130 J SCI IND RES VOL 68 FEBRUARY 2009

Journal of Scientific & Industrial Research

Vol. 68, February 2009, pp.130-134
*Author for correspondence
E-mail: manjit_csr@rediffmail.com
Activation of fluorogypsum for building materials
M Singh* and M Garg
Central Building Research Institute, Roorkee 247 667, India
Received 08 July 2008; revised 20 November 2008; accepted 02 january 2009
Fluorogypsum, a waste product of hydrofluoric acid industry, has been blended with Ca(OH)
2
and chemical additives
followed by fine grinding to give plaster/binder of low consistency, high compressive strength and low water absorption.
Addition of lime sludge waste (15-20%) makes suitable binder for building bricks and plastering works.
Keywords: Building materials, Chemical additives, Compressive strength, Fluorogypsum
Introduction
Fluorogypsum (FG), a waste of hydrofluoric acid
industry, has been studied for use as building material
1-
3
. Water-resistant binding materials
4-7
can be produced
from phosphogypsum, slag, cement, fly ash and lime
sludge. Impurities (fluoride) present in FG may interfere
with setting and strength development of plaster/
building components.
This paper presents characterization of FG to make
high strength binding plaster, effect of various chemical
activators/additives on setting, strength, water
absorption, porosity, etc. of FG plaster, hydration and
microstructure properties of binder, and suitability of
FG plaster for making building bricks and its use in
plastering work.
Materials and Methods
Raw Material
FG sample was collected from M/s Navin Fluorine
Industries, Bhestan, Gujarat. Chemical analysis
8-10
of
FG (Ph, 5.0) gave: fluoride, 1.32; SiO
2
(+insolubles in
HCl), 0.65; Al
2
O
3
+ Fe
2
O
3,
0.65; CaO, 41.19; SO
3
,
56.10; and loss on ignition, 0.61%. Low pH shows
presence of free acidity. Chemical activators of
laboratory grades, sulphates to chloride of alkali and
alkaline earth hydroxides, were used to activate
hydration of fluoroanhydrite. Scanning electron
microscopy (SEM, LEO 438VP) of FG sample (Fig. 1)
shows that majority of crystals in FG are anhedral to
subhedral prismatic interspersed with lath in
agglomerated form. Addition of Ca(OH)
2
(1.0%) to FG
gave a neutral pH (7.0). SEM of activated FG (Fig. 2)
shows gypsum crystals euhedral platy prismatic and lath
shaped without agglomeration and any exotic impurity.
Preparation of Gypsum Binder / Plaster
FG dried at 42 + 2C, was ground in ball mill to a
fineness of 99% passing through 90 sieve. Ground
material was then blended with different chemical
activators (1-3 %) for 1 h in blender / powder mixer to
get a uniform binder for testing and evaluating
11,12
. Water
absorption and porosity of FG plaster was examined by
immersing plaster cubes (2.5 cm x 2.5 cm x 2.5 cm) in
water (curing time 28 days) for a period of 2 h, 8 h and
24 h. Porosity of cubes was evaluated by multiplying
water absorption with bulk density of hydrated plaster.
Lime sludge, obtained from M/s Rashtriya Chemicals
& Fertilizers, Mumbai, has following chemical
composition: P
2
O
5,
2.01; F, 0.12; Na
2
O + K
2
O, 0.026;
organic matter, 0.06; SiO
2
(+insolubles in HCl), 1.50;
CaO, 50.50; Al
2
O
3
+ Fe
2
O
3,
0.026; MgO, 0.64: SO
3,
0.98;
and LOI, 44.50 wt%. Effect of addition of lime sludge
was examined on compressive strength, bulk density,
water absorption and porosity of FG plaster/binder on
cubes (2.5 cm x 2.5 cm x 2.5 cm) having curing time of
3, 7 and 28 days.
Preparation of Bricks
To study effect of sawdust, rice husk, exfoliated
vermiculite etc. on properties of FG binder to get optimum
mix composition for casting bricks, cubes (5 cm x 5 cm x
SINGH & GARG: ACTIVATION OF FLUOROGYPSUM FOR BUILDING MATERIALS 131
5 cm) were cast at workable consistency for measuring
compressive strength, bulk density, water absorption and
porosity. Based on cubes data, bricks (19 cm x 9 cm x 9
cm) were cast by hand molding.
Plastering of Brick Wall
To study suitability of FG binder for internal
plastering, mortars of mix proportions (1:1, 1:2 and 1:3,
by vol) were prepared to plaster burnt brick wall. Mortar
mixes and binder-sand (thickness, 12 mm) were applied
over internal brick wall. Fineness modulus of sand was
kept at 1.91. Brick wall was well watered so that water
in mortar may not be evaporated before mortar was set.
Finish coat of neat binder (3 mm) was applied over
binder-sand under coat (1:2, 9 mm). Plastered patches
were examined for various characteristics after 24 h and
onward.
Results and Discussion
Characterization of Fluorogypsum Plaster
Using (NH
4
)
2
SO
4
activator, setting time of FG plaster
was beyond maximum specified limit (6.0 h) as per
ASTM C 61-50 (Table 1). Compressive strength was also
much less. Using combined chemical activators
[(Ca(OH)
2
:CaCl
2
:Na
2
SO
4
)], setting time got accelerated.
FG binders produced with [(Ca(OH)
2
:CaCl
2
:Na
2
SO
4
)]
possess lower water absorption and porosity than
(NH
4
)
2
SO
4
activator (Table 2).
Effect of Lime Sludge on Fluorogypsum Binder Produced by
Blending Activators
FG binder containing activator
[(Ca(OH)
2
:CaCl
2
:Na
2
SO
4
)] shows (Table 3) an increase
in consistency and decrease in strength values with
addition of lime sludge. However, attainment of strength
is quite high. With increase in addition of lime sludge,
water absorption and porosity increased with
enhancement of immersion period. Thus, FG plaster
may partly be replaced with lime sludge to economize
use of such binder.
Effect of Sawdust, Rice husk and Exfoliated Vermiculite on
Properties of Fluorogypsum Binder
Compressive strength and bulk density (Table 4) were
found higher in case of addition to FG of rice husk than
that of sawdust. However, there was decrease in bulk
density of plaster with increase in sawdust and rice husk.
With increase in vermiculite content (Table 5),
compressive strength and bulk density got reduced.
However, there was an increase in compressive strength
and density values with increase in curing period.
Fig. 1SEM of fluorogypsum
Fig. 2SEM of activated fluorogypsum
Fig. 3Building bricks cast from fluorogypsum binder/plaster

132 J SCI IND RES VOL 68 FEBRUARY 2009
Table 1Effect of chemical activators on the properties of fluorogypsum
Chemical Properties
activators
(by wt.%) Consistency Setting Compressive Bulk density Cold
time strength, MPa g/cm
3
expansion
h %
3 d 7 d 28 d 3 d 7 d 28 d
(NH
4
)
2
SO
4
1.0 24.5 7.0 4.2 9.32 27.7 1.89 1.90 1.92 0.080
2.0 25.7 8.0 4.9 10.3 12.2 1.66 1.95 1.95 0.088
3.0 25.0 8.5 6.0 11.8 12.5 1.88 1.88 1.87 0.070
Ca(OH)
2
CaCl
2
-
Na
2
SO
4
3 0.5 1.5 29.0 1.58 41.9 44.3 45.2 1.93 1.97 2.20 0.060
3 0.5 1.0 32.0 2.20 42.9 44.0 49.9 1.83 1.97 2.08 0.065
3 0.5 0.5 26.0 2.13 36.2 47.8 50.3 1.97 2.08 2.11 0.060
ASTM 61-50 (1981) limits 0.20-6.0 Min.17.0
Max.
IS:2547 (Part-1) 1976 limits 0.5 at 96 hrs.
Table 2Water absorption and porosity of fluorogypsum binders in presence of different chemical activators
Chemical Water absorption, % Porosity
activators
(%) 2h 8h 24h 2h 8h 24h
(NH
4
)
2
SO
4
1.0 8.69 8.69 8.7 16.24 16.3 16.4
2.0 18.72 18.8018.8 34.2 34.2 34.3
3.0 13.70 13.7013.75 26.5 26.5 26.6
Ca(OH)
2
CaCl
2
Na
2
SO
4
3.0 0.5 1.5 4.48 4.48 4.90 9.38 9.38 9.38
3.0 0.5 1.0 5.29 5.29 5.30 10.19 10.19 10.20
3.0 0.5 0.5 3.12 3.12 4.68 6.25 6.25 9.35
Table 3Effect of addition of lime sludge on the properties of fluorogypsum
binder containing Ca(OH)
2
:CaCl
2
:Na
2
SO
4
Lime Consistency Compressive strength Bulk density
sludge % MPa g/cm
3
% 3d 7d 28d 3d 7d 28d
0.0 26.0 36.1 47.8 50.4 1.97 2.08 2.11
5.0 33.7 36.5 40.8 40.0 1.96 2.06 2.00
10.0 34.3 32.6 39.0 41.8 1.93 1.96 2.00
15.0 37.1 30.4 38.0 40.2 1.81 1.85 1.85
20.0 38.5 24.9 32.5 33.5 1.73 1.75 1.87
SINGH & GARG: ACTIVATION OF FLUOROGYPSUM FOR BUILDING MATERIALS 133
Increasing vermiculite content can further reduce density,
but this increased cost of composition. However, at
10.0% addition of vermiculite, adequate strength and
density values are achieved.
Preparation of Full Size Bricks
On the basis of properties obtained by addition of an
optimum quantity of sawdust (10%), rice husk (5%) and
vermiculite (10%) to FG binder, full size bricks (19 cm
x 9 cm x 9 cm) were cast at normal consistency (Fig. 3).
Table 4Effect of saw dust and rice husk on the properties of fluorogypsum binder containing
Ca(OH)
2
:CaCl
2
:Na
2
SO
4
activators
Materials Compressive strength Bulk density
(by Wt. %) MPa g/cm
3
3d 7d 28d 3d 7d 28d
Saw dust
5.0 8.0 19.1 24.5 1.81 1.82 1.82
10.0 6.26 11.2 16.4 1.60 1.65 1.66
Rice husk
5 .0 8.42 10.6 11.0 1.77 1.86 1.87
7.5 4.30 4.91 7.6 1.64 1.71 1.75
10.0 1.83 1.92 2.40 1.52 1.60 1.52
Table 5Effect of exfoliated vermiculite on the properties of fluorogypsum binder containing
Ca(OH)
2
:CaCl
2
:Na
2
SO
4
activators
Vermiculite Compressive strength Bulk density
(by Wt. %) MPa g/cm
3
3d 7d 28d 3d 7d 28d
5 .0 17.98 23.11 29.28 1.95 2.08 2.12
7.5 17.86 22.53 26.07 1.85 1.92 1.95
10.0 17.67 19.30 20.00 1.82 1.85 1.87
15.0 16.36 18.13 18.63 1.75 1.76 1.85
Table 6Properties of bricks produced by admixing saw dust, rice husk and vermiculite with
fluorogypsum binder
Property Bricks
Saw dust Rice husk Vermiculite
Physical state Sharp edges, corners Sharp edges, corners Sharp edges, corners
Compressive strength, MPa
7days 4.27 6.36 11.5
28 days 10.84 6.60 12.0
Bulk density, g/cm
3
7days 1.16 1.17 1.81
28days 1.16 1.16 1.87
Water absorption, %
7days 16.0 19.2 18.2
28days 18.0 20.0 19.8
Efflorescence Slight Slight Slight
134 J SCI IND RES VOL 68 FEBRUARY 2009
These bricks were tested
13,14
for physical appearance,
compressive strength, water absorption and
efflorescence (Table 6)
Suitaility of Fluorogypsum Binder in Plastering
Plastered patches, examined for various
characteristics after 24 h and onward, developed
adequate strength and hardness. Plaster texture was
smooth, hard and showed good adhesion with bricks.
Cost of FG binder/plaster of a plant (capacity, 1000
tonnes per day) in three shifts has been estimated to be
Rs 1800/-per tonne taking cost of FG at Rs 500 / tonnes.
Conclusions
High strength plaster can be developed from FG
waste. A mixture of chemical activators l[Ca(OH)
2
,
CaCl
2
and Na
2
SO
4
] has been found strengthening
compound to convert waste anhydrite into strong gypsum
matrix at faster pace. Addition of lime sludge (15-20%)
to binder can economize production of FG plaster
without sacrificing strength. adding an optimum quantity
of sawdust (10%), rice husk (5%) or exfoliated
vermiculite (15-20%) to FG binder can produce building
bricks. FG, on admixing with river sand, lime sludge
and exfoliated vermiculite (in optimum proportion) is
suitable for plastering (finish & undercoat) over internal
brick wall.
References
1 Singh M, From Waste to Wealth- Developing Potential
Construction Materials from Industrial Wastes, edited by P C
Trivedi (Avishkar Publishers & Distributers, Jaipur) 2006, 36-
62.
2 Taneja C A et al, Supersulphated cement from waste anhydrite,
Res Ind, 19 (1974)51-52.
3 Swanski A, Fluorogypsum binder, Chem Abstr, 98 (1983)
16603.
4 Gnyra B & Aitcin P C, Preparation from waste fluoroanhydrite
of cementitious powders suitable for casting into dense and /
or foamed anhydrite panels, Chem Abstr, 95 (1981) 137299.
5 Singh M & Garg M, Gypsum binders and fibre reinforced
gypsum products, Indian Concr J, 8 (1989) 387-392.
6 Singh M & Garg M, Investigations of a durable gypsum binder
for building materials, Constr Bld Mater, 6 (1992) 52-56.
7 Valentini G & Santaro L, Hydration of granulated blast furnace
slag in the presence of phospho-gypsum, Thermichemica Acta,
78 (1984) 101-112.
8 IS: 1288-1983, Specification for methods of chemical analysis
of mineral gypsum, (Bureau of Indian Standards, New Delhi)
1983.
9 Scott W W & Furman N H, Standard Methods of Chemical
Analysis, vol 1, 5th edn (Lond) 1952, 214-216.
10 Vogel A I, A Text Book of Quantitative Inorganic Analysis, 3
rd
edn (Longmans & Green Co, Lond) 1960, 575.
11 IS: 2542 (Part 1) -1978, Methods of test for gypsum building
plaster, excluding premixed plaster (Bureau of Indian
Standards, New Delhi) 1978.
12 ASTM C 61-50, Specification for Keene cement, 1990.
13 IS: 3495 (Part 1)-1976, Methods of Test for Burnt Clay Building
Bricks: Parts 1 & 2, Determination of compressive strength
and Water absorption (Bureau of Indian Standards, New Delhi)
1976.
14 IS: 12894-1990, Specifications for Fly ash-Lime Bricks,
(Bureau of Indian Standards, New Delhi) 1990.