > 2013
Figure 2. Sulphur recovery unit.
accounts for equipment rental and third-party purchases,
while Controlling established RHI US Ltd., business/contrac-
tor licenses and created workers insurance cover. New
roles and responsibilities were added to current positions in
Canada regarding estimates, customer sales representa-
tives, and accounts receivable. RHIs tailored Project Track-
ing System (PTS) was uploaded with project details prior to
Authors
Joseph Plunkett, RHI Canada Inc., Industrial Division, Sarnia, Canada.
Friedrich Schweighofer, RHI Canada Inc., Industrial Division, Burlington, Canada.
Corresponding author: Joseph Plunkett, joseph.plunkett@rhi-ag.com
the job start, which enabled daily cost monitoring and com-
parison of the actual performance against budgeted
resources.
The on-site project execution presented challenges because
a top priority was to respect the local environment, culture,
and resources. However, RHI personnel adapted to the vari-
ous demands and were successful in completing the project
on time and within budget.
Customer Satisfaction
The feedback from Chemtrade was very positive, with state-
ments including RHI can work on this site anytime, as they
demonstrate safe, professional work ethics, and are forth-
coming with immediate creative solutions. An additional
comment from Chemetics was RHI has shown us a new
avenue that we will certainly use for our future projects.
RHI will promote its Modular Solution System to the global
EEC, and cement and lime markets through RHI Canada,
RHI US Ltd., and Marvo operations, with the objective of
securing large capital projects, multi-year maintenance con-
tracts, and providing all key components for a value-added
service.
> 41
 RHI Bulletin > 2 > 2013, pp. 4243

Joseph Plunkett and Dieter Pirkner

American Petroleum Institute Refractory

Installation Certification Programme
Introduction Since its existence the group has developed the API STD
936 standard specification (Refractory Installation Quality
Oil refineries and the petrochemical industry require high-
Control-Inspection and Testing Monolithic Refractory Lin-
performance refractory products for numerous processes
ings and Materials), which is widely used throughout the
operating under severe conditions and correct installation is
petrochemical industry around the world, and the API 936
essential in the various application areas including all types
Refractory Personnel Certification Program (API 936 RPCP).
of cracking units, gasification reactors, and sulphur recov-
The practices and guidelines introduced by the group have
ery units (Figure 1). However, over the years development
been shown to improve reliability and extend refractory life.
of on-site quality control and assurance guidelines regard-
There has also been involvement in modifying or improving
ing refractory installation received minimal attention and
American Society for Testing and Materials (ASTM) stan
relied on interpreting installers and/or equipment manufac-
dards related to refractories.
tures operator manuals. Based on these very wide unre-
stricted practices, refractory materials would fail to meet
API STD 936 details installation quality control procedures
their anticipated performance or complete lining failure
for monolithic refractory linings and can be used to supple-
would occur requiring either repair or total replacement.
ment owner specifications [1]. Materials, equipment, and
These incidents would subject plant owners to valuable pro-
personnel are qualified according to the described methods,
cess downtime, refractory manufactures to the costs of
and the quality of installed refractories can be closely moni-
defending or replacing products, and installers with the
tored on the basis of defined procedures and acceptance
labour costs to reinstall materials. These shortfalls in quality
criteria (Figure 2). The responsibilities of inspection person-
control and assurance were identified by refinery owners
nel who monitor and direct the quality control process are
and refractory manufactures affiliated with the American
also defined in the standard.
Petroleum Institute (API) and resulted in formation of the
current Refractory Task Force.
API 936 RPCP refractory personnel must have knowledge
of installation, inspection, testing, and refractory lining
Refractory Task Force repair [2]. The API 936 Personnel Certification requires an
The Refractory Task Force comprises oil and gas refinery examination that is designed to identify applicants possess-
owners (e.g., ExxonMobil, Shell Global Solutions, Conoco- ing the required knowledge. The 4 hour examination
Phillips, Chevron, Valero, Phillips 66, and Marathon), refrac- focuses on the content of API STD 936 and consists of 75
tory producers (e.g., RHI, Vesuvius, Morgan Thermal Ceram- multiple choice questions. No reference information is per-
ics, Spar, UOP Callidus, Unifrax, Resco Products, and ANH mitted in the exam.
Refractories), and refractory installers (e.g., RHI, JT Thorpe
and Son, Thorpe Specialty Services, RECON, and Clayburn RHI Personnel Training
Refractories).
RHI has been actively involved with API 936 due to its major
contracts for maintenance and capital projects at various
petrochemical facilities globally. As a result it has built up
excellent relationships with refinery owners and refractory
installers in addition to developing complete turnkey

Figure 1. Fluid catalytic cracking unit: A typical application area Figure 2. Qualification test according to API 936: Gunning a test
where API certified personnel are required. panel.

42 <
 RHI Bulletin > 2 > 2013

packages involving installation. RHI has also provided

refractory training that encompasses the API 936 RPCP both
independently as well as in partnership with plant owners.
Recently, RHI was the first to perform this certification in
Germany with its manufacturing, laboratory, and field ser-
vice employees in the German language. It was also instru-
mental in getting the examination provided in French to
accommodate RHI customers and employees.

The internal selection process for API 936 training at RHI

has focused on laboratory technicians involved with associ-
ated refractory materials, construction managers, supervi-
sors, general foreman, field quality managers, and support
staff such as purchasers, customer service personnel, and
estimators. In total, RHI has successfully trained and certi-
fied over 250 people worldwide. Constant involvement in
the programme has enabled installation warranty services
or re-work to be eliminated, provides up-to-date informa-
tion, and generates continual improvements through the
service experiences and ongoing communication.

While other industries outside the environmental, energy,

and chemical (EEC) sectors do not have the resources to
perform such a training programme, RHI has adopted the
installation knowledge gained from API STD 939 as the
basis for quality control and assurance measures in other
refractory-related areas.

References
[1] http://www.techstreet.com/products/1587645
[2] http://www.api.org/certification-programs/individual-certification-program-icp

Authors
Joseph Plunkett, RHI Canada Inc., Industrial Division, Sarnia, Canada.
Dieter Pirkner, RHI AG, Industrial Division, Wiesbaden, Germany.
Corresponding author: Joseph Plunkett, joseph.plunkett@rhi-ag.com

> 43
 RHI Bulletin > 2 > 2013, pp. 4449

Olaf Krause, Gerhard Urbanek and Hartmut Krber

Determining Resistance to Abrasion at Ambient

TemperatureImproving Comparability Between
Laboratories
To gain a deeper understanding of how highly accelerated particles affect the surface of a
refractory material during service, two test methods, ASTM C704 and EN ISO 16282, were
established. When performed as described, the tests provide informative data regarding
material abrasion, although it became evident there was a lack of interlaboratory comparabili-
ty. In order to enhance reproducibility, the latest revisions of ASTM C704 in 2009 and 2012
resulted in a more rigid definition of the testing device. However, this paper proposes a dif-
ferent route to perform blast abrasion tests that generates highly reproducible abrasion val-
ues even if the tests are performed in different laboratories. The key to obtaining consistent
values is that prior to the test the pressure supply for the blast gun must be adjusted until
the abrasion value of a standard float glass sample is 9.3 cm3 0.3 cm3 using 1000 g of SiC
particles. The results of a round robin test performed at 10 laboratories with 6 different types
of refractory material confirmed that this alternative method increases interlaboratory test
reproducibility and is sufficiently robust to recommend revision of the current standards.

Introduction ASTM C704M - 09 in 2009. In this update the blast gun and
venturi system dimensions were defined in more detail and
Refractory resistance against abrasion is a key issue for
a new clause was added that describes known factors that
many industrial furnace applications where particle-loaded
affect the results. The findings in this clause are based on
gas jets are expected during the process. For example, they
a ruggedness test performed using float glass samples.
occur in furnaces for the petrochemical industry, waste
incineration, coal-fired power plants, and in steel reheating
pusher furnaces.
Pressure gauge

In the past, two test methods to evaluate abrasion resis

tance were established, namely ASTM C704 first published
in 1972 and EN ISO 16282 published in 2008. More precisely
EN ISO 16282 is derived from the older ASTM C704 - 01
with minor editorial and technical changes. Basically the
tests determine the volume (cm3) of material abraded from
the flat surface of a sample positioned at right angles to a
nozzle through which 1000 g of size-graded SiC grain is
blasted by air at a defined air pressure using a blast gun
and venturi system (Figure 1). The bulk density, B, of the
Air supply
sample material is determined prior to the test by measur-
ing the sample weight, M1, and volume. The sample is also
weighed after the test, M2. The abraded volume loss, A, is
Venturi housing
calculated using the equation:
Venturi nozzle
A = (M1 M2)/B (1)
Abrasive supply
Whilst the procedure generates reliable and reproducible
results within a single laboratory, when the values are com-
pared between different laboratories they show significant
and repeated deviations. This imprecision has led to unjus-
tified complaints from refractory user industries when a
third-party laboratory crosschecked the specified values for Glass tube and
abrasion resistance. The economic impact resulting from metal stabilizing
the test variability can be considerable for both refractory sleeve
producers and consumers.

To improve the reproducibility, the ASTM Committee C08

on Refractories revised ASTM C704 - 01 and published Figure 1. Schematic diagram of a blast gun and venturi system.

44 <
 RHI Bulletin > 2 > 2013
Statistically significant effects were reported if the inside
diameter of the inlet air nozzle and the air pressure were
not as defined in the standard. In the latest revision ASTM
C704M - 12, published in 2012, precision of the apparatus
setup was further defined. Supplementary requirements for
highly abrasion-resistant materials were also added. The
major task of this clause is to more precisely describe the
testing conditions that are attained, for example by mount-
ing additional pressure gauges. It is evident from the inclu-
sions that the ASTM Committee C08 is heading toward a
more rigid definition of the apparatus dimensions, espe-
cially the particle acceleration system.
Main Factors Influencing Abrasion
During the Test
The refractory material volume loss is dependent principally
on the impact energy that is discharged when highly accel-
erated SiC particles hit the sample surface. It is proportional
to both the particle velocity and weight (i.e., grain size).
Therefore, only narrow SiC grain distributions are suitable
for the test. It is also necessary to examine the grain size
distribution within one batch if disintegration effects are
obvious. In addition, the particle surface plays a role. The
particles should have angular, jagged edged surfaces and
therefore only be used once. The general grain shape can
be checked by measuring the bulk density.
Many factors affect the particle velocity during acceleration.
Of major importance is the standard air pressure provided
to the venturi system and both standards specify 4.5 bar.
However, particle acceleration inside the blast gun is not
only dependent on the pressure but also on the chamber
dimensions inside the blast gun and the specific dimen-
sions of the venturi nozzle. The latter is described in detail
in ASTM C704M - 09. However, for as long as ASTM C704
has existed, a simple but essential problem has been dis-
cussed among those applying the standard outside the US:
The specified blast gun is not available in Europe. More
over, since 2009 the ASTM has stated that the described
blast gun is the only one permitted.
After the particles have been accelerated in the venturi
chamber, they pass through a glass tube with strictly
defined dimensions (i.e., length and diameter). Due to vari
able surface roughness, the specific material used to manu-
facture the tube can cause different friction effects and may
decelerate the SiC grains to a greater or lesser degree dur-
ing their passage through the tube. Since 2007, these and
additional factors known to affect the results have been
listed in ASTM C704, but without any quantification.
In summary, the evolving standards have defined the test
conditions and the apparatus setup more and more strictly
in order to get better interlaboratory reproducibility. How-
ever, as a result it has become more difficult to assure the
apparatus achieves the predefined conditions and the
method has become more error-prone. Therefore, this
paper presents an alternative solution that is much easier to
perform and leads to highly reliable results. It proposes
deregulating the apparatus setup specifications but defining
a preliminary step and adjusting the gas pressure to
achieve defined abrasion of a float glass test specimen,
described as the calibration standard in ASTM C704. This
material, broadly used as a reference standard, is particu-
larly suitable because it is highly homogenous. To obtain
the designated abrasion value of 9.3 cm3 0.3 cm3 for this
material, the standard air pressure is altered, which is con-
trary to the established standards where the pressure is fixed
at 4.5 bar. Using the new method, the apparatus setup details
are of secondary importance. A number of tests were per-
formed to examine various aspects of this approach in detail,
including a round robin test that clearly demonstrated cali-
brating the system on the basis of a defined abrasion value
provides reliable data to examine abrasive wear of refractory
materials.
Preliminary Examinations
Prior to the round robin test, investigations were undertaken
to understand how variable air pressures and different
amounts of abrasive material affect the results. In addition,
an alternative material (i.e., B4C) was used for the nozzle
tube.
Air Pressure Influence
In this preliminary test performed at two laboratories, boro-
silicate glass samples from a European producer with a bulk
density of 2.22 g/cm3 were abraded at predefined air pres-
sures between 3 and 6 bar. All the other parameters were
kept constant and in accordance with the procedure
described in ASTM C704M - 09.
The results show there is a linear ascending correlation
between the volume loss and increasing air pressure over
the measured range (Figure 2). However, the measurements
from the two laboratories have a different slope, indicating
a slightly different setup of the testing devices. For example,
if an abrasion value of 7.4 cm3 is required, the air pressure
must be adjusted to approximately 5.50 bar at Laboratory
A and 4.56 bar at Laboratory B.
Influence of the Abrasive Material Amount
and Nozzle Tube Material
In the subsequent evaluation, borosilicate float glass samples
from the European producer detailed above and standard float
glass samples as recommended by ASTM C704M - 09 were
abraded with different amounts of SiC (i.e., 8001200 g).
10.0
n Laboratory A
9.0 n Laboratory B
8.0
y = 2.1255x - 2.2325
Abrasion [cm3]
R2 = 0.99439
7.0
6.0
y = 1.5113x - 0.8143
R2 = 0.98207
5.0
4.0
3.0
3 4 5 6
Air pressure [bar]
Figure 2. Linear relationship between borosilicate glass plate vol-
ume loss (cm3) and the air pressure (bar) used to accelerate the
abrasive particles. The results were derived in two independent
laboratories.
> 45
 RHI Bulletin > 2 > 2013

Two sets of tests were performed, one with conventional deeper pits with a smaller eroded area at the surface, namely
glass nozzle tubes and a second with abrasion resistant B4C the blast jet appeared to be more focused. However, the
nozzle tubes. Each test was repeated twice with the same slope of all the tests was very similar. Therefore, it can be
tube. All other parameters were kept constant and in accord- concluded that the nature of the blast jet is of minor impor-
ance with the procedure described in ASTM C704M - 09, for tance for reproducibility of the method, if the air pressure or
example the predefined air pressure was 4.5 bar. All tests the amount of abrasive material is the adjustable parameter.
were performed using the same abrasion tester.
Interlaboratory StudyRound Robin Test
In all the tests performed, the abrasion loss showed a strict
As previously described, the performance and reproducibility
linear correlation with the amount of SiC used over the
of the standard test methods according to ASTM C704 or ISO
measured range (Figure 3). Therefore, the amount of SiC
16282 are highly dependent on the particle size and velocity
can also be used to standardize the abrasion tester. For this
before they hit the sample surface. Therefore, it is very diffi-
approach, the mass of SiC has to be adjusted until the mea
cult to reproduce the precise test conditions defined in the
sured abrasion value is equivalent to the standard value of
standards. As the preliminary test results described above
9.3 cm3 0.3 cm3, as defined in ASTM C704M - 09 for the clearly show, the abrasion loss is significantly and systemati-
reference float glass plate. cally controlled by the air pressure, which generates the SiC
particle acceleration in the venturi system. The round robin
The linear correlation between the amount of SiC used and test was performed to examine the interlaboratory reproduci-
the abrasion level indicates that materials with a low abra- bility of the test when performed according to ASTM C704M
sion resistance (> 20 cm) can be tested using a decreased - 09 and how the reproducibility is affected if prior to testing
amount of SiC (e.g., 500 g instead of 1000 g). This would the air pressure is adjusted until the abrasion value of a
reduce the possibility of blasting through the sample. Fur- standard ASTM float glass sample is 9.3 cm3 0.3 cm3.
thermore, abrasion values obtained using a different amount
of SiC can be used to determine the equivalent values for
Round Robin Test Setup
1000 g SiC.
In the round robin test, 6 different shaped and monolithic
In addition, Figure 3 clearly demonstrates that the actual refractories were examined in 10 laboratories. The materials
abrasion values measured are influenced by the nozzle tube were selected with the aim of covering a wide range of
material used. For example, the B4C tubes typically led to abrasion values (i.e., 530 cm3). Table I details the refractory
higher abrasion loss than the conventional glass tubes. How- materials tested.
ever, it was also evident that B4C tubes increased the repro-
ducibility of individual measurements since the results from
Sample Bulk density Refractory type Abrasion
repeat tests had the same linear regression. In contrast, the
(g/cm3) (cm3)
results obtained using glass tubes showed variations of up
A 2.15 Fireclay FC40 brick 30
to 2% for the same test conditions. As a result of the stan
dard glass tube erosion after a single test, this nozzle type B 3.00 Alumina-chromia ACr80/5 brick 15
must be changed after every test whilst the B4C nozzles CD 3.15 Magnesia-chromite MCr50 brick 7
have the advantage that they can be used approximately E 3.00 Sintered magnesia based brick 15
100 times because the erosion rate is very low. F 2.20 Conventional refractory concrete 8
G 2.80 Ultra low cement castable 5
When the erosion pits were examined after the test it was
evident that the blast jet slightly differed according to the Table I. Overview of the refractory materials examined in the
tube type. For example, the B4C tubes typically produced interlaboratory test, including the approximate abrasion value.

Prior to the round robin test, the various material samples

12.0
AS1 AN1 were cut or cast to meet the regulations defined in ASTM
11.0 AS2 AN2 C704M - 09 and ISO 16282. To determine the homogeneity
ES3 EN3 of the samples, they were examined using the impulse exci-
10.0
ES4 EN4
Abrasion [cm3]

9.0
tation technique (IET) and ultrasonic measurements were
also performed in three dimensions. The results of these
8.0
tests enabled the dynamic Youngs modulus to be calcu-
7.0 lated and compared (Figure 4). Determining this material
6.0 property was important because the abrasion resistance is
highly dependent on the homogeneity of the test samples.
5.0
This is exemplified by the series of fireclay brick FC40 sam-
4.0 ples (i.e., refractory sample A) that were examined in one
800 900 1000 1100 1200
laboratory and show that the abrasion resistance is strongly
SiC [g] dependent on the sonic velocity (Figure 5). A scatter in the
sonic velocity of 10% for any refractory sample set was
Figure 3. Linear relationship between the volume loss (cm3) and
amount of SiC abrasive (g) accelerated using a constant air pres-
regarded as admissible for the round robin test.
sure of 4.5 bar. Standard float glass (A/continuous lines) and boro-
silicate glass (E/dashed lines) samples were tested using standard A preliminary result at this stage in the investigation was
glass nozzle tubes (S/blue lines) and B4C nozzle tubes (N/red lines). that determining the sonic velocity is a powerful tool to
All the conditions were measured twice without changing the
tube. The repeat measurements determined with B4C tubes were evaluate the abrasion resistance of a single refractory mate-
very close; therefore, only a single regression line is visible. rial type, for example material A.

46 <
 RHI Bulletin > 2 > 2013

For the round robin test, every laboratory was instructed to
follow the same procedure. Initially, a test run was performed
with the standard ASTM float glass plates using the test con-
ditions defined in ASTM C704M - 09 (i.e., at a fixed air pres-
sure of 4.5 bar). The measurements were repeated multiple
times. Since the samples were highly homogeneous, the
results obtained were particularly useful to examine the inter-
laboratory reproducibility. Duplicate refractory samples (see
Table I) were then examined under the standard test condi-
tions. Subsequently, a second series of duplicate tests was
performed on standard ASTM float glass plates and the six
different refractory materials. However, prior to the tests the
air pressure was adjusted to attain an abrasion value of
9.3 cm3 0.3 cm3 with ASTM standard glass samples.
In summary, 10 laboratories examined 6 different refractory
materials under standard conditions and with the adjusted
air pressure. Typically, three glass plates were necessary to
adjust the air pressure to within the tolerance range. In addi-
tion, the standard glass plates were tested at least 4 times.
The results were evaluated with the PROLab Plus (QuoData
GmbH, Germany) software, which is in accordance with ISO
5725-6:1994. The results and precision statistics are detailed
in Table II.

Abrasion resistance test Sample Average abrasion SR Sr R r

(cm )
3
(%) (%) (%) (%)
ASTM C704M - 09 A 30.857 14.11 11.9 39.51 33.31
B 14.518 26.72 26.72 74.81 74.81
C 7.902 62.65 7.96 175.42 22.29
D 7.62 34.9 2.48 97.72 6.93
E 13.859 31.5 5.73 88.2 16.04
F (mould side) 6.284 28.25 79.1
G (mould side) 5.054 30.74 86.06
Standard float glass 8.998 28.25 1.87 79.1 5.24
Average 31.48 8.19 88.15 22.92
Adjusted air pressure A 33.911 7.05 2.52 19.74 7.06
(sample yields 9.3 cm3 0.3 cm3)
B 12.872 23.31 23.31 65.27 65.27
C 7.72 9.45 6.57 26.46 18.4
D 6.93 19.86 1.82 55.6 5.08
E 12.841 9.18 5.47 25.71 15.32
F (mould side) 8.56 22.01 7.94 61.63 22.24
G (mould side) 5.304 23.85 4.31 66.78 12.06
Standard float glass 9.266 1.72 1.57 4.82 4.4
Average 14.81 7.54 41.46 21.1

Table II. Results of the round robin test conducted at 10 laboratories on the 6 refractory samples detailed in Table I and standard float
glass samples. The abrasion tests were conducted according to ASTM C704M - 09 or using the modified test procedure where the air
pressure was adjusted so a standard float glass sample had an abrasion value of 9.3 cm3 0.3 cm3. Abbreviations include standard
deviation of reproducibility (SR), standard deviation of repeatability (Sr), reproducibility interval (R), and repeatability interval (r).

90 3300
Median
Dynamic Youngs modulus [MPa]

80 25%75% 3200
70 Range without
Sonic velocity [m/s]

outlier
3100
60 Outlier
50 3000
40
2900
30
2800
20
10 2700
A B C D E F G 22 24 26 28 30 32 34 36 38
Refractory type Abrasion [cm3]

Figure 4. Box plot of the dynamic Youngs modulus determined Figure 5. Approximate linear relationship between the abrasion
using the impulse excitation technique. The results are shown loss and sonic velocity for six different fireclay brick FC40 sam-
for the six different refractory materials detailed in Table I, name- ples (i.e., refractory type A) within the range defined.
ly fireclay FC40 brick (A), alumina-chromia ACr80/5 brick (B),
magnesia-chromite MCr50 brick (C and D), sintered magnesia
based brick (E), conventional refractory concrete (F), and an ultra
low cement castable (G).

> 47

Round Robin Test Results
Standard Glass Samples
The round robin abrasion results for the standard ASTM
float glass material are shown in Figure 6. The mean
empirical value was 9.294 and the tolerance limits were
fixed at 8.620 and 9.992 cm3, which corresponds to a
Zu-score of < 2.00. With a single exception, only the abra-
sion values determined after calibrating the equipment by
adjusting the air pressure fell within the statistical tolerance
limits. The scatter of results in a single laboratory is indi-
cated by the boxes. Laboratory 5 showed the widest scat-
ter. On further examination, it transpired that this labora-
tory had specific problems with fluctuations in the air pres-
sure supply that were solved by installing a pressure ves-
sel. In summary, when the standard glass material abrasion
results from all the laboratories were combined it was clear
that calibrating the equipment by adjusting the air pressure
significantly reduces the scatter of results (Figure 7).
0 12
11
Tolerance threshold (9.992 cm3)
10
Average
Abrasion [cm3]
9 in ASTM C704M - 09, the advantages of the gas adjust-
Tolerance threshold (8.620 cm3)
8 standard deviations between laboratories for the plate
7 1.72% for the improved method reported in this paper.
0
L1 L2 L3 L4 L5 L6 L2 L1 L3 L10 L5 L9 L7 L8 L9 L7
st st st ad ad ad ad ad ad ad st ad ad ad st st
Laboratory
Figure 6. Round robin abrasion results for standard ASTM float
glass material. The tests were performed at 10 laboratories
according to ASTM C704M - 09 with a fixed air pressure (st) or
using the modified test procedure where the air pressure was
adjusted so a standard float glass sample had an abrasion value
of 9.3 cm3 0.3 cm3 (ad). The triangles indicate measured
results.
0 tor of 2 when refractory materials were tested (i.e., SR
12
Abrasion value [cm3]
11
10
9
8
7
0 loss showed a linear correlation with the air pressure and
Standard
Figure 7. Box plot of all the standard glass sample measure-
ments performed at the 10 laboratories according to ASTM
C704M - 09 with a fixed air pressure (standard) or using the
modified test procedure where the air pressure was adjusted
so a standard float glass sample had an abrasion value of
9.3 cm3 0.3 cm3 (adjusted).
48 <
RHI Bulletin > 2 > 2013
Refractory Materials
The refractory material abrasion results from the round
robin test are summarized in Table II. Whilst the data
shows that calibrating the equipment by adjusting the air
pressure only slightly enhances the repeatability (Sr)
within laboratories (i.e., 7.54% compared to 8.19%), it is
clearly evident that this procedure significantly decreases
the standard deviation between laboratories (SR). Across
all the tested samples, the average relative standard devia-
tion between laboratories was more than halved from
31.48% to 14.81%. Furthermore, the results clearly show
that the abrasion testers are capable of producing reliable
and consistent results.
If only the results of the standard glass plates are consid-
ered, the enhancement achieved by adjusting the air pres-
sure is profound. While the standard deviation for all the
sample types between laboratories was improved by a fac-
tor of 2, the highly homogenous glass plates really dem-
onstrate the improvement, namely the relative SR was
decreased almost 20 fold from 28.25% to 1.72%. This
clearly indicates that the gas adjustment method can pro-
duce very precise results and that the heterogeneity
between refractory samples is the limiting factor.
When compared to the round robin test results published
ment method are also evident from the average relative
glass plates, namely 16.27% using the ASTM test and
Conclusions
The round robin test was performed using a broad range
of shaped and unshaped refractory materials that had
diverse blast abrasion resistances (i.e., 530 cm3). The
major outcome of this work is that to provide interlabora-
tory comparability it is better to adjust the air pressure of
the venturi system and calibrate the equipment with
respect to the abrasion rate of a standard float glass sam-
ple rather than define rigid regulations for the apparatus
setup as recommended by ASTM C704M - 12. When the
air pressure was adjusted in this manner the overall stan
dard deviation between laboratories was reduced by a fac-
Median
25%75% decreased from 31.48% to 14.81%) and by a factor of 20 if
Range without outlier only the results of the standard glass samples are consid-
Outlier
ered (i.e., SR decreases from 28.25% to 1.72%). The poorer
precision regarding the refractory materials can be attri
buted to the heterogeneity inherent in the samples. Sonic
velocity measurements prior to the abrasion test can help
identify outlier samples. The SR can also be positively
influenced by multiple measurements due to enhanced
repeatability.
Over the measured range, the refractory material abrasion
Adjusted the amount of abrasive used. Therefore, these parameters
can be adjusted over a broad range without a significant
decrease in the precision of the method. However, it is
important to note that the air pressure supply should be
checked carefully. Temporary pressure fluctuations caused
by an insufficient air supply will cause poor repeatability
and deliver in most cases lower values.
 RHI Bulletin > 2 > 2013

The linear correlation between the amount of SiC used and

the abrasion values indicates that materials with a low
abrasion resistance (> 20 cm) may be tested with an alter-
native amount of SiC (e.g., 500 g instead of 1000 g). This
would reduce the possibility of blasting through the sample
as well as avoid swirling of the SiC particles in deeper
holes. The abrasion values obtained using a different
amount of SiC can be used to recalculate the values equiv-
alent to abrasion with 1000 g SiC.

The test results also showed that the use of abrasion-resis

tant materials for the venturi nozzle are beneficial to pro-
duce constant operating conditions during the test and that
tubes made of B4C can be highly recommended. Further-
more, if the air pressure is appropriately adjusted, highly
abrasion resistant refractory materials can be effectively
examined.

The study findings will be relayed to the national and inter-

national standardization boards for evaluation. Changes to
the current version of ISO 16282 will be proposed and dis-
cussed by the ISO Technical Committee (i.e., ISO/TC 33
Refractories) and the European Committee for Standardiza-
tion (i.e., CEN/TC 187) during forthcoming meetings.

Authors
Olaf Krause, University of Applied Sciences Koblenz, Hhr-Grenzhausen, Germany.
Gerhard Urbanek, RHI AG, Technology Center, Leoben, Austria.
Hartmut Krber, Deutsches Institut fr Feuerfest und Keramik GmbH, Hhr-Grenzhausen, Germany.
Corresponding author: Gerhard Urbanek, gerhard.urbanek@rhi-ag.com

> 49
 RHI Bulletin > 2 > 2013, pp. 5053

Klaus Gamweger

New Innovative Gas Purging System for

Stationary and Tilting Copper Anode Furnaces
The use of gas purging plugs in the copper industry is a widely employed practice. They pro-
vide substantial improvements especially in anode refining furnaces, where savings in pro-
cess time and energy are obtained as well as refractory wear and buildups inside the furnace
are minimized. A newly developed system enables purging plugs to be implemented for the
first time in both stationary and tilting furnaces. An additional advantage in these vessels,
above all other benefits, is the significantly improved melting rate. This innovative and patent-
ed gas purging system consists of a purging plug cooling device and slidable, cooled piping
system. The novel development compensates for any thermal expansion in the furnace lining
and minimizes the risk of undesirable copper infiltration.

Introduction The Gas Purging System

The pressure for process optimization in the copper industry
is still very high. Energy and time savings are required to
increase the productivity of copper production and remain
competitive in a challenging economic environment. The
application of purging plug systems has demonstrated its
advantages in many copper processing units for more than
a decade [13], principally in anode furnaces and ladles. The
main benefits are faster process steps and lower energy
consumption due to the introduced nitrogen bubbles [4].
One development resulting from productivity improvements
is the furnace dimensions have increased significantly in the
last years. This has challenged both refractory design and
purging system installation. For example, the common con-
figurations are no longer suitable for the huge tilting and
stationary furnaces.
In a drum-type anode furnace, the purging plugs are
changeable and can be removed from the outside. How-
ever, this system is not possible for a tilting furnace
because the plugs must be out of the bath during exchange
otherwise liquid metal can run through the opening. In the
case of a drum-type anode furnace, it can be rotated until
the plugs are almost in a horizontal position and no longer
in contact with the metal. However, this procedure is not
possible with a tilting furnace, where the plugs remain cov-
ered with copper, even at the end of casting when the fur-
nace has been tapped. As a result, extracting the plugs
externally would be too dangerous, especially because the
work has to be performed overhead. Therefore, only a non-
changeable system with the piping integrated in the lining
is possible. The plugs and piping arrangement inside a tilt-
ing furnace are shown in Figure 1. The pipes run

Figure 1. Tilting furnace with gas purging system.

50 <
 RHI Bulletin > 2 > 2013
longitudinally down the mid section of the furnace bottom
towards the endwalls and through the steel shell to the
outside.
The main problem with implementing such a gas purging
system in a tilting or stationary furnace is the difference
between the thermal expansion of the wear lining and the
permanent lining, which becomes more and more critical the
larger the furnace. The bricks in the wear lining must be very
tightly connected to each other to prevent metal penetration
in between the bricks. Therefore, the refractory layout in the
furnace is designed to provide significantly higher thermal
expansion in the wear lining than in the permanent lining
during heat-up and operation. Usually the bottom lining
moves from the centre of the furnace bottom towards the
endwalls, where the expansion is partially compensated.
The purging plug and well block are installed in the wear lin-
ing whilst the system piping is located below in the perma-
nent lining. Since the plug piping crosses the boundary layer
between the wear and permanent lining, high tensions are
introduced that can cause damage to the welding or even the
pipes. In this case, a nitrogen leak would occur at this spot,
subsequently resulting in the plug becoming infiltrated with
copper. Therefore, the relative movement of the two lining
layers has to be compensated to prevent pipe damage. The
Figure 2. Conical purging plug with well block, supporting brick,
and gas connections.
Temperature [C]
30 600 1200
Figure 4. CFD simulation. Air-cooling of the plug bottom, surrounding region, and pipe.
patented solution to this problem is a slidable, air-cooled pip-
ing system (Figure 2).
The angled pipe connection from the plug is inserted into a
protection pipe, which provides an air-tight seal and is
affixed in the permanent lining. The space between the pro-
tection pipe and the surrounding brickwork is filled with ram-
ming mix. Since the angled pipe from the plug can slide
within the larger protection pipe, this compensates for any
plug movement caused by thermal expansion (Figure 3). The
nitrogen supply is realized with a flexible metal hose. Addi-
tionally, the plug bottom is cooled to minimize the risk of
copper leakage into the pipe system as a result of metal pen-
etration between the bricks in this area. For this purpose, the
purging plug is equipped with a double-layered steel bottom.
Compressed air is connected to the plug using a second flex-
ible metal hose and is blown between the two steel plates,
cooling the lower plug area and surrounding region. The
cooling effect has been visualized in computational fluid
dynamics (CFD) simulations, as shown in Figure 4. In situa-
tions where the piping is long and the cooling air line could
overheat, an additional compressed air line is incorporated
within the protection pipe to facilitate cooling. Due to the
overall cooling effect, the temperature underneath the plug
falls below a critical value so if metal infiltration occurs, the
copper freezes and a molten metal leak is avoided.
Double-layered
steel bottom
Protection pipe
Compressed air
Thermocouple
Nitrogen supply
Figure 3. Purging plug gas piping system.
> 51
 RHI Bulletin > 2 > 2013
Online thermocouples monitor temperatures at two posi-
tions in the system. The first measures the temperature
inside the purging plug, which indicates plug wear, whilst
the second records the bottom plate temperature, monitor-
ing the air-cooling efficiency.
Purging Plug Exchange
The lifetime of purging plugs used for this application is
between 18 months and 3 years. In some cases the furnace
lining has a longer durability so plug replacement may be
necessary. Due to the modular setup it is possible to replace
a worn out or blocked plug without renewing a large area
of the furnace hearth; only about one square metre has to
be removed and rebuilt. Furthermore, the piping remains
untouched in the permanent lining. This can be easily exe-
cuted during periodic repair to the tuyere zone.
Flow Pattern Simulation
Purging plugs have shown numerous positive effects on the
anode furnace process [4] including:
>> Improvement of the melting rate.
>> Faster and easier slag skimming.
>> More efficient oxidation and reduction.
>> Prevention of buildups and accretions.
>> Homogenization of the chemical composition and
temperature.
>> Time and energy savings.
To gain all benefits from installing a gas purging system, an
optimal number and positioning of the purging plugs is
essential. This optimization is performed with the aid of CFD
simulations [5]. The positive effect of gas purging on the
(a)
(b)
Figure 5. CFD simulation of a tilting anode furnace (a) with and (b) without purging plugs.
52 <
melting rate is an inherent result of the metal movement.
However, the impact on oxidation and reduction processes
requires more detailed examination. Especially in tilting
anode furnaces, with a high number of tuyeres in the side-
wall, an interfering effect from the plugs has to be avoided.
Figure 5 shows the difference in flow velocity with and with-
out the use of a gas purging system during reduction in a
tilting anode furnace. The red areas indicate the most rapid
melt flow, with the highest reaction kinetics occurring in
these regions. In these areas the most material exchange
occurs, the poling effect is very high, and a shorter reduc-
tion time is necessary to get these areas to react with the
tuyere gas. Therefore, these zones have to be maximized by
appropriately positioning the purging plugs and adjusting
the gas flow rate.
Results
The innovative gas purging system with a cooling device
and slidable, cooled piping system has been installed in
more than 10 stationary and tilting anode furnaces on 3 con-
tinents, and has generated energy savings of up to 30% dur-
ing smelting. The process time for oxidation and reduction
can be shortened by between 1018% and the skimming
time can be reduced by approximately half. If the anode fur-
nace is the bottleneck in the production line, these time sav-
ings contribute directly to the productivity. In addition, the
production rate is increased because the plugs keep the fur-
nace free from buildups so the furnace capacity remains at
the maximum level. In contrast, if buildups are allowed to
occur, the tonnage per heat can decrease dramatically over
the furnace lifetime, depending on the charged material and
temperature distribution.
Velocity [m/s]
0.0 0.5 1.0
 RHI Bulletin > 2 > 2013

Conclusion
The new cooled, slidable piping technology enables gas
purging systems to also be installed in stationary and tilting
furnaces. The system can withstand all expansion-induced
tensions in the furnace lining and has proven to be a safe
and long-lasting solution. It enables all the benefits of inert
gas purging in anode furnaces to be realized and is provid-
ing process improvements and energy savings in multiple
applications worldwide.

References
[1] Rigby, A.J. and Lanyi, M.D. Porous Plugs in Molten Copper Production and Refining. Smelting Operations and Advances: Proceedings of the
Copper 99-Cobre99 International Conference, Phoenix, Arizona, Oct., 1013, 1999; pp. 505516.
[2] Lee, S.S., Kim, B.S. and Choi, S.R. Application of the Porous Plug System in the Anode Furnace at Onsan Smelter. Proceedings of the Yazawa
International Symposium on Metallurgical and Materials Processing Principles and Technologies. Vol. 2: High-Temperature Metal Production, San
Diego, California, March 36, 2003; pp. 447458.
[3] Acuna, C. and Sherrington, M. Efficiency of Porous Plugs in Fire Refining of Crude Copper. Proceedings of the Yazawa International Symposium
on Metallurgical and Materials Processing Principles and Technologies. Vol. 2: High-Temperature Metal Production, San Diego, California, March
36, 2003; pp. 265279.
[4] Gamweger, K. Evaluation of the Efficiency of a Gas Purging System in a Copper Anode Furnace. Proceedings of the Sohn International
Symposium on Advanced Processing of Metals and Materials. International Symposium on Sulphide Smelting, Vol. 8, San Diego, California,
Aug., 2731, 2006; pp.499508.
[5] Zach, O., Gamweger, K., Lukesch, G. and Filzwieser, A. CFD-Modelling in the Non Ferrous Metals Industry. Proceedings of EMC 2005, European
Metallurgical Conference, Dresden, Germany, Sept., 1821, 2005; pp. 13171324.

Author
Klaus Gamweger, RHI AG, Industrial Division, Vienna, Austria.
Corresponding author: Klaus Gamweger, klaus.gamweger@rhi-ag.com

> 53
 RHI Bulletin > 2 > 2013, pp. 5458

Sonja Breyner, Klaus Santowski, Thomas Prietl, Alfred Spanring and Anna Franzkowiak

Thermal Shock Resistant Alumina-Chromia

Products for the Copper Industry
Conventional alumina-chromia materials are characterized by a high resistance to acidic
slags due to the formation of an Al2O3-Cr2O3 solid solution during brick firing. Typical applica-
tion areas for such products are glass tanks, waste incinerators, and taphole areas of pyro-
metallurgical vessels. However, in other regions, where not only corrosion due to chemo-
thermal load but also thermal shock predominates, these products suffer from discontinu-
ous spalling and exhibit poor refractory service life. Therefore, research and development
activities were focused on increasing the thermal shock resistance of shaped alumina-chro-
mia products. Since physical investigations and pilot scale slag tests indicated the properties
of these improved materials were at a sufficiently high level, a field trial was conducted at a
copper smelter. The mineralogical and chemical analyses of postmortem bricks installed in
the tuyere zone of a Peirce-Smith converter demonstrated that the material properties of a
new alumina-chromia brand met both the corrosion and thermal shock resistance required
for this application.

Introduction Laboratory Investigations

The main raw materials used in alumina-chromia products
are fused or calcined, based on alumina, chromium oxide,
and prereacted (Al,Cr)2O3 solid solution materials. During
brick firing an (Al,Cr)2O3 solid solution is additionally
formed from pure Cr2O3 and Al2O3 materials. Furthermore,
the presence of Cr2O3 reduces the dissolution potential
when in contact with acidic slags, as demonstrated in
several studies [12].
Besides the most common application areas in the glass
and chemical industry, there is an increasing demand for
alumina-chromia materials in the base metal industry, for
example in copper production processes. Compared to
basic bricks, alumina-chromia products are resistant to
hydration. However, during service in chemically and ther-
mally stressed areas conventional alumina-chromia prod-
ucts suffer from discontinuous spalling as a result of high
and frequent thermal loads. As a consequence, products
with sufficient resistance to both corrosion and thermal
shock are required for these operating conditions.
To develop refractory products tailored to specific service
conditions it is important to have a profound knowledge
of the metallurgical processes and furnace conditions
[34]. This enables the specific refractory consumption to
be minimized and increases the overall operational effi-
ciency. Economic considerations such as steadily increas-
ing energy and resource costs have resulted in companies
investing in recycling processes. In the base metal indus-
try like copper, recycling operations involve modifications
to the smelter feed, process conditions, and the chemical
composition of process slags. This adversely affects the
performance of standard linings and drives refractory pro-
ducers to search for material innovations. To achieve this
goal, laboratory investigations enabling brick develop-
ment and experimental testing in RHIs Pilot Plant at the
Technology Center Leoben were performed before evalu-
ating the material under practical conditions in a customer
field trial.
The laboratory investigations comprised development, pro-
duction, and physical evaluation of alumina-chromia materi-
als, including rotary kiln slag tests to examine the corrosion
resistance.
Product Development
During the alumina-chromia material development phase,
the Cr2O3 content, fused grain content, content of thermal
shock reducing components, as well as grain size distribu-
tion and firing conditions were identified as key factors influ-
encing performance. Since modification of each parameter
affects both the corrosion and thermal shock resistance of
the refractory material, an appropriate balance between
these key factors is indispensable. By controlling the grain
size distribution, space can be created to accommodate ther-
mal expansion or prevent crack propagation. However, the
resulting surface area increases the dissolution potential
with infiltrating liquids and gases. Therefore, the addition of
fused grain is necessary to increase corrosion resistance by
minimizing the specific crystal surface area. Ceramization of
the products is influenced by the firing intensity; however,
increasing this process results in the formation of stronger
sinter bridges between the coarse grains and reduces ther-
mal shock resistance. To increase thermal shock resistance,
zirconia-containing components can be added, for example
synthetically produced zirconia mullite. The mechanism is
based on the irregular thermal expansion behaviour of bad-
deleyite (ZrO2) with increasing temperature: At room temper-
ature the monoclinic form has a density of 5.6 g/cm3 and is
stable up to 1000 C. Between 1000 C and 1150 C baddeley-
ite undergoes a tetragonal modification resulting in a density
increase to 6.1 g/cm3. The structural transformation is revers-
ible and as a consequence of the thermal expansion mis-
match, microcracking occurs in the material that can dimin-
ish crack propagation during abrupt temperature changes.
Laboratory trials were conducted to find the most effective
balance between the aforementioned key parameters. The

54 <
 RHI Bulletin > 2 > 2013

ideal composition was found when the Cr2O3 content was provide fresh material and prevent saturation of the slag
between 1030 wt.% and the zirconia component exceeded with refractory material oxides.
10 wt.%. In addition, > 20 wt.% fused alumina-chromia grain
was added to maintain the corrosion resistance at an appro- After testing, the samples were cut in half and macroscopi-
priate level. cally analysed. Cross sections of the samples can be seen in
Figure 2. The wear and infiltration results measured from
Physical Testing the cross-sectional profiles are presented in Figure 3 and
Table III.
In order to evaluate the material properties of a thermal
shock resistant (SR) alumina-chromia product, the test
results were compared to a standard alumina-chromia
grade based on the same Cr2O3 content.

The test for thermal shock resistance was performed

according to DIN 51068-1, whereby the samples were
heated to 950 C and then cooled to room temperature by
quenching in water. The samples were subsequently dried
and reheated in the next cycle. Both the SR and standard
grades withstood 30 cycles. To further evaluate the thermal
shock resistance, the residual samples were subjected to a
compression test. The retained cold crushing strength
was 111 MPa for the standard grade, equivalent to 68% of
the initial strength, and 135 MPa for the newly developed
SR grade, which was equivalent to 89% of the initial
strength.

When the physical properties of a 10 wt.% Cr2O3 SR grade

are compared to the standard grade it is evident that the
bulk density and cold crushing strength are slightly lower
(Table I) whilst the refractoriness under load (T0.5) values
are comparable (Table II). The hot modulus of rupture of the
SR grade is lower compared to the standard material (see
Table II).

Rotary Furnace Test With Fe-Silicatic (a)

(Fayalithic) Slag
The rotary furnace test enables the corrosion resistance of
refractory materials in contact with slag to be evaluated at
temperatures ranging between 15001700 C. For each cycle
the furnace is charged with 35 kg of slag and heated with a
gas mixture of propane and oxygen (Figure 1). Up to six dif-
ferent grades can be tested simultaneously. For the test
described, a fayalithic-type slag enriched with SiO2 (43 wt.%
SiO2) was used and the operating temperature was 1600 C.
The slag was exchanged 10 times in order to constantly

Sample BD AP CCS
(g/cm3) (vol.%) (MPa)
Standard 3.50 15.0 160
SR 3.47 15.0 140

Table I. Comparison of the SR and standard grade physical prop-

erties evaluated at room temperature. Abbreviations include bulk
density (BD), apparent porosity (AP), and cold crushing strength
(CCS).

Sample RuL 0.2 MPa HMoR 1400 C

(C) (MPa)
Standard T0.5 > 1704 9.7
SR T0.5 > 1705 4.6 (b)

Table II. Comparison of the SR and standard grade hot physical Figure 1. Rotary furnace test (a) in operation and (b) gas burner.
properties. Abbreviations include refractoriness under load (RuL)
and hot modulus of rupture (HMoR).

> 55
 2 cm 2 cm

(a) (b)

Figure 2. Cross section through the (a) standard and (b) SR grade samples after the rotary furnace test.

(a) (b)

Figure 3. Wear (red section) and infiltration (dashed line) graphic measurements of the (a) standard and (b) SR grade samples after
the rotary furnace test.

sintered magnesia-chromite grade (26 wt.% Cr2O3) with a

Sample Wear area Wear depth Infiltration area Infiltration depth
(cm2) (mm) (cm2)
Standard 13.5 7.5 45.3
SR 18.1 10.6 54.7
Table III. Wear and infiltration measurements after the rotary fur-
nace test.
Field Trial
Test Conditions
The trial was performed with a newly developed SR grade,
RESISTAL RK30SR, in the tuyere zone of a copper converter
to evaluate the suitability of alumina-chromia material in
this new application area. Typically, the standard grades
used in a copper converter are magnesia-chromite bricks
(19 wt.% Cr2O3), and a thermal shock resistant grade based
on chrome ore and high purity sintered magnesia (26 wt.%
Cr2O3) at the tuyere line, since refractory bricks in tuyere
zones have to withstand a highly oxidizing atmosphere
combined with considerable temperature changes and faya-
lithic slag (2FeOSiO2) attack. Therefore, a 30 wt.% Cr2O3
alumina-chromia grade with increased thermal shock resis
tance was chosen for the trial. The bricks were installed in
the converter both directly at the tuyere line and in the
region surrounding the tuyeres.
Field Trial Results
The first evaluation took place during the scheduled con-
verter shutdown after 11 weeks in operation. Samples for
further analysis were taken from both test areas, although
bricks at the tuyere line were only examined macroscopi-
cally. In this region the SR alumina-chromia bricks had a
residual thickness of 80 mm, compared to the high purity
residual thickness of 30 mm. The bricks installed above the
(mm)
tuyere line were analysed in detail. In this region, the resid-
23.4
ual thickness of the SR alumina-chromia grade was signifi-
28.4 cantly higher (175 mm) compared to the standard magne-
sia-chromite grade (19 wt.% Cr2O3) with 95 mm; namely
47% of the SR alumina-chromia grade remained relative to
the initial thickness, whilst the standard magnesia chromite
grade had retained only 25% of the original thickness.
When the converter was stopped after 117 heats, a second
evaluation was performed. The SR alumina-chromia grade
from the area surrounding the tuyeres exhibited a residual
thickness of 240250 mm, representing 65% of the initial
thickness. The cross section through the sample is provided
in Figure 4. On visual inspection an infiltration depth of
70 mm was determined. This sample was also analysed by
reflected light and scanning electron microscopy (energy-
dispersive X-ray spectroscopy).
Mineralogical Analysis
Several zones could be distinguished in the polished sec-
tions for the mineralogical analysis. Below the slag/metal
coating, covering the immediate brick hot face, there was
a 12 mm thin reaction seam. In this reaction zone the
Cr-corundum rims were enriched with Fe-Ni-Cu-Zn-oxide.
In addition, the Zr-mullite had been completely destroyed
upon direct contact with the slag. At a depth of up to 2 mm
from the brick hot face the microstructure had recrystallized
and Zn-Cu-Mg-Fe-Al-Cr-oxide had formed in the matrix.
Cracks that had formed 10 mm parallel to the hot face were
completely filled with slag. At a depth of approximately
30 mm from the hot face Cr-corundum had additionally
reacted with Cu-oxide and formed Cu-Al-Cr-oxide. The infil-
tration of Cu-sulphide could be traced up to a depth of

56 <
 RHI Bulletin > 2 > 2013

approximately 60 mm from the hot face. Below this and

through to the cold face the brick microstructure was infil-
A 1 trated with Ca-Mg-sulphate and Na-Mg-Al-Cr (Fe)-sulphate.
These results are visible in Figures 57.
2
3 Oxide content A B C D
(wt.%) 025 mm 100125 mm 125150 mm Cold face
4 Na2O 0.75 0.55 0.74
B 5 MgO 0.53 0.71 0.62
C Al2O3 43.05 55.94 56.08
6 SiO2 5.48 4.02 3.99
CaO 0.42 0.32 0.33
TiO2 0.19 0.25 0.29
Cr2O3 23.81 30.44 29.84
Fe2O3 5.94 0.55 0.56
ZrO2 3.09 5.60 5.92
D 7
SO3 0.47

Figure 4. Cross section through a SR alumina-chromia grade
after 117 heats in the area surrounding the tuyeres. Samples for
chemical analysis (AD) and microscopic polished sections (17)
are indicated.
Table IV. Chemical analysis of the SR alumina-chromia grade
after 117 heats in the area surrounding the tuyeres. The tests
were performed according to DIN 51081 and DIN 51085 on ignit-
ed samples (1050 C) by X-ray fluorescence analysis and on orig-
inal samples using C-S elemental analysis, respectively.

100 m 1000 m

(a) (b)

Figure 5. Microstructure of the SR alumina-chromia grade after 117 heats in the area surrounding the tuyeres. (a) Immediate hot face:
Reaction zone with partial slag coating (R) and a thin Fe-Ni-Cu-Zn-oxide rich seam (arrows) around a Cr-corundum grain (1).
(b) 10 mm from the hot face: Crack running parallel to the brick hot face filled with slag and Cu-sulphide (red lines).

5
2

3 1
4 3
2
1 50 m 500 m

(a) (b)

Figure 6. Microstructure of the SR alumina-chromia grade after 117 heats in the area surrounding the tuyeres. (a) 50 mm from the
hot face: Corroded Zr-mullite visible, corundum (1), corroded Zr-oxide (2) with Zr-silicate at rims (3), Cu-sulphide (4), and Cr-corun-
dum in the matrix (5). (b) 80 mm from the hot face: Brick joint (red rectangle) free from infiltration, Cr-corundum (1), Zr-mullite (2),
and Ca-Mg-sulphate (3).

> 57
 RHI Bulletin > 2 > 2013

2 1

3
5
1 2
1000 m 10 m

(a) (b)

Figure 7. Microstructure of the SR alumina-chromia grade after 117 heats in the area surrounding the tuyeres. (a) and (b) cold face:
Cr-corundum (1), Zr-mullite (2), Na-Mg-Al-Fe-Cr-sulphate (3), glassy phase (4), and pore (5).

It can be concluded that the alumina-chromia brick infiltra- Summary and Conclusions
tion was comparably lower than in the sintered magnesia-
Alumina-chromia grades underwent further development to
chromite grade. Nevertheless, effects of high chemical and
combine high acidic slag resistance with improved thermal
thermal load on the microstructure (e.g., recrystallization
shock resistance. Whilst the materials were found to exhibit
and mullite degeneration) could be found as far down as
a decrease in bulk density as well as hot modulus of rupture
the middle section of the postmortem sample. In addition,
compared to the standard products, laboratory investiga-
traces of sulphate were detected at the brick cold face. How-
tions demonstrated both improved corrosion and thermal
ever, the average residual thickness of several postmortem
shock resistance of these hydration-resistant materials. To
samples was relatively high compared to the sintered mag-
evaluate this brick type in a highly oxidizing atmosphere
nesia-chromite grade.
combined with significant temperature changes and acidic
slag, a 30% Cr2O3 alumina-chromia grade, RESISTAL
Chemical Analysis
RK30SR, was installed in the tuyere zone of a copper con-
Four sampling positions for the chemical analysis were verter. The field trial results, including detailed chemical
chosen to generate comprehensive data through the post- and mineralogical investigations of postmortem samples,
mortem sample (see Figure 4). The results are provided confirmed that the thermal shock resistant alumina-chromia
in Table IV. It is evident that directly at the brick hot face products can be successfully applied in areas experiencing
there was a loss of Al2O3 (~ 13 wt.%), Cr2O3 (~ 6 wt.%), high thermal stress combined with chemical attack from
and ZrO2 (~ 3 wt.%) when compared to the middle section acidic melts and sulphur. Therefore, these new products will
(125150 mm). In addition, there was a significant supply also be suitable for a number of other application areas in
of Fe2O3 to the hot face (~ 6 wt.%) from the slag. At the cold primary copper smelting, converting, and refining.
face 0.47 wt.% SO3 was detected. This represents a lower
value than usually observed with magnesia-chromite bricks
due to lower penetration into the alumina-chromia brick
microstructure.

References
[1] Emblem, H.G., Davies, T.J., Harabi, A. and Tsantzalou, V. Alumina-Chrome Refractories. Proceedings of UNITECR 91, Aachen, Germany, Sept.,
2326, 1991; pp. 415421.
[2] Fraser, T. M. Development and Application of Chrome-Alumina Refractories. Application of Refractories: Ceramic Engineering and Science
Proceedings, Vol. 9, Issue1/2, 1988; pp. 110.
[3] Davenport, W.G., King, M., Schlesinger, M. and Biswas, A.K. Extractive Metallurgy of Copper. 4th Edition; Elsevier Science Ltd: Oxford, 2002.
[4] Routschka, G. (Ed) Pocket Manual Refractory Materials. 2nd Edition; Vulkan-Verlag: Essen, 2004.

Authors
Sonja Breyner, RHI AG, Technology Center, Leoben, Austria.
Klaus Santowski, RHI AG, Technology Center, Leoben, Austria.
Thomas Prietl, RHI AG, Industrial Division, Vienna, Austria.
Alfred Spanring, RHI AG, Industrial Division, Vienna, Austria.
Anna Franzkowiak, RHI AG, Industrial Division, Vienna, Austria.
Corresponding authors: S
 onja Breyner, sonja.breyner@rhi-ag.com
Alfred Spanring, alfred.spanring@rhi-ag.com

58 <
RHI Bulletin > 2 > 2013, pp. 5962

Hans Ulrich Marschall, Daniel Kreuzer and Alfred Spanring

Thermomechanical Finite Element Simulation of

Heat-Up Processes in a Lead Rotary Furnace
A customer observed three cases of damage to the steel shell of a lead rotary furnace. A
thermomechanical model was established to determine the root cause of the failures using
finite element analysis (FEA). The FEA model provided an insight into the thermomechanical
stresses in the refractory lining and steel shell, resulting in guidelines to optimize the heat-up
procedure and lining design. This led to an improved lifetime of the rotary furnace.

Introduction One of the furnace endwalls, for example the right-hand

The short rotary furnace is one of the units used in the lead
battery recycling process. After renewing the furnace lining
it is common practice to perform a procedure called slag
washing. This involves heating the furnace up to tempera-
tures in the region of 11001250 C and using a high melt-
ing point slag to infiltrate the lining and joints between the
bricks in order to generate a tight lining when the furnace
cools down to operating temperatures in the range of 800
900 C. The lining concept for this type of furnace is shown
in Figure 1.
side one in Figure 1, is removable and attached to the cylin-
drical furnace section using bolts. Several hours after com-
pleting the heat-up process to slag washing temperature, a
customer observed bolt failure. Since such failure implies a
12 day operating downtime, a thermomechanical finite ele-
ment analysis (FEA) was requested by the customer in
order to determine the root cause for this failure and possi-
ble solutions to avoid the issue. As a first step, FEA was
performed to help understand why failure occurred several
hours after the end of the heat-up procedure. A second
question was whether the rapid heat-up procedure
employed was responsible for the damage. An additional
aim of the modelling was to provide guidelines that would
improve the furnace lifetime.

The Thermomechanical Model

A simplified model was set up to perform the thermome-
chanical analysis (Figure 2a). Under the applied boundary
conditions, the model represented the furnace in Figure 2b.

The FEA investigated mechanical stresses occurring during

Figure 1. Lining concept for a lead short rotary drum furnace.
the heat-up procedure, using transient thermal analysis. The
grey planes in Figure 2a are rigid surfaces, enabling the
joints between the bricks and expansion allowances in the
lining to be incorporated into the model. The model slice
was chosen to represent one half of the bricks in the cylin-
drical part of the lining.

(a) (b)

Figure 2. (a) thermomechanical FEA model and (b) furnace represented by this model.

> 59
 RHI Bulletin > 2 > 2013
As discussed in a previous issue of the RHI Bulletin [1], the
thermomechanical behaviour of refractory materials is very
complex and includes temperature dependencies, plasticity,
visco-plasticity, and time-dependent effects like relaxation.
The target of the simulation discussed here was to find the
cause of high stresses and to minimize them. Therefore, a
temperature-dependent linear elastic approach for the
description of the material behaviour was considered suffi-
cient and was chosen knowing that such an assumption
would result in the model predicting much higher stresses
than those expected in reality. However, independent of the
absolute stress levels, minimizing them would reduce the
risk of further failures, even if it is not possible to prove
whether failure would be expected.
In the first set of models, the influence of the following
heat-up procedures was investigated:
>> Slow heat-up in 48.5 hours to 1200 C (heating rate
~ 22 C/hour).
>> Rapid heat-up in 33 hours to 1200 C (heating rate
~ 40 C/hour).
>> Rapid heat-up procedure with holding times used for
refractory monolithics, with a total heat-up time of 58
hours (final heating rate ~ 40 C/hour).
All the heat-up procedures were followed by a 72 hour
dwelling time, at a constant temperature of 1200 C.
Initial Determined Stresses in the Steel Shell
The von Mises stress is a stress calculated according to the
formula below (1) [2], and represents the load on plastic
deformable materials. It was created to provide a scalar
value that can be used to compare the three-dimensional
stress in a structure with the tensile strength of for example
steel.
1 up procedure. When the stresses are compared after 120
sV = ( s1 s2 ) 2 +( s2 s3 ) 2 +( s3 s1 ) 2 (1)
2 procedures. In summary, the models described above were
In this formula the index V indicates the von Mises stress
and the indices 1, 2, and 3 are the three principal stresses.
Figure 3. Von Mises stresses in the steel shell after the 72 hours
holding time at 1200 C, namely the end of the modelled time
frame. Relative high stresses are indicated in red.
60 <
From the formula it is apparent that the von Mises stress
is independent of the mathematical sign of the principal
stresses, implying that tensile stresses (positive sign) and
compressive stresses (negative sign) are treated the same
way. Based on the theory behind the von Mises stress this
is valid for plastic materials like steel. However, brittle
materials like ceramics, concretes, and refractories are sig-
nificantly more sensitive to tensile stresses than to com-
pressive stresses, since the tensile strength of refractory
materials is typically one-tenth of the compressive
strength. Hence the von Mises stress is not appropriate to
describe the failure behaviour of refractory materials,
instead the maximum principal stress, the largest tensile
stress, is typically used in a first approach to evaluate the
risk of crack formation.
The von Mises stresses in the steel shell after the 72 hour
holding time at maximum temperature are shown in Figure 3.
The highest stresses in the steel shell were observed in
the bolts, represented by the red areas. In order to compare
the stresses caused by the three different heat-up proce-
dures, the average stresses in a bolt were plotted over time
(Figure 4). As discussed in the previous section, the abso-
lute values of the stresses should be considered too high.
Therefore, the average von Mises stresses in the bolts are
presented relative to the stress level at the end of the slow
heat-up procedure modelling time.
As shown in Figure 4, prior to the heat-up procedure the
bolts in the model were pretensioned at about 15% of the
final stresses. At the end of each heat-up procedure (58
hour time point on the graph) the stresses were at approxi-
mately 80% of the final values, and continued to increase
for the next 50 hours after the end of the heat-up proce-
dures. Assuming that the stresses at the end of the heat-up
were below but close to the tensile strength of the bolts, the
further stress increases provide an explanation for the
observed bolt failure several hours after the end of the heat-
hours, it is evident that they were almost the same for all
able to explain why failure occurred several hours after the
end of the furnace heat-up and that the rapid heat-up proce-
dure was not responsible for the observed damage.
1400 140
Relative averaged von Mises stress in a bolt [%]
1200 120
Hot face temperature [C]
1000 100
800 80
Temperature slow heat-up
600 Temperature rapid heat-up 60
Temperature rapid heat-up
400 with holds 40
Stress slow heat-up
Stress rapid heat-up
200 Stress rapid heat-up 20
with holds
0 0
0 24 48 72 96 120 144
Time [hours]
Figure 4. Development of the relative von Mises stresses (solid
lines) in a bolt over time during and after the different heat-up
procedures (dashed lines).
 RHI Bulletin > 2 > 2013

Stresses in the Refractory Brick Lining stress-free lining. Furthermore, the unique slag washing
procedure used in this type of furnace results in a very spe-
The observations then raised the question of whether it
cific situation regarding the furnace and refractory lining
would be possible to shorten the heat-up time in order to
design: Not only must it be able to withstand the stresses
minimize furnace downtime and energy consumption.
caused by thermal expansion of the refractory material dur-
However, prior to discussing this point it is necessary to
ing the slag washing procedure at 11001250 C, but a tight
highlight that the model assumed a linear elastic behav-
lining is required after cooling down to operating tempera-
iour of the refractory materials, neglecting relaxation.
tures in the range of 800900 C.
Since the refractory brick relaxation is in part significantly
shorter than the modelled time frame, the comparative
In order to investigate the stresses in the steel shell and
stresses and interpretation of the modelling results are refractory bricks that are expected to occur in these two
valid. temperatures ranges, an additional FEA was performed to
investigate a slow heat-up to 850 C. This simulation indi-
The main reason for a slow furnace heat-up procedure is cated that the stresses after a heat-up to 850 C are about
the requirement to avoid thermomechanical overload of 50% of those generated by the heat-up to 1200 C, high-
the refractory lining bricks. This can result in damage to lighting the challenge regarding furnace design and brick
the brick structure, a reduced furnace lifetime, and in the grade selection for such a procedure.
worst-case scenario in brick spalling during heat-up. In
order to examine the potential risk of the three heat-up
Lining Design to Minimize Potential Failure
procedures causing brick damage, the maximum principal
stresses were modelled for each scenario (Figure 5). To address the final question of how to minimize the risk of
further failures, four different lining designs were
The stresses in Figure 5 are shown at time points during
the three different heat-up procedures when the highest
maximum principal stresses were observed. Those
stresses observed with the rapid heat-up procedure were
about 30% higher than with the slow heat-up schedule.
Therefore, the slower procedure decreases the risk of brick
damage compared to rapid heat-up. The stresses occur-
ring during the procedure with holding times, which
addresses the requirement for drying times in the case of
water-containing refractory monolithics, were in the same
region as those observed with the rapid heat-up without
holding times, indicating that the heat-up rate is the domi-
nant factor creating these stresses.
(a)

Stresses in the Bricks and Steel Shell

So far, two different types of stresses have been discussed
in this paper: Those that are generated within the individ-
ual bricks by the rapid heat-up procedure and those
caused by the interactions between individual parts of the
furnace. The first ones develop because the thermal con-
ductivity of the brick is insufficient to create a quasi-sta-
tionary temperature distribution in the brick that would
result in an almost stress-free state of an individual non-
constrained brick. These stresses are balanced within one
brick. The second type of stresses, for example those in
the bolts, are caused by the constraining effect of the steel (b)

shell on the lining that is trying to expand. These stresses,

which in a global view can be considered as tensile
stresses in the steel shell, are balanced by compressive
stresses at the brick hot face.

While the only possibility to avoid the first type of stresses

is an appropriate selection of the heat-up rate, the second
type is independent of the heat-up procedure. The com-
mon method to minimize the second type of stresses is
introducing expansion joints to provide the refractory
material with additional space for thermal expansion. The
expansion provision required is correlated to the expected
(c)
thermal expansion determined by the brick material prop-
erties and the temperature inside the furnace. Since an
essential point when selecting the appropriate expansion Figure 5. Highest maximum principal stresses occurring in the
bricks at various time points during the three heat-up proce-
allowance is the requirement to create a tight lining at dures: (a) slow heat-up, (b) rapid heat-up, and (c) rapid heat-up
operating temperatures, it is not possible to create a with holding times.

> 61
 RHI Bulletin > 2 > 2013

compared using FEA. One was the standard refractory lin- The modelling showed that while introduction of expansion
ing modelled in the initial analysis that did not include any allowances between the bricks within specific rings (orange
expansion allowances in the endwalls. Two additional mod- line) resulted in minor stress reduction, including them in
els enabled different expansion allowance possibilities in between the rings resulted in a significant decrease in the
the endwall to be investigated: The first involved including stresses (green line). Based on the experience that the fur-
expansion allowances in between the bricks of specific nace failed a number of hours after the end of the heat-up
rings at the endwall while the second introduced expansion procedure at a stress level exceeding 80%, the reduction of
allowances between the specific rings. For reference, a the stresses in the design with the expansion allowances in
fourth model without any expansion allowances in all areas between the rings to approximately 60% at the end of heat-
of the furnace lining was examined. Development of the rel- up and less than 80% multiple hours later infers a signifi-
ative averaged von Mises stresses in a bolt over time for cant reduction of failure risk with this lining design. A more
the four different lining designs is shown in Figure 6. The detailed analysis of stresses in the different lining designs
plotted stresses are relative to the stresses in the standard confirmed compressive stresses in all directions at the lin-
design (blue line) at the end of the modelling period. The ing hot face, indicating that all expansion allowances were
red line shows the stress development that would be closed.
expected without any expansion allowances.
Summary
180 The thermomechanical FEA of a lead short rotary furnace
Relative averaged von Mises stress in a bolt [%]

provided a reasonable explanation for the observed furnace

160 damage, based on the development of stresses in the bolts
140 after the end of the heat-up procedure. The FEA also con-
firmed that stresses in the bolts were independent of the
120 heat-up rate. Nevertheless, a slow heat-up is required in
100 order to avoid high stresses in the lining bricks that could
result in a reduced lining lifetime or brick spalling. Addi-
80
tional FEA revealed that the introduction of expansion
60 n No expansion allowances allowances in between the rings at the endwall should
n Standard reduce the risk of failure.
40 n Expansion allowances
in rings in endwall
20 n Expansion allowances Based on the results of the thermomechanical simulations
between rings in endwall described, the expansion allowances were modified in a
0
customers furnace lining. According to feedback from the
0 24 48 72 96 120 144
Time [hours] customer, this modified design has avoided further endwall
damage and in combination with a slow heat-up procedure
Figure 6. Development of the relative von Mises stresses in a improvements in the lining lifetime have also been
bolt over time for different expansion allowance designs. achieved.

References
[1] Marschall, H.U. Finite Element Simulation of RefractoriesThe Challenge. RHI Bulletin. 2012, No. 2, 4144.
[2] Beitz, W. and Kttner, K.-H.(Eds). Dubbel: Taschenbuch fr den Maschinenbau; Springer Verlag: Berlin, 1990.

Authors
Hans Ulrich Marschall, RHI AG, Technology Center, Leoben, Austria.
Daniel Kreuzer, RHI AG, Industrial Division, Vienna, Austria.
Alfred Spanring, RHI AG, Industrial Division, Vienna, Austria.
Corresponding authors: H
 ans Ulrich Marschall, ulrich.marschall@rhi-ag.com
Daniel Kreuzer, daniel.kreuzer@rhi-ag.com
Alfred Spanring, alfred.spanring@rhi-ag.com

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RHI Bulletin
The Journal of Refractory Innovations
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RHI Bulletin >2>2013
The Journal of Refractory Innovations