SELF-COMPACTING CEMENTITIOUS SYSTEMS INCORPORATING

MARBLE POWDER, FLY ASH AND SILICA FUME

Syed Ali Rizwan (1),Hafiz Farhan Iqbal (2), Jaleel-ur-Rehman (2) and Thomas A.Bier(3)
(1)

Professor of Civil Engineering and HoD Structural Engineering Department, NICE(NUST)

H-12, Islamabad. Member ACI Committees 237,234 and 232. Email: syedalirizwan@hotmail.com
(2)

Professional Engineer NESPAK Pvt. Limited Email: farhan.iqbal@engineer.com

(2)

Professional Engineer NESPAK Pvt. Limited Email: jaleel.rehamn@engineer.com

(3)

Chair Construction Materials Technology, IKGB, TU Freiberg. Germany Email:

thomas.bier@ikgb.tu-freiberg.de
Abstract
Self-Compacting Cementitious Systems (SCCS) fall in the realm of modern concrete
technology which has been used effectively all over the world. Such systems offer uniform
compaction and therefore uniform durability and are characterized by higher powder content
with lower w/p ratio compared with the conventional concrete.
Effect of Marble Powder, Fly Ash and Silica Fume as cement replacement on response of
self-compacting cement paste systems was studied with a view to study their suitability for
making SCC locally and to encourage use of recycled industrial byproducts like inert marble
powder resulting in environment friendliness, economy and ease of placements. Water
demand, super-plasticizer demand, setting times and strength tests on self-compacting paste
systems (SCP) were conducted in addition to scanning electron microscopy (SEM) to study
the hydration products.
It can be stated that the SRMs investigated in this research program can be used in Pakistan as
cement replacement successfully in self-compacting concrete systems as these seem to
improve certain properties of such systems.
Keywords:
Self-Compacting Cementitious Systems, Self-Compacting Paste System, Secondary Raw
Materials, Scanning Electron Microscopy (SEM)
RESEARCH SIGNIFICANCE
Pakistan is faced with huge electricity shortfalls for the last two decades. So the efforts should
be made in every field to conserve energy. In construction industry we can do so my using

less clinker with SRMs as partial cement substitutes while making concrete so that
environmental related issues are also addressed. This research focuses on the fresh and
hardened state properties of self-compacting cementitious systems (SCCS) using different
SRMs.
1. INTRODUCTION
Pozzolanic and inert materials have been used in cement industry since two decades to
improve the response of self-compacting cementitious systems (SCCS) [1]. Use of secondary
raw materials (SRMs) like marble powder (MP), fly ash (FA) and silica fume (SF) are
increasingly used as partial cement replacement for the construction and repair of civil and
military infrastructure using sustainable SCC wherein mineral and chemical admixtures are
used to obtain superior concrete performance. The reduction in quantity of Portland cement
used in cementitious matrix decreases energy consumption and
emissions. The use of
mineral admixtures also improves the durability of cementitious systems [2].
Marble powder (MP) is a waste product of the marble industry. During the cutting and sawing
process of the marble, MP is produced. Disposal of this very fine material is a big problem as
it causes environmental related issues. It is estimated that millions of tons of MP is being
produced by the marble industry all over the world [3]. MP is non pozzolanic and inert filler
and is sometimes termed as marble dust. It has been reported that MP has properties like
limestone and it participates in early hydration reaction through physical filler and chemical
nucleation effects.
Fly ash is the most commonly used SRM in HPC /SCC and is a bye-product of coal
combustion in thermal power plants. During the combustion process the mineral impurities
are separated and carried away with exhaust gases which get solidified into glassy circular
particles which are then collected using electrical precipitators. The quality and size of FA
particles are greatly dependent on the quality and type of coal, operation and process of the
thermal power plant [4]. FA contains silica, alumina, iron oxide and calcium oxide as main
constituents. ASTM C 618 classifies FA as class C and F. If the sum of three oxides is
greater than 50 %, then it is called class C FA. Class F FA has this sum as more than
70%.
Silica Fumes (SF) or micro silica is produced as a by-product of smelting process i.e.
production of silicon metal and Ferro-silicon alloys. Its use started in the concrete industry
after being identified as potential health and environment hazard due to stringent enforcement
of environmental laws in Scandinavian countries. Production of SF involves reduction of
quartz in electric arc furnace at temperature greater than 2000 C. Due to very small particle
size, it has very high specific surface area (15,000-25,000 m2/kg).The pozzolanic effect of
silica fume mainly depends on the amount of silica which in turn depends on the type of alloy
being produced [2]. The strength of SCC systems incorporating SF increases due to both
pozzolanic and filler effect of SF.SF is usually added to replace a part of cement. Despite
dilution, Pozzolanic effect due to the reaction between and calcium hydroxide and silica in
addition to physical filler and presence of nucleation sites are the effects produced during
hydration. Usually powdered SF around 10% cement replacement improves concrete
performance. SF has a pronounced effect on hydration kinetics [5].

2. EXPERIMENTAL PROGRAM
2.1 Materials and Formulations
Materials used in this research included local ordinary Portland cement type I (OPC), grade
43 as per ASTM standard C150-04 and marble powder from local marble industry of
Islamabad. Silica fume (SF) which was imported from RW-Fuller Silicium GmbH Germany
and Fly Ash (FA) was also imported from Germany. Third generation Superplasticizer
Melflux from BASF Germany was used for producing requisite flow determined by
Hagemans mini slump cone. Chemical composition of these powders is shown in Table 1.
Table 1.Physical and chemical analysis (in terms of per cent) of powders used.
Parameters

CEM 1

MP

FA

SF

Particle Size (micron)

15.41

8.922

26.56

8.66*

Silicon dioxide

18.23

2.93

51.44

95

Aluminum Oxide

4.36

26.13

0.2

Ferric Oxide

3.53

5.55

0.05

Calcium Oxide

66.67

94.34

4.03

0.25

Magnesium Oxide

3.15

2.73

2.51

0.4

Sulfur trioxide

2.42

1.89

Sodium Oxide

1.23

0.1

1.64

2.63

1.2

Chemical Analysis
(Per cent)

Potassium Oxide
*

This is the size of primary group of agglomerates of SF particles

Marble Powder from different sources was brought and was analyzed physically by visual
inspection for the color and fineness. Some samples were having some impurities and a
blackish color. Analyses showed that these samples had some impurities most probably
remains of iron oxides. Finally MP from Islamabad marble industry was selected as it fulfilled
the requirements. The color of this sample was white and free from impurities like iron oxide.
Referring to Table 1, LOI of MP due to calcination is not included which is nearly 40%.
Four formulations were tested in this study including C-O, C-MP-10%, C-FA-10%
and C-SF-10%.The code of this formulation can be comprehended as the first alphabet refers
to cement, the second is for SRM. In first formulation O represents Ordinary Portland
Cement or neat cement paste. The number 10% indicates the amount of SRM that was
added.
3. RESULTS AND DISCUSSION
3.1 Particle characterization

It is perhaps the most vital process in making HPC/SCC as it helps explain various results
of SCC in fresh and hardened states simply on the basis of physical interpretations suited to
civil /construction engineers. It has been reported in the literature that powder particles shape,
size and morphology affect the properties like water demand, setting times and super
plasticizer content. [6, 7]

Fig.1 SF (Rizwan S.A 2006)

Fig.2 FA (Rizwan S.A 2006)

The Particle shape of FA and SF is circular. MP particles have irregular and edgy shape and it
shows a high internal friction during flow. SF particles are of submicron size as seen in SEM
picture. SF particles are inter-wound to form primary agglomerates due possibly to the
presence of some electrical bonds.
3.2 Water demand
The WD of all the formulations was found out according to ASTM C187 using Vicat
apparatus. The results of WD of different formulations are shown in fig.3. Maximum WD
is shown by C-SF-10% which necessitates in depth study of this SRM.

Water Demand (WD)%

C-0

C-MP-10%

C-FA-10%

C-SF-10%

40%
30%
20%
10%
0%
C-0

C-MP-10%

C-FA-10%

C-SF-10%

Fig.3 WD of Different Formulations

A very sticky paste was observed for C-SF-10%. Very fine particle size and hence greater
surface area is instrumental for a higher WD of concrete containing SF [8]. Amorphous nature
of SF is also responsible for increased water demand.
Excessive addition of fine SRM particles results in increase in Specific surface area of the
binder phase which ultimately increases the water demand of the system. FA showed a
comparatively lower WD which can be attributed to its larger particle size, hollow circular
particle shape and glassy surface so it has a less affinity for water.
3.3 Setting Times
The effect of SP on setting times was also studied and reported. For this purpose
setting times with super plasticizer and without super plasticizer at WD were determined. The
results of this study are shown in Fig.4 and Fig.5.

Setting Times Without SP At WD

Final Setting Time

250
200
150
100
50
0

Initial Setting Time

Final Setting Time

450
Time (minutes)

Time (minutes)

Initial Setting Time

Setting Times With SP At WD

400
350
300

C-0

C-MP-10% C-FA-10% C-SF-10%

Fig.4 (Setting Times without SP at WD)

C-0

C-MP-10% C-FA-10% C-SF-10%

Fig.5 (Setting Times With SP at WD)

Formulation having 10% MP accelerated the setting time of the SCP system [9]. FA has
been known to retard to hydration of the system and hence the setting times are delayed. It has
been reported in the literature that FA acts as Calcium sink in the sense that it removes C
ions and this reduces the concentration of Ca+ ions in the early hours and delays the
crystallization of CH and CSH hence retarding possibly the C3S hydration [10]. SF on the
other hand has shown acceleration in setting times. The reason associated with this
acceleration may be that during first few minutes release of C and alkali ions from cement
particles is rapid, the reduction in C in the solution increases the rate of release and amount
of heat evolution giving accelerated hydration [10,11]. Moreover it seems to uptake water.
Usually most of SPs are known to retard the setting times. The level of retardation depends
upon type of cement, temperature and the type of SP itself. It is reported that SP generally
retard the conversion of ettringite to monosulfate. The retardation effect of ettringitemay
be caused by the adsorption of the SP on the hydrating
surface [12].
3.4 Flow Tests

Plasticizer Content(% of Cement Mass)

Flow tests were conducted to find out the required dose of SP for targeted flow of
1 cm.
These tests were performed at WD for all the investigated SCP systems and at W/C of 40%
and 50% as well. SF required a highest dose of SP because of its extremely high surface area
and due to peculiar nature of its particles. It is also reported that because of very fine nature of
SF it reduces the size of the flow channels by occupying the empty spaces and hence increase
the contact points between solid particles resulting in more cohesive paste [13]. From the
following graph it can also be deduced that as we increase the W/C ratio the doze of SP
reduces to achieve the target flow. But overall, the demand of SP mainly depends on the
shape, size, surface morphology and internal porosity of the SRMs being used. Because of
circular nature of the hollow glassy hydrophilic FA particles, the amount of SP is low to
achieve target flow.
Required SP Dose for Different
W/C
C-O

0.3

C-MP10%

0.2

C-FA-10%
C-SF-10%

0.1
0
W/D

40%

50%

Mixing water (% of Cement Mass )

Fig. 6 Required SP Dose for Different W/C

Fig.7 (Rizwan S.A 2006)

It is reported in the literature that SCC systems should have the water content equal to WD of
the system which is the divorcing water content below which system is uneconomical and
adds negative effect on the system and water content above WD affect the strength and
durability adversely. Rizwan S.A [4] reported that it is not the only cement grains upon which
SP is grafted but SP seems to be adsorbed on the surface of powders also, the content of SP
depends upon the shape, size, texture and internal voids or fissures. The partial MIP diagram
for various SRMs is presented. Fig 8 shows the Partial MIP diagram wherein SF has a very
small internal pore size with high mercury intruded volume. The question may arise where
does this water/SP go? On the other hand, FA has the largest maximum pore size.
It is considered that high pore size of powder with low mercury intruded volume will need
small amount of SP for the target flow as nearly all of the SP will be available in solution for
dispersion purpose.

Fig.8

Fig.9

Fig. 8 & Fig.9 (Partial & Cumulative SRMs Porosimetry curves (Rizwan S.A 2006))
SEM studies shows that FA has hollow particles and has small circular voids in the walls. So
FA would require minimum SP content because all of the SP would be available for the
dispersion of the cement grains.
3.5 Strength
Compressive strength tests were performed on the broken samples in the flexural test.
Results are shown in fig.10 Formulation with Marble powder showed overall decrease in
strength gain rate as compared to cement control formulation but early age strength was
significant when compared with fly ash. It is well conversant with the published results in the
past.

Compressive Strength (MPa)

Compressive Strength (MPa) at WD

1 day strength

3days strength

28 days strength

56 days Strength

7 days strength

100
80
60
40
20
0
Formulation : Formulation : Formulation : Formulation :
C-O
C-MP-10%
C-FA-10%
C-SF-10%

Fig.10 Compressive Strength (MPa) at WD

MP shows filler behavior and acts as nucleation site and accelerates the hydration of
clinkers phases mainly of
and improvement in early strength was reported [14].MP if
used alone reduces the setting times and decreases the strength when it replaced a part of
cement. It has been reported that blends of MP and FA improves the strength and overall

response of the system.[15]. Silica fume showed an overall increase in strength as compared
to all others formulations both at early and later ages. It has been reported that replacement of
10% SF gave a greater compressive strengths at all ages [16]. SF has very fine particles, at
early ages it provides filler effect and due to its very fine size and amorphous nature it is very
reactive so it has pozzolanic activity as well which contributes in later age strength
development. In case of Fly Ash rate of strength gain is low at early age but long term
compressive strength (28 days and beyond) is significant.
3.6 Microstructure (Hydration Products)
Microstructure of the SCP system was studied for hydration products using SEM technique.

Fig. 11 SEM of C-O at 3 days

showing Portlandite and Ettringite

Fig. 12 SEM of C-MP-10% at 1

days showing Portlandite

Fig. 13 SEM of C-FA-10% at 3

days showing Portlandite and
Ettringite crystals

Fig. 14 SEM of C-FA-10% at 1 day

showing production of hydration
products on the FA particles.

Fig. 15 SEM of C-SF-10% at 3 day Fig. 16 SEM of C-SF-10% at 1 day

showing CSH gel and ettringite.
showing CSH gel and ettringite
All formulations exhibited the growth of ettringite in the form of needle like cubic crystals,
calcium hydroxides large hexagonal crystals and the calcium silicate hydrate gel which does
not possesses a well-defined crystalline structure. The growth of crystals corresponds to the
specified ages in the images. It is clear from the figures that at day 3 the crystals of ettringite
are more clear and strong. From the figures it is clear that formulation of SF does not have
calcium hydroxide crystals. It only has CSH gel and ettringite crystals. A more dense
structure is formed when SF is incorporated. In fig. 11 and fig. 13 growth of calcium
hydroxide is in layer form and that it can be sheared so it can reduce the strength of the
system.
4. CONCLUDING REMARKS
When SRMs are added as cement replacement then dilution, physical filler effect,
nucleation effect and pozzolanic effects are exhibited depending upon the type of SRM,
packing of the aggregate and binder phases, amount of effective water available. The
inclusion of SRMs changes the response of self-compacting cementitious systems in both
fresh and hardened states. Marble powder (MP) more or less behaves as limestone powder
especially at lower contents. Class F fly-ash (FA) when incorporated as cement
replacement gives enhanced strengths beyond the age of 28 days. Silica fume gives
enhanced strengths both in early and long terms but this SRM needs special investigation.
5. ACKNOWLEDGEMENTS
We express our gratitude and sincere thanks to the laboratory staff of different schools of
NUST.
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