CHAPTER-1

INTRODUCTION

1.1 DEFINITION:
Concrete as is well known heterogeneous mix of cement, water and aggregates.
The admixtures may be added in concrete in order to enhance some of the properties
desired specially. In its simplest form, concrete is a mixture of paste and aggregates.
The growth in infrastructure sector leads to scarcity of cement because of which the
cost of cement increased incrementally. In India, demand for cement is more. Due to
this construction cost of the structure increases.

In today’s world, there is an ever-increasing demand for construction due to

population expansion and shortage of building materials. The growth in infrastructure
sector led to scarcity of cement because of which the cost of cement increased incre-
mentally. In India, the cost of cement during 1995 was around Rs. 1.25/kg and in now
day 2014 the price increased approximately six times and increasing day to day. De-
mand of cement is more. Due to this construction cost of the structure increases.

In order to overcome the scarcity of cement and decrease the cost of concrete
under these circumstances the use of solid wastes, agricultural wastes, and industrial
by-products like fly ash, blast furnace slag, silica fume, rise husk, phosphogypsum,
etc. came into use. Utilization of industrial waste such as phosphogypsum not only
solves environmental problems but also provides a new resource for construction in-
dustry.

Phosphogypsum (PG) is a waste by-product from the processing of phosphate

rock by the “wet acid method” of fertiliser production, which currently accounts for
over 90% of phosphoric acid production. World phosphogypsum production is vari-

1
ously estimated to be around 100-280 Mt per year. The phosphate industry is also an
important contributor to national economies in many developing countries.
The mineralogical composition of phosphate ore, as described by various re-
searchers is dominated by fluorapatite [Ca10F2(PO4)6·CaCO3], goethite and quartz,
with minor amounts of Al-phosphates, anatase, magnetite, monazite and barite. Heavy
metals and trace elements such as cadmium (Cd) and nickel (Ni) are also detected.
Phosphate ores are naturally highly radioactive and their radioactivity originates main-
ly from 238U and 232Th.

In order to produce phosphoric acid, phosphate ore is processed either by dry

thermal or wet acid methods. The dry thermal method produces element phosphorus
using an electric arc furnace. The wet chemical phosphoric acid treatment process, or
“wet process”, is widely used to produce phosphoric acid and calcium sulphate –
mainly in dihydrate form (CaSO4.2H2O)
Ca5F(PO4)3 + 5H2SO4 + 10H2O → 3H3PO4 + 5CaSO4.2H2O + HF

In India, in excess of 10 million huge amounts of waste gypsum at the bit of

phosphogypsum, flourogypsum, etc., are being made yearly. Phosphogypsum is a
subordinate in the wet philosophy for age of phosphoric ruinous (ammonium pho
phate fecal matter) using the improvement of sulphuric dangerous at the stone pho
phate. It is passed on by the use of several systems related to di hydrate, hemihydrates
or anhydrite methods. In India the general masses of phosphogypsum is made through
utilizing the utilization of the di-hydrate structure because of its simplicity in errand
and lower upkeep in assessment to earth shattering strategies. The elective wellsprings
of phosphogypsum are through-eventual outcomes of hydrofluoric dangerous and bo-
ric damaging associations.

There are unquestionable methodology for accumulating of phosphoric ruious,

particularly the di-hydrate machine and the hemihydrate system. Total of di-hydrate
and hemi-hydrate procedures is likewise utilized for time of phosphoric damaging to

2
obtain increasingly raised measure of P2O5 recuperation. In India the general masses
of phosphogypsum is passed on through the di-hydrate gadget.

A) Di-hydrate method (DH):

This fuses reaction among floor shake phosphate and sulphuric ruinous under-
neath 80°C, in each a solitary or multi tank reactor structure. Thing dangerous of 26-
32 rate fixation (as P2O5) is sifted from the gypsum important stones. The channel
cake is exhibited to counter present day washing with water on the channel and inca-
pacitate ruinous so verified is indeed to the reactor. The phosphoric dangerous from
the channel is routinely vanished to around 40 % in a particular degree. In the event
that 54 % P2O5 ruinous is required, likewise vanishing is fundamental. The eye of
damaging depletes remarkable centrality. So in like manner at some phase in certifica-
tion, cycle 70-80 percent of fluorine present in the ruinous is discharged this is recu-
perated as hydrofluosilicic damaging (H2SiF6). Hydrofluosilicic dangerous can be uti-
lized to make cryolite, AIF3 or emerge fluorine mixes.

The basic central purposes of the unmarried-degree di-hydrate approach are

identified with flexibility and unwavering quality parts. Inside the di-hydrate tech-
nique additional soaked quality is worthy inside the phosphate feed, and there might
be continuously noteworthy flexibility to the use of powerless sulphuric damaging, for
the reason that the general water unwavering quality inside the contraption isn't so
fundamental.

The di-hydrate strategy other than has additional adaptability with secure to
shake phosphate stunning in any case, it could reason for fact be a consequence of the
way that, the di-hydrate philosophy to-date being the most uncommon gotten contrap-
tion, progressively perceptible strolling revel in has been assembled with severa shake
types than for explicit methodology. Inside the di-hydrate course, the working temper-
atures are low and the start up and shutdown are faultless and require the most unim-
portant operational aptitudes. The P2O5 revamping generally speaking execution is 94-

3
96 percent. A colossal fragment of the greenery inside the district have watched di-
hydrate method.

Di-hydrate approach remains the most fundamental as a result of its low capital
cost, low running temperatures and flexibility of activity. Headway gained in ground
phosphoric ruinous were attempting to get filterable gypsum significant stones, lower
P2O5 fiascos and thing damaging of better side interest. The di-hydrate method expe-
riences as a substitute low P2O5 recouping and coffee noteworthiness of ruinous.

B) Hemi-hydrate gadget (HH):

This wires the response among shake phosphate and sulphuric damaging above
eighty°C. Unequivocal strolling conditions are kept up to set calcium sulfate hemi-
hydrate, in zone of the di-hydrate structure. The unmarried degree hemi-hydrate ma-
chine makes a response slurry which, while detached, passes on right now a phosphor-
ic dangerous manufactured from 40-52% P2O5 fervor with broad cash related mone-
tary spare resources in impact necessities. In the wake of washing the get out cake to
dispose of further P2O5, weaken ruinous is again to the response sort out. P2O5 fixing
execution is lower than di-hydrate technique at 90-94 rate. The unrecovered P2O5 is
held in phosphogypsum hemihydrate and as a quit outcome its trade or use can be a
trouble.

The methodology is definitely not hard to perform and may utilize coarse
shake. The favors of this method are lower capital regard, high flawlessness and
thought than di-hydrate device and utilization of a ton coarser shake. A segment of the
dangers of thusly are: hemi-hydrate slurry are difficult to get out because of reality the
important stones are humbler and out and out less particularly limited curiously with
the di-hydrate, better P2O5 occurrences, breaking down of occupies and mechanical
get together in context on development at better temperature and higher damaging in-
terest, etc.

4
 Fig 1.1: manufacturing process of phosphoric acid and output waste gyp-
sum stack

The wet process is economic but generates a large amount of phosphogypsum.

The nature and characteristics of the resulting phosphogypsum are strongly influenced
by the phosphate ore composition and quality. Phosphogypsum is mainly
CaSO4·2H2O but also contains impurities such as H3PO4, Ca(H2PO4)2.H2O, Ca-
HPO4.2H2O and Ca3(PO4)2, residual acids, fluorides (NaF, Na2SiF6, Na3AlF6,
Na3FeF6 and CaF2), sulphate ions, trace metals (e.g. Cr, Cu, Zn and Cd), and organic
matter as aliphatic compounds of carbonic acids, amines and ketones, adhered to the
surface of the gypsum crystals. Furthermore, wet processing causes the selective sepa-
ration and concentration of naturally occurring radium (Ra), uranium (U) and thorium
226
(Th): about 80% of Ra is concentrated in phosphogypsum while nearly 86% of U
and 70% of Th end up in the phosphoric acid.

Only 15% of world phosphogypsum production is recycled as building materi-

als, agricultural fertilisers or soil stabilisation amendments and as set controller in the
manufacture of Portland cement. The remaining 85% is disposed of without any
treatment. This by-product is usually dumped in large stockpiles exposed to weather-

5
ing processes, occupying considerable land areas and causing serious environmental
damage (chemical and radioactive contamination), particularly in coastal regions.

Fig 1.2: Phosphogypsum

Calcium sulfate can be either in dihydrate (CaSO4.2HO) or hemihydrate

(CaSO4.0.5H2O) form depending on there action temperature used to produce phos-
phoric acid. Usually free moisture content between 25-30% exists in the gypsum cake
after filtration. The generated hemihydrate form of phosphogypsum, in the presence of
free water can rapidly convert to dehydrate form. Moreover, if the process is left un-
disturbed it will set up into a relatively hard cemented mass. Di-hydrate consists prin-
cipally silt-size (<0.075mm) and appear as soft aggregates of crystals. It depends on
the source of the phosphate rock and the reactor conditions. Phosphogypsum consists
mainly calcium sulphate dehydrate with small amount of silica. X-ray Diffraction pat-
tern of obtained phosphogypsum is given in Fig. 1.3 indicating the material mainly
composed of Gypsum.

6
Fig 1.3: X-ray Diffraction pattern of the Phosphogypsum sample

7
1.2 OBJECTIVES

 Modifying the properties of the concrete and controlling the concrete produc-
tion cost.

 To overcome the scarcity of cement and also the advantageous disposal of in-
dustrial wastes.

 The use of phosphogypsum as a stabilization material reduces drying shrink-

age. A mixture prepared with 25% phosphogypsum seems to give the lowest
shrinkage values.

 Phosphogypsum has been used in the cement industry as a setting regulator in

place of natural gypsum and in the gypsum industry to make gypsum plaster.

 Phosphogypsum presence in the cement increases its initial strength rapidly.

 Heated phosphogypsum used as a binder, improved the compressive and flex-

ure strength of the material.

 Phosphogypsum also used as fertilizer in agricultural industry.

8
 CHAPTER-2

LITERATURE REVIEW

2.1 T. Siva Sankar Reddy:

This research deals with the experimental investigation on compressive tensile
and flexural strength characteristics of partially cement replaced phosphogypsum con-
crete using 0%, 10%, 20% replacement with different water binder ratio 0.40, 0.45,
0.50. The strength characteristics are studied by casting and testing a cube for 7, 28
days. It is shown that the part of Portland cement can be replaced with phosphogyp-
sum to develop well and harden concrete to achieve economy. Experimental investiga-
tion shows that on replacement of cement by phosphogypsum by 10% gives compres-
sive strength 49.3 N/mm2 at 28th day of curing. Author found that the compressive
strength at 7th day increased significantly around 20% at water binder ratio 0.5 and
marginally around 10% increase of the water binder ratio. The split tensile strength at
28th day increased marginally around 3 to 10 % at different water binder ratio.

2.2 S. S. Bhadauria, Rajiv Gandhi, Rajesh B. Thakare:

This research deals with the mixture in which cement replaced with 5% phos-
phogypsum having almost same standards or normal consistency than that of plain
cement. The cast specimen with concrete mixes mentioned and cured for 28 days in
the laboratory on completion of curing period and specimen were taken out and tested
for compressive strength. Concrete mix For M20 grade compressive strength was
19.00N/mm² at 28th day of curing for 5% replacement and for 15% replacement it
was 14.00N/mm².for mix design M25 for 5% replacement compressive strength was
found 26.40N/mm2 at 28th day of curing while for 20% replacement compressive
strength was 13.00N/mm2.Hence there is constant increase in compressive strength of
concrete containing five percent of phosphogypsum as compared to conventional con-
crete. Further increase in phosphogypsum content causes decrease in compressive
strength, but rate is slow as compared with previous mix.

9
2.3 Mahesh A. Bagade, S. R. Satone (July, 2012):
This research deals with cement replaced with phosphogypsum concrete using
10%, 15%, 20% with replace water binder ratio of 0.40. The part ordinary Portland
cement can be replaced with phosphogypsum to develop good and hardened concrete
to achieve economy. Phosphogypsum in ordinary Portland cement mixes considerably
retards setting time but does not contribute to produce unsound cement paste. The
compressive strength of phosphogypsum cement concrete with 5% and 10% are im-
prove it indicates phosphogypsum concrete used in mass concrete work.

2.4 S. Deepak, c. Ramesh (March, 2016):

This research deals with the effect of replacing 10%, 20%, replacement of ce-
ment by phosphogypsum at two different water cement ratio (0.4 and 0.5) on strength
characteristic namely split tensile strength and flexural test of beam goes increasing 28
days.

2.5 Koduru. Srinivasalu (March 2017):

This research deals with experimental investigation on durability characteristic
of hardened concrete, compressive strength. The study aims to determine the optimum
amount of phosphogypsum can give maximum strength of concrete. The experiment
consists of testing concrete using 0%, 2.5%, 5%, 7.5%, 10% replacement of phos-
phogypsum for M20, M25, M30 grade of concrete. It is observed that cement can be
replaced by phosphogypsum to develop too good and hardened concrete to achieve
economy.
In recent years, a great deal of researchers devoted themselves to the utilization
of PG and have gained positive results. Sunil Kumar utilized PG as raw material for
manufacturing of hollow blocks. Shen et al. prepared a new type of lime– fly ash–
phosphogypsum binder to improve the performances of lime–fly ash binder, the PG
content was 18–23%.

10
2.6 Degirmenci (2012):
This research investigates that the utilization of PG was divided into two as-
pects, one was used as raw material directly, and the other was calcined. PG can be
used for preparing binder, building block, and so on, however, the report of utilization
of PG for manufacturing non-autoclaved aerated concrete is little known.

2.7 Roy, Kalvakaalava and Seals (1996):

This research deals with micro structural and phase characteristics of phos-
phogypsum cement mixtures. The effect of tricalcium aluminate (C3A) content of the
stabilizing cement (with two different C3A percentage), curing time (7, 28, 45 and 90
days), proportion of phosphogypsum (5% to 60%), grain size, impurities in phos-
phogypsum on microstructure (SEM) and phase properties of mix was studied. Deriv-
ative Thermo gravitimetric Analysis (DTA) was used in this study for hydrated prod-
ucts of these mixes. The study was concluded the addition of phosphogypsum to Port-
land cement produced large amount of ettringite. Phosphogypsum increased the de-
gree of hydration of cement in the mixtures in the long term. The amount of carbona-
tion in phosphogypsum based mixture was found relatively low.

2.8 Yun Yan (2013):

In order to make clear the role of phosphogypsum in cement– PG–slag–lime
system, the following scheme was established: kept the proportion of cement–slag–
lime invariant, added phosphogypsum whose content was 0–50% multiply by the total
amount of cement, slag and lime, at the same time, the ratio of water to raw materials
was also consistent. Effect of phosphogypsum content from 0% to 10% on compres-
sive strength increases, however, when phosphogypsum content exceeds 10% it de-
creases. This shows that a part of phosphogypsum plays the role of activator in the
system, besides; redundant phosphogypsum plays the role of filler. When phos-
phogypsum content exceeds 10%, the compressive strength goes down due to the rela-
tive volume of binder reduce with phosphogypsum content increasing.

11
2.9 Lin Yang, Zhihua Hu (2013):
Phosphogypsum (PG) was used as raw material for the preparation of non-
autoclaved aerated concrete, a series of technological parameters, such as water to sol-
id ratio (W/S), quick lime content, steam temperature, and chemical activators, were
investigated based on the density and compressive strength of specimens in this paper
and the performances of products were also tested. The optimal mix proportion for
preparing PG non-autoclaved aerated concrete (about 700 kg/m3) is as follows: ce-
ment 15%, Ground Granulated Blast Furnace Slag (GGBFS) 30%, PG 55%, quick
lime 7%, Na2SO4 1.6%, aluminium powder 0.074%, W/S 0.45. The best steam tem-
perature used for curing the specimens is 90 C. The compressive strength, frost-
resistance and thermal conductivity of products meet the requirements of Chinese au-
toclaved aerated concrete blocks standard; however, the shrinking of non-autoclaved
aerated concrete is still a challenge and the durability also must be observed in the
next work. The results also show that phosphogypsum not only plays the role of filler
but also plays the role of activator.

2.10 Ong, Metcalf, Seals and Taha (2014):

This research deals with the unconfined compressive strength of various ce-
ment stabilized Phosphogypsum (CSPG) and it was shown that the mix behaves like
cement-stabilized soil. The strength and its relation between parameters were studied
for different curing conditions. It was concluded phosphogypsum could be stabilized
with cement to produce an adequate material for road base construction to the re-
quirement of the local codes.

2.11 Zong Shou Lin (2009):

This research investigates a cementitious material by utilizing two industrial
wastes, phosphogypsum (PG) and steel slag (SS), combined with another industrial
by-product ground granulated blast-furnace slag (GGBFS) and limestone (LS). The
28days compressive strength of a mixture of 45% PG, 10% SS, 35% GGBFS and 10%
LS exceeded 40 MPa. XRD and SEM analyses showed that the main hydration prod-

12
ucts were ettringite and C–S–H gel. Part of PG reacted with GGBFS and SS to form
ettringite, the residual PG was wrapped by hydration products. SS in the cement acted
as an alkalinity activator. Over dosage of SS may cause unsoundness.

2.12 Chang, Chin and Ho (2006):

This research deals with the state of art on phosphogypsum for secondary road
construction. It was concluded phosphogypsum when subjected to compaction could
be transformed into a solid of valuable strength. It could be used very effectively as
binder to stabilized soil, replace shell or clay in secondary road and aggregate and wa-
ter. A base course was built by spreading 5 inch of loose phosphogypsum on existing
soil, over which the concrete was laid. This pavement was tested for abrasion, durabil-
ity, shrinkage, compensation, onsite deflection and radiation monitoring. The project
demonstrated that PG based RCC was suitable for construction of parking facilities.
PG without was detrimental to strength contributed to good mix and surface finish be-
cause of fine grinding.

2.13 Smadi et al. (2003):

This research deals with the setting times increased with using PG for calcined
and unclaimed samples. Heat treatment of PG has resulted in the highest improvement
in latter’s flexural strengths and the lowest improvement in compressive strengths. Al-
so, the curing method was found to greatly affect the strengths. The samples, which
were cured in damp room, showed lower strength as compared to those cured in air.

2.14 Thakre et al. (2001):

This research deals with carried out an experimental study on compressive
strength and chemical properties of partially mix phosphogypsum mix concrete. The
authors work covers the material properties and the mix proportion, and the influence
of various parameters on the properties of fresh and hardened concrete. The experi-
mental programmed consist testing of 5, 10, and 15% replaced phosphogypsum mix
concrete for M15, M20, M25, and M30 grades of concrete at the age of 28, 35, and 45

13
days. The chemical analysis of ordinary Portland cement, phosphogypsum and cement
plus phosphogypsum was carried out and on the basis of chemical analysis the
Bogue’s compounds were calculated.
The results of chemical analysis indicates cement and 5% phosphogypsum mix
produce appropriate quantities of C3S and SO3 which are mainly responsible for pro-
duction of C-S-H (calcium-silicate-hydrate) and ettringite (Calcium-Sulpho-Alumino
hydrate) hydration, strength and durability. And therefore, the concrete produced by
this mix must have greater strength and durability than standard mix with further in-
creased in phosphogypsum %, C3S drastically decreased and there is increased in
SO3, which result in internal sulphate attack and hence loss of strength and durability.

2.15 Reddy et al:

This research investigates that the compressive, tensile and flexural strength
characteristics of partially cement replaced phosphogypsum concrete using 0%, 10%,
20%, 30% and 40% replacement with different water-binder ration of 0.40, 0.45, 0.50,
0.55, 0.60 and 0.65.The characteristics strength studied by casting and testing of cube,
cylinder and beam specimen for 7, 28 and 90 days, and shown that a part of Portland
cement can be replaced with phosphogypsum to develop a good and hardened con-
crete to achieved economy; above 10% replacement of phosphogypsum in concrete
lead to drastic reduction not only in the compressive strength but also in the split ten-
sile strength; the flexure strength decreases as width and number of cracks increases
significantly at replacement above 10% of cement with phosphogypsum at different
water-binder ratios.

2.16 Dr. Manjit Singh:

This research shows that gypsum produced from Phosphogypsum can used for
making blocks and boards suitable for internal partition wall and in false ceiling
works. Blocks of different densities (900-1100 kg/m3) have been prepared by adjust-
ing the consistency of slurry. Fibrous gypsum plaster board have also been prepared
from gypsum slurry and reinforced with sisal/coir/jute fibre. A process for manufac-

14
turing of board of size 120×60×12mm has been developed. a high strength hemihy-
drates plaster(a- plaster)has been developed from the beneficiated Phosphogypsum us-
ing autoclave process. Recently cementitious binder has been produced using a-plaster
for use in boards, blocks, masonry, plastering works etc.
A review also shows that water resistant gypsum binder has been developed by
blending ground granulated blast furnace slag or fly ash, opc and chemical additive
with calcined phosphogypsum. Phosphogypsum has been used for glass reinforced
gypsum binder boards (GRGB) of dimensions 400×750mm by reinforcing E-type of
glass fibers in gypsum binder matrix by suction process.

2.17 S. S. Bhadauria and Rajesh B. Thakare:

This study shows that the mixture in which cement replaced with five percent
phosphogypsum having almost same standard or normal consistency than that of plain
cement and thus water requirement of the cement – phosphogypsum mix minutely af-
fected. But, further replacements of ordinary Portland cement with raw PG seriously
affect the consistency. Phosphogypsum in ordinary Portland cement mixes considera-
bly retards setting time but does not contribute to produce unsound cement paste.
Phosphogypsum can be economically used up to five percent as an ingredient or ad-
mixture of cement-mortar mix, both for stone and brick masonry work. The degree of
workability of concrete mix with five percent phosphogypsum decreases as compared
to conventional concrete, but it improves cohesiveness of the concrete mix and thus
reduction in segregation and bleeding. The compressive strength of phosphogypsum
cement concrete (with five percent PG) is improved indicates that phosphogypsum has
immense potential to be utilized in concrete applications, especially mass concrete
work.

2.18 Ouyang, Nanni and Chang:

This research deals with sulphate attack resistance of Portland cement mixture
containing phosphogypsum and conventional aggregate. A wide range of SO3 and
C3A contents were investigated with respect to linear expansion and compressive

15
strength development for specimen submerged in fresh and seawater. The cement con-
tents were varied between 10% - 30% by weight, whereas phosphogypsum varied
from 0 – 50%, lime rock aggregate was used. The results indicated that, the optimum
C3A content, which corresponds to minimum expansion, is about 1.1% for Portland
cement having C3A content less than 7%. And phosphogypsum contents directly pro-
portional to expansion in cement mixes. Seawater immersion decreases the strength
development rate of cylinders and increases linear expansion of bars.

2.19 Adnan Cloak lan (1988):

This research deals with the effect of phosphogypsum – Portland cement – nat-
ural pozzolanic ratios on the mechanical and durability properties of gypsum. The re-
sults indicate that the setting time of these pastes decrease with the increase of gypsum
content in the mixture ranging from 8 to 11 minutes. The addition of super plasticizers
increases the setting time approximately from 11 to 35 minutes. This increase is great-
ly dependent on the plasticizer admixture dosage. The gypsum-Portland cement
blends themselves possess good water resistance which is further enhanced by the ad-
dition of natural pozzolanic and super plasticizer. The water cured blends with the
composition of 41:41:18 on gypsum Portland cement: These blends give excellent
properties retention after again in water at 20 degree for 95 days.

2.20 NadarGhafoori and Wen F. chang:

This experimental investigations state that, standard proctor value of dry densi-
ty of phosphogypsum is 14.52 KN/m3 for compressive strength 1789.50Kpa and split
tensile strength was found 165.40Kpa and for modified proctor test dry density of
phosphogypsum was 15.17KN/m3. whereas compaction strength was found 2452.8
Kpa and split tensile strength was 227.40 Kpa and hence test results indicates that
phosphogypsum is highly compressible material and its strength improves by increas-
ing compaction energy and hence it is comparable to the compressive strength of good
quality concrete. Experimental study also states that, the 28th day compressive
strength of all compacted samples have shown considerable compressive strength con-

16
sidering the percentage level of cement in mixture, strength above 20.67 and 31.00
Mpa can be readily obtained by using 7.5% and 10% cement content respectively. The
use of limited amount of phosphogypsum (20-25%) by weight of total solid appears to
be beneficial for strength characteristics of phosphogypsum concrete.Test results ob-
tained from strength versus time diagram indicates that the concrete mixture contain-
ing phosphogypsum continue to gain strength with curing age, if proper curing condi-
tion is provided.

2.21 Ouyang, Nanni and Chang (2010):

This research deals with the sulphate attack resistance of Portland cement mix-
ture containing phosphogypsum and conventional aggregate. A wide range of SO3
and C3A contents were investigated with respect to linear expansion and compressive
strength development for specimen submerged in fresh and seawater. The cement con-
tents were varied between 10% - 30% by weight, whereas phosphogypsum varied
from 0 – 50%, lime rock aggregate was used. The results indicated that, the optimum
C3A content, which corresponds to minimum expansion, is about 1.1% for Portland
cement having C3A content less than 7%. And phosphogypsum contents directly pro-
portional to expansion in cement mixes. Seawater immersion decreases the strength
development rate of cylinders and increases linear expansion of bars.

17
 CHAPTER 3

METHODOLOGY

ABSTRACT

LITREATURE COLLECTION

COLLECTION OF MATERIAL

TESTING OF MATERIAL

MIX DESIGN

CONCLUSION

FUTURE WORK

18
 CHAPTER 4

MIX DESIGN

4.1 Designing mix step wise

1. Stipulations for proportioning
Grade of designation : M25
Grade ratio : 1:1:2
Type of cement : Ordinary Portland cement
Nominal size of aggregate : 20mm
Maximum water-cement ratio : 0.45
Exposure condition : Medium
Degree of quality control : Fair
Type of aggregate : Crushed angular aggregate

2. Test data for materials

Type of Cement used : Ordinary Portland cement
Specific gravity of cement : 3.15
Specific gravity of coarse aggregate : 2.6
Specific gravity of fine aggregate : 2.65

3. Water absorption
Coarse aggregate : 0.209 %
Fine aggregate : 0.65 %

4. Target strength for mix proportioning

fck = fck + 1.65s
Where
fck = Target average compressive strength at 28 days.

19
fck = Characteristic compressive strength at 28 days.
s = Standard deviation.
From Table I of IS 456:2000,
Standard deviation = 4 N/mm2
Therefore, target strength = 25+1.65x4
= 31.60 N/mm2

5. Selection of water-cement ratio

From table 5 of IS 456:2000, maximum water cement ratio = 0.45

6. Selection water content

From table 2 of IS456:2000,
Maximum water content = 186 litre
= 186+ (6/100) x186
= 197 litre
7. Calculation of cement
Water cement-ratio = 0.45
Cementations material content = 312 Kg/m3
From table 5 of IS 456:2000,
Minimum cement = 290 Kg/m3
Content for “severe” exposure condition
312 Kg/m3 > 290 Kg/m3. Hence ok.

8. Proportion of volume of Coarse Aggregate and Fine aggregate content

From table 3, volume of coarse aggregate corresponding to size aggregate and
fine aggregate of zone I for water-cement ratio of 0.45-0.62
Therefore, volume of coarse aggregate = 0.62x0.9
= 0.56
Volume of fine aggregate = 1-0.56
= 0.44

20
Mix calculations
The mix calculations per unit volume of concrete shall be as follows:
Volume of concrete = 1.0 m3

Volume of cement =

= (312/3.15) x (1/1000)
= 0.10 m3

Volume of water =

= (197/1) x (1/1000)
= 0.20 m3

Volume of all in aggregate = (a-(b+c+d))

= (1-(0.10+0.20+0.006))
= 0.69 m3
Mass of coarse aggregate = f x volume of coarse aggregate x spe-
cific gravity of coarse aggregate x
1000

= 0.69 x 0.56 x 2.6 x 1000

= 1004.64 Kg/m3
Mass of fine aggregate = f x volume of fine aggregate x specific
gravity of fine aggregate x 1000
= 0.69 x 0.44 x 2.65 x1000
= 813.86 Kg/m3

21
9. Mix proportions
Cement = 312 Kg/m3
Fine aggregate = 813.86 Kg/m3
Water = 140 Kg/m3
Coarse aggregate = 1004.64 Kg/m3
Water-cement ratio = 0.45
Grade = M25
Mix ratio = 1:1:2

22
 CHAPTER-5

MATERIALS USED

5.1 CEMENT
Cement is the most important ingredient and acts as a binding material
(having adhesive formed and cohesive properties). Cement is obtained by palaver-
ing clinker formed by calamine raw materials primarily compromising of liming
(CaO), silica (SiO2), Alumina (Al2O3) and Ferric oxide (Fe2O3) along with some
minor oxides. Joseph Asp Din, a brick layer in England, developed Portland ce-
ment in 1824.
Ordinary Portland cement (53 Grade) is used in the investigation. The
cement used has been tested for various properties as per IS:4031-1988 and found
to be confirming to various specifications of IS:12269-1987. The cement has a
specific gravity of 3.15, 38% of water content for standard consistency and 3%
fineness.

Figure 5.1 Cement

23
 TABLE 5.1 PROPERTIES OF 53 GRADE CEMENT
SI. PHYSICAL PROPERTIES OF REQUIREMENTS AS
NO GRADED CEMENT RESULTS PER IS: 8112-1989
1 Specific gravity 3.10 3.10-3.15
2 Standard consistency (%) 30.5% 30-35
3 Initial setting time (hours, min) 32 min 30 minimum
4 Final setting time (hours, min) 610min 600 maximum
Compressive strength N/mm2 at 28
5 days 58 N/mm2 53 N/mm2 minimum

5.1.1Tests on cement:
• Fineness test.
• Consistency test.

5.1.1.1 FINENESS TEST ON CEMENT DESCRIPTION:

Cement is in the form of powder, which is obtained by grinding the various
raw materials after calcimining. The grinding produces finer particles of cement.
The degree to which the cement is ground to smaller and smaller particles is called
fineness of cement.

The fineness of cement has more importance on the rate of hydration and on
the rate of gain of strength IS 269-1976 prescribes that the weight retained on IS
sieve no. 90 µ shall not exceed 10% of ordinary cement.

24
OBSERVATION:
Weight of cement taken = 100g
Weight of cement retained on IS sieve No.90 µ=3g

RESULT:
Fineness test on cement = 3%

5.1.1.2 CONSISTENCY TEST ON CEMENT DESCRIPTION:

The standard consistency of a cement paste is defined as that consistency
which will permit the vicat plunger to penetrate to a point 5-7mm from the bottom
of the vicat mould when the cement paste is tested. The ratio between the amount of
water and the amount of cement by weight is known as water cement ratio. Weight
of water cement ratio controls the strength of the mix consistency test help us in
finding the quantity of water to be added to produce a cement paste of standard.

TABULATION:
TABLE 5.2 CONSISTENCY TEST ON CEMENT
WEIGHT OFWATER
PENETRATION
SI.NO DESCRIPTION CEMENT TAK- ADDED
(MM)
EN (g) (%)
1. OPC53 GRADE 500 30 12
2. OPC 53 GRADE 500 35 7
3. OPC 53 GRADE 500 34 6

RESULT:
The value for consistency test on cement is 8 mm.

25
5.2 PHOSPHOGYPSUM
Phosphogypsum is a spinoff of phosphate fertilizer flowers and chemical indus-
tries. Phosphogypsum is a grey coloured, damp, fine grained powder, silt or silty-sand
material with a maximum size ranges between 0.5 mm (No. 40 sieve) and 1.0 mm
(No. 20 sieve) and the majority of the particles (50-75 %) are finer than 0.075 mm
(No. 200 sieve). The specific gravity of phosphogypsum ranges from 2.3 to 2.6. The
maximum dry bulk density is likely to range from 1470 to 1670 kg/m3. The gypsum
cake, after filtration, usually has free moisture content between 25 and 30%.

Hemihydrate, in the presence of free water will rapidly convert to dihydrate and in the
process, if left undisturbed will set into a relatively hard cemented mass and does not
cause dust problem unless disturbed. Phosphogypsum consists of primarily of calcium
sulphate dihydrate with small amounts of silica, usually as quartz and unreacted phos-
phate rock, radioactive material (like radium, uranium), heavy metals namely arsenic,
cadmium, chromium, mercury and fluoride. The concentration of the metals depends
on the composition of the phosphate rock.

TABLE 5.3 CHEMICAL COMPOSITION OF PHOSPHOGYPSUM

PERCENTAGE
SI.NO CHEMICAL CONSTITUENTS CONTENT

1. CaO 31.2

2. SiO2 3.92

3. SO3 42.3

4. Al2O3 & Fe2O3 3.6

5. MgO 0.49

6. Phosphates, fluorides, etc,. 18.4

26
5.2.1Tests on phosphogypsum:
• Fineness test.
• Setting time test.
• Consistency test.
• Soundness test.

5.2.1.1 FINENESS TEST ON PHOSPHOGYPSUM DESCRIPTION:

Phosphogypsum is in the form of powder. The degree to which the Phos-
phogypsum is ground to smaller and smaller particles is called fineness of cement.

The fineness of Phosphogypsum has more importance on the rate of hydra-

tion and on the rate of gain of strength IS 269-1976 prescribes that the weight re-
tained on IS sieve no. 90 µ shall not exceed 10% of ordinary cement.

OBSERVATION:
Weight of Phosphogypsum taken = 100g
Weight of Phosphogypsum retained on IS sieve No.90 µ=2.5g

RESULT:
Fineness test on Phosphogypsum = 2.5%

27
 5.2.1.2 SETTING TIME TEST ON PHOSPHOGYPSUM:
The setting time was conducted as per IS: 4031-1988. It was observed
that even for five percent replacement of cement with raw of impure phos-
phogypsum the initial and final time was increased beyond standard value for
Ordinary Portland Cement as specified in IS:12269-1987.

TABULATION:
TABLE 5.4 SETTING TIME TEST ON PHOSPHOGYPSUM
% replacement of cement Initial setting Final setting
time (min) time(min)

0 32 610

5 45 650

10 56 677

15 70 710

20 85 734

25 100 786

5.2.1.3 CONSISTENCY TEST ON PHOSPHOGYPSUM:

The normal consistency was conducted as per IS: 4031-1988. It was observed
that phosphogypsum provides additional stiffness to the paste and therefore it was re-
quired to add water for desired penetration of Vicats plunger. However, for five pe-
cent replacement of raw phosphogypsum the normal consistency is very close to

28
standard value and for further addition of phosphogypsum the value increased beyond
limit specified in IS:12269-1987 i.e. 30% as per Indian standards.

TABULATION:
TABLE 5.5 CONSISTENCY TEST ON PHOSPHOGYPSUM
NORMAL CON-
SI.NO % REPLACEMENT OF CEMENT SISTANCY

1 0 27

2 5 29.7

3 10 32.4

4 15 33.5

5 20 35.2

6 25 36.1

5.2.1.4 SOUNDNESS TEST ON PHOSPHOGYPSUM:

The soundness of cement was conducted as per IS: 4031-1988. It is very
important to measure soundness of paste made with replacing cement. The test
results are presented in the table below. The results indicated that even 25% re-
placement of cement does not contribute to unsound paste.

29
 TABULATION:
TABLE 5.6 SOUNDNESS TEST ON PHOSPHOGYPSUM

SI.NO % REPLACEMENT OF CEMENT SOUNDNESS

1 0 0.55

2 5 1

3 10 3

4 15 6

5 20 8.5

6 25 9

5.3 AGGREGATE
5.3.1 Coarse aggregate:
The coarse aggregate of 20mm and down size, having a specific gravity of
2.83 and a fineness modulus of 4.12, tested as per IS:2386-1963 is used.
TABLE 5.7 PHYSICAL PROPERTIES COARSE AGGREGATE

SI.NO PHYSICAL PROPERIES RESULT

1. Specific gravity 2.6
2. Fineness modulus 2.98
3. Water absorption 0.50%
4. Free moisture content 0.10%
5. Aggregate impact value 12
6. Aggregate crushing value 23

30
5.3.1.1 Tests on coarse aggregates:
• Fineness Modulus Test
• Water Absorption Test

5.3.1.1.1 FINENESS MODULUS TEST:

Fineness modulus is an empirical figure obtained by adding the total percent-
age of the sample of an aggregate retained on each of specified serious sieves and di-
viding the sum by 100. Fine aggregates range from fineness modulus of 2 to 4 and
coarse aggregates smaller than 38.1 mm range from 6.5 to 8.

FORMULA USED:
Fineness modulus of coarse aggregate = (W2/W1) *100
TABULATION:
TABLE 5.8 FINENESS MODULUS OF COARSE AGGREGATE
SI. Sieve size (mm) Weight of % of Cumulative Percent of
NO Aggregate Weight % of finer
(g) retained (g) Retained Y=(100-x)
1. 40 5000 250 250 5
2. 20 5000 1750 2000 40
3. 10 5000 1600 3600 72
4. 4.75 5000 1400 5000 100
5. 2.36 5000 0 5000 100
6. 1.18 5000 0 5000 100
7. 0.6 5000 0 5000 100
8. 0.3 5000 0 5000 100
9. 0.15 5000 0 5000 100

RESULT: Fineness modulus of the coarse aggregate is 7.17.

31
 5.3.1.1.2WATER ABSORPTION TEST ON COARSE AGGREGATE
DESCRIPTION:
Water absorption is used to determine the amount of water absorbed under
specified conditions. Factors affecting water absorption include: additives used,
temperature and length of exposure.
Capillary absorption is the movement of water through the small pores in
concrete in the absence of an externally applied hydraulic head, and is the result of
surface interactions between the water and the pore wall.

TABULATION:
TABLE 5.9 WATER ABSORPTION TEST OF COARSE AGGREGATE
Weight of % of water
Weight of oven
Samples Saturated Weight of water absorption
dried Specimen
No Specimen absorbed =(w3/w1)
(w1) g
(w2) g W3=(W2-W1) *100
1. 2404 2409 5 0.208
2. 2375 2380 5 0.210

RESULT:
Water absorption of the coarse aggregate is 0.209%

5.3.2 Fine aggregate:

Natural river sand with specific gravity of 2.63 and confirming to IS: 383
zone II is used. The sand was tested as per IS: 2386 (Part III) -1963. The sand is
having percentage of water content at maximum bulking equal to 7%.

32
 TABLE 5.10 PHYSICAL PROPERTIES OF FINE AGGREGATE
SI.NO Physical properties Test result
1 Specific gravity 2.65
2 Fineness modulus 2.8
3 Water absorption 0.65%
4 Free moisture content 0.20%

5.3.2.1 Tests on Fine aggregates:

• Specific gravity test
• Sieve analysis test

5.3.2.1.1 SPECIFIC GRAVITY OF FINE AGGREGATE DESCRIPTION:

The fine aggregate specific gravity is used to calculate the specific gravity
of a fine aggregate sample by determining the ratio of the weight of a given volume
of aggregate to the weight of an equal volume of water saturated surface dry (water
fills the aggregate pores).

TABULATION:
TABLE 5.11 SPECIFIC GRAVITY OF FINE AGGREGATE
SI.NO DESCRIPTION WEIGHT(g)
1. weight of empty pycnometer, (W1) gm. 658
2. weight of pycnometer + FA, (W2) gm. 1054
3. weight of pycnometer+ FA + water, (W3) gm. 1755
4. weight of pycnometer+ water, (W4) gm. 1508

FORMULA USED:
Specific Gravity (W2-W1) (W4- W1) / (W3-W2) = 2.657

33
RESULT:
The specific gravity of the fine aggregate =2.65

5.3.2.1.2SIEVE ANALYSIS OF FINE AGGEGATE DESCRIPTION:

An analysis is a practice or procedure used to assess the particles
size distribution of a granular material. The size distribution is often of
critical importance to the way the material performs in use.
A sieve analysis can be performed on any type of non-organic or organic
granular materials including sand, crushed rock, clays, granite, feldspars, coal
and soil.

TABULATION:
TABLE 5.12 SIEVE ANALYSIS FOR FINE AGGREGATE
Cumulative
IS Weight re- % of weight % of Pass-
SI.NO of weight re-
Sieve(mm) tained (gms) retained ing Finer
tained
1 4.75 7 1.4 1.4 98.6
2 2.36 12 2.4 3.8 96.2
3 1.18 20 4 7.8 92.2
4 0.60 65 13 20.8 79
5 0.30 292 58.4 79.2 30
6 0.15 90 18 97.2 2.8

RESULTS:
The value of fineness modulus of fine aggregate (sand) =5.1

34
5.4 WATER
Locally available portable water confirming to standards specified in IS: 456-
2000 is used.

5.4.1 TEST ON WATER

TABLE 5.13 TESTS ON WATER

TAP WATER
S.NO TEST DETAILS RANGE
Ppm

1 Chloride test 1050 1000

2 Hardness test 13.797 0 to 60

Titration 1
4.375
3 Alkality test 0 to 20
Titration 2
10.75

4 pH test 8.5 Not less than 6

35
 CHAPTER-6

CONCLUSION

The phase1 of this research work deals with the experimental investiga-
tion of concrete by partially replacing the cement by phosphogypsum with 0%,
5%, 10%, 15%, 20%, 25%. In this work, the materials are collected and various
material tests are done. Mix design for M25 grade concrete is calculated. It was
concluded that,

 Phosphogypsum in ordinary Portland cement mixes considerably retards

setting time.
 The type and amount of Portland cement will significantly influence the
performance of stabilized phosphogypsum mixtures.
 By replacement cement in concrete by phosphogypsum, reduces the con-
sumption of cement.
 Partial replacement cement by phosphogypsum increase setting time, in-
crease standard consistency, but not effect on soundness property.
 Partial replacement of PG reduces the environmental effects, produces
economical and eco-friendly concrete.

In next semester, the phase II of the project work involves testing of the
concrete specimens. The fresh concrete as well as hardened concrete properties
of the phosphogypsum with different percentages of replacement are needed to
be tested with the reference mix. The main aim of the project is to find the op-
timal percentage of replacing cement with phosphogypsum

36
 CHAPTER-7

REFERENCE

1. IS456: 2000, Plain and Reinforced Concrete Code of Practice Bureau of Indian
Standards. Fourth Revision.
2. "Recommended Guidelines for Concrete Mix Design”. IS10262-1982 (2009).
3. IS383 1970, Specification for Coarse and Fine Aggregate from Natural Sources
for Concrete Bureau of Indian Standards". Second Revision.
4. T. Siva Sankar Reddy, “A Study on Strength Characteristics Of Phosphogyp-
sum Concrete” Department Of Civil Engineering, Asian Journal Of Civil Engi-
neering 2010.
5. Mahesh A Bagade And S.R.Satone,“An Experimental Investigation Of Partial
Replacement Of Cement By Various Percentage Of Phosphogypsum In Ce-
ment Concrete.”, International Journal Of Engineering Research And Applica-
tions 2012.
6. Degirmenci Nurhayat, Okucuarzu, Turabiayse. Application Of Phosphogypsum
In Soil Stabilization. Build Environ 2014;42(9):3393–8.
7. A. B. Mahesh, And S. A. Satone, “An Experimental Investigation Of Partial
Replacement Of Cement By Various Percentage Of Phosphogypsum In Ce-
ment Concrete”, International Journal Of Engineering Research And Applica-
tions, Vol.2, Issue 4, 2012.
8. W. F. Chang, And M. I. Mantell “Engineering Properties and Construction Ap-
plications of Phosphogypsum”, University Of Miami Press, Florida, 1990.
9. Asokan P, Mohini S, Shyam Ra. Solid Wastes Generation In India And Their
Recycling Potential In Building Materials, Building And Environment,
42(2007) 2311–20.
10. A. Roy, R. Kalvakaalava, And R. K. Seals., Microstructural And Phase Charac-
teristics Of Phosphogypsum – Cement Mixtures, Asce Journal Of Materials In
Civil Engineering, Volume 8, Number 1, (February 1996) 11 – 18.

37