You are on page 1of 4

Point of View

These columns of ICJ offer an opportunity to the


engineering fraternity to express their views on the
current practices in design, construction and
management being followed in the industry.
To share your opinion with our readers, you may send
in your inputs in about 1500 words via E-mail to
editor@icjonline.com

Dual role of gypsum: Set retarder and


strength accelerator

N. Bhanumathidas and N. Kalidas

Gypsum plays a crucial role in cement. reactions, in the absence of gypsum, totally lead to a misunderstanding that the
Though it is used in a small quantity, in vetoes the commercial use of cement. The addition of more gypsum means
following chemical reaction, in the absence additional retardation in setting, which is
the range of 2.5-3.0 percent in terms of
of gypsum, is explanatory in this regard. not true. The formation of ettringite at
SO 3 , gypsum’s role in cement is threshold levels accelerates the hardening
significant, more predominantly at early process and thus hastens strength gain at
3 CaO. Al2O3 + n H2O fast reactions
ages. Gypsum renders workability to early ages. In view of this behaviour, the
mortar or concrete by keeping the cement CAH + profuse exothermic heat latest European code on cement — ENV
in plastic state at early age of hydration. 197 - 1 stipulates higher dosages of SO3
Hence, it was found essential to change (between 3.5 to 4 percent by mass)1. As
This is achieved by changing the course the reaction course of C3A, and this was against this, the Indian specifications on
of hydration of calcium aluminate that met by the use of sulphate salts. Due to its both 43 and 53 OPC grade (IS 8112 : 19892
manifests as retardation in cement affinity with SO3 , aluminate tends to react and IS 122269 : 1987 3 ) specify the
hydration. This is how gypsum is readily with the former and in this process maximum SO3 content of 2.5 percent by
the reactions of aluminate with water are mass (for C3A< 5 percent) and 3 percent
identified as a set regulator or retarder, prevented. Ultimately, gypsum was
as known popularly . Nevertheless, by mass (for C 3 A> 5 percent). The
identified as the most effective form of specification on portland pozzolana cement
gypsum also contributes for strength sulphate to control hydration reactions of (IS 489 : 19914) and that on portland slag
acceleration in the early stages of C3A that incidentally resulted in better cement (IS 455 : 19895) stipulates SO3 level
hydration. This dual role of gypsum is workability for a longer duration. of 3 percent by mass.
discussed in the feature. Chemical reaction in the presence of In the manufacture of blended cements,
gypsum is given below by virtue of reactive aluminates from fly
Gypsum is the set retarder for ordinary ash and slag that leads to ultimate cement,
portland cement (OPC). Without gypsum, 3CaO. Al2O3 + 3CaSO4. 2H2O + nH2O →
the chances for existence of resultant
ground clinker exhibits flash setting in a 3CaO. Al2O3. 3CaSO4. 32H2O calcium aluminate hydrates are more than
few minutes, due to the rapid hydration of what is generally available in OPC, as shown
calcium aluminates to form calcium (Ettringite : calcium trisulpho aluminate
hydrate) + moderate exothermic heat in the Table 1.
aluminate hydrate (CAH). The hydration
of C3A releases profuse exothermic heat Hence, the increasing positive threshold
Many in the cement and concrete
making the matrix stiff, minimising the levels of gypsum is one of the solutions to
industry know the role of gypsum as set
chances for remixing. The CAH, thus overcome the weakness of strengths at early
retarder or set regulator. But the
formed, does not contribute for strength of ages in mortar/concrete with blended
complementary role of gypsum, as
the matrix and, moreover, hampers the hy- cements. This aspect is also of significance
accelerator to render high early strengths, is
dration of calcium silicate. The sequence of when the blending is done in ready mix
generally unnoticed. This knowledge gap

March 2004 * The Indian Concrete Journal 1


Point of View
Table 1: Need of SO 3 corresponding to calcium aluminates formation in the blends matrix. This activity was sustainable for
Type of cement C3 A CA As monosulphate Need of SO3 longer ages in low grade cements, accredited
3CaO.Al2O3.CaSO4.12 H2O for final phase for their durability, which is explained in
terms of heat bank and lime bank by the
OPC 5.00 9.28 11.50 1.47
authors7. In contrast, accelerated reactions
OPC(70) + FA(30)* 3.50 16.70 29.40 6.40 take place in high grade cements for
OPC(50) + Slag(50)** 2.50 38.40 8.35 relatively shorter periods, leading to the
complications and decrease in durability.
Note: CA - Reactive calcium alumino silicate, *Fly ash with 30 percent reactivity containing 25 percent Al 2O3,
**Slag with 90 percent reactivity containing 14 percent Al 2O3.
Ettringite in pre-hardened
concrete plants. While all fly ashes may and ettringite precipitate out and a dense and post-hardened
not need additional gypsum, care has to be C-S-H gel coating is formed on the cement concrete.
taken not to deprive those fly ashes in need grains. This coating as well as ettringite
It is observed that the ettringite formed in
of additional gypsum. coating on C 3 A grains retard further
pre-hardening stage is conducive for the
hydration, and this explains the existence
FaL-G technology, developed by the matrix formation in comparison to the same
of dormant period, that is, the period of
authors, achieved its breakthrough by formed in post-hardening stage. The sim-
relative inactivity lasting for one to two
tapping the potential of calcium aluminates ple reason is its volume expansion by tak-
hours. During this dormant period the paste
towards the formation of ettringite and ing almost 32 molecules as water of crys-
remains plastic and workable. The end of
mono-sulphate; thus changing the pace of tallisation. As already mentioned, in a hy-
the dormant period can be identified as
lime-fly ash chemistry. Gypsum plays a drated cement paste, the level of imperme-
initial set. This is attributable to the break
predominant role as the strength- ability increases through volume expansion
up of C-S-H and ettringite coatings, and
accelerator in the context of hydrated of hydrated phases and the resultant
the resultant continuation of hydration
mineralogy in FaL-G. Moreover, gypsum densification through the process of cur-
process. Due to the osmotic pressure the
works as set-accelerator in lime-pozzolana ing. In the initial ages of hydration this ex-
gel coating gets ruptured, exposing the
binders in contrast to its role as set-retarder pansion contributes for the internal
cement grain, wherein hydration is resumed
in OPC. compaction of matrix, resulting in
and setting takes place.
densification and strength. These phenom-
Consequently, as the hydration ena lead ultimately to impermeability of
Calcium aluminate the matrix. However, if the same expan-
proceeds, the hydration products gradually
sulphate chemistry fill in the spaces of the cement grains. Points sion occurs after the matrix attains volume
Before getting into the details of the min- of contact are formed resulting in stiffening stability then the matrix is subjected to in-
eralogical formations, it is essential to briefly of the paste, which is identified as the
go through the chemistry and hydration of setting. At some
OPC, which is a product of four principal later stage, the
mineralogical phases, namely, concentration of
hydration products
3CaO. SiO2: C3S (Tricalcium silicate) and resultant
concentrations of
2CaO. SiO2: C2S (Dicalcium silicate) points of contact
restrict the mobility
3CaO. Al2O3: C3A (Tricalcium aluminate)
of cement grains to
4CaO.Al 2 O 3 .Fe 2 O 3: C 4 AF (Tetracalcium such an extent that
aluminoferrite) the paste becomes
rigid, reaching the
Upon adding water, the anhydrous state of final set.
mineralogy gets dissociated as CaO, SiO2,
Al 2 O 3 and Fe 2 O 3 for associating into The volume of
hydrated mineralogy. Setting is the interface the hydration
for this transformation. Soroka 6 gave products, through
sequential illustrations for working period, the process of
initial setting and final setting for cement crystallisation and
paste, by graphic representation of the matrix formation, is
mineralogical phase formations as shown more than twice to
in Fig 1. that of the
anhydrous cement.
As explained by Soroka in the first The dissociation
phase, when water is added to cement, as a and association of
result of the hydrolysis of the calcium mineralogy continue
silicates, a super-saturated solution of as long as the
calcium hydroxide is formed. Sulphate and moisture is
alkali ions, as well as small amounts of available and
silica, alumina and ferric oxide are also release of lime is
present in the solution. Calcium hydroxide continued in the

2 The Indian Concrete Journal * March 2004


Point of View

Table 2: Relation of strength and heat of hydration to increase in SO 3 in OPC attributed to the presence of higher reactive
SO3, Setting time, min Compressive strength, MPa Heat of hydration, kCal/kg amorphous alumino silicates in LT fly ashes
percent Intial Final 1-day 3-day 7-day 28-day 12-hour 1-day 3-day 7-day 28-day
which produces CAH that can further form
ettringite with gypsum.
1.80 115 150 17.7 37.4 53.8 61.6 22.5 33.2 45.4 59.3 67.2
2.10 130 165 20.9 40.2 59.0 65.4 28.2 33.2 44.5 63.0 65.7 Gypsum in blended cements
2.40 135 180 20.9 32.1 47.8 62.0 46.0 54.2 63.2 80.3 88.5 The hydration chemistry of blended ce-
2 ments is a two-phase mechanism. In the
Surface area of OPC : 320 kg/m
first phase, the OPC chemistry surfaces and
in the second phase pozzolanic chemistry
ternal expansive pressures that result in as heat of formation. The threshold dose of comes into force. This is represented as fol-
cracking of the concrete. gypsum regulates the heat of hydration as lows:
also the ettringite formation for progressive
If the hydration chart of Soroka is chemistry. In the anxiety of not to retard OPC + H fast
observed for the formation of various cement if the gypsum is reduced below the
mineralogies, the formation of threshold level, heat of hydration is Primary hydrated mineralogy + CH
sulphoaluminate hydrates is predominant commensurately profuse leading to internal
till the final set that is followed by calcium thermal stresses and incohesiveness. This Pozzolana + CH + H slow
silicate hydrates. As ettringite descends is where the role of gypsum is evident as
from its peak of formation by first or second Secondary hydrated mineralogy
retarder.
day, the formation of monosulphate does
commence. What does it mean? It means Maximum amount of gypsum is In pozzolanic reactions, alumina is
that gypsum gets largely exhausted for the engaged into ettringite in the first two to noticed but the addition of commensurate
formation of tri-sulphate. At this stage three days. Thus, matrix becomes more gypsum is not given much weightage. Even
calcium aluminate hydrates continue to be cohesive with improved strength the ASTM definition of pozzolanic
available with affinity to form development. Nevertheless, each clinker has chemistry is silent on this issue, which says,
sulphoaluminate hydrates. Due to their its own optimum level of demand for “Siliceous or siliceous and aluminous
affinity for sulphate ion these aluminate gypsum that decides the other materials, which, though not cementitious
hydrates react with ettringite. This is characteristics. The data in Table 2 elucidate themselves, react with lime, when in finely
manifested as the commencement of the same. divided form, in the presence of water at
monosulphate formation. These reactions ordinary temperature, and form stable and
concur with the physical status of the matrix In the above studies on OPC, addition insoluble mineralogical phases, possessing
where porosity of the matrix is largely filled of SO3 beyond 2.1 percent is proving adverse cementitious characteristics”.
up by ettringite at early age, beyond which both in strength and heat of hydration
the reduced porous spaces are though the one-day strength is impressive. But the principle behind use of
progressively occupied by monosulphate. Hence, it would be highly inappropriate to additional gypsum in blended cements lies
Thus, the three-day strength is largely decide the quality of cement based on one- in the capability of SO3 to break the glass of
attributable to the formation of calcium day strength alone, which unfortunately is pozzolana. This occurs due to the affinity
sulphoaluminate hydrates. projected as a quality parameter by many. between SO3 and alumina that facilitates
the formation of calcium sulphoaluminate
The transformation of ettringite to Strength data of calcium hydrates. The indirect benefit is the
monosulphate is as follows: availability of reactive silica, freed from
aluminates to calcium
glass of pozzolana, for reactions. The
3CaO.Al2O3.3CaSO4.32H2O + sulpho aluminates formation of additional ettringite and CSH
2(3CaO.Al2O3) + x H2O →
Gypsum in FaL-G makes the cement matrix more densified
3(3CaO.Al2O3.CaSO4.12H2O) and impermeable at early ages. The studies
In FaL-G studies, two formulations were
This is a slow reaction that either leaves on fly ash blended mortars and concrete
made for fly ash lime mixes with and with-
monosulphate as the ultimate mineralogy substantiate this phenomenon as shown in
out gypsum. The predominant difference
of sulphoaluminates or makes the same into Table 4.
is the formation of calcium aluminate hy-
hexagonal plate solid solution with CAH, drate where there was no gypsum; and the
probably C4AH13, to result in a stable stage. formation of calcium sulphoaluminate hy-
In the sequence of calcium aluminate Table 3: Increase in strength upon
drate where gypsum was available. These
hydrate chemistry, ettringite (trisulphate) addition of gypsum in fly ash-lime mixes
mineralogical formations were substanti- both in LT and HT fly ashes
formation is an in-built mechanism or a boon ated by XRD. Notwithstanding these for-
to render high early strengths to the matrix. mations, the strength data also substanti- Source Compressive strength MPa
This can be achieved only in the presence of ate the observation both at 7-day and 28- Fly ash + lime FaL-G
gypsum, which also hastens the CSH day as shown in Table 3. In the light of mod- 7-day 28-day 7-day 28-day
chemistry8. This is how gypsum’s role is erate performance by calcium silicate chem-
LT fly ash 1 9.0 17.9 25.0 32.0
upheld as early-strength accelerator. istry in fly ash lime mixes at early ages, the
credit of the early strength goes to ettringite. LT fly ash 2 11.0 15.8 20.0 25.8
At the early ages, the cementitious
HT fly ash 1 2.6 7.8 8.4 24.0
matrix needs heat for rapid hydration of Table 3 shows that LT fly ashes show higher
chemistry. This is rendered by the hydration reactivity than HT fly ashes. This could be HT fly ash 2 3.3 4.9 6.5 24.8
of C3A, which is commensurately availed

March 2004 * The Indian Concrete Journal 3


Point of View
Table 4: Impact of gypsum on compressive strength at different inputs of fly ash 2. ______Indian standard code for 43 grade ordinary
portland cement, IS 8112 : 1989, Bureau of Indian
OPC Compressive strength of mortar, MPa Standards, New Delhi.
Fly ash 7-day 14-day 28-day 60-day 270-day
(a) (b) (a) (b) (a) (b) (a) (b) (a) (b) 3. ______Indian standard code for high strength
ordinary portland cement, IS 12269 : 1987, Bureau
50 : 50 24.4 20.0 32.4 22.8 40.8 29.6 50.8 44.4 56.8 48.0
of Indian Standards, New Delhi.
(PPC-I)
40 : 60 21.2 15.2 29.6 22.0 38.0 34.0 45.2 44.4 56.0 47.8 4. ______ Indian standard code for fly ash based
(PPC-II) cement, IS 1489 : 1991, Bureau of Indian
Standards, New Delhi.
100 : 0 27.2 35.2 40.4 48.0 54.4
(control mortar) 5. ______Indian standard code for blast furnace slag
(a): Added with anhydrite commensurate to fly ash quantity, (b): Without anhydrite based blended cement, IS 455 : 1989, Bureau of
Indian Standards, New Delhi.

6. Soroka I: Portland Cement Paste and Concrete;


Table 5: Improvement in lime reactivity hydration also, which is evident from the Chemical Publishing Co.,Inc. New York, 1979.
strength with the addition of gypsum data already given in Table 2. 7. BHANUMATHIDAS, N and KALIDAS, N Metabolism
Fly ash Lime reactivity strengths MPa of cement chemistry, The Indian Concrete Journal,
This means, gypsum liberates more heat September 2003, Vol 77, No 9, pp. 1304-1306.
Without gypsum With gypsum of hydration on account of rapid chemistry.
10-day 90-day 10-day 90-day However, beyond a threshold level of SO3, 8. MEHTA, P.K. and MONTEIRO, PAULO J.M. Concrete:
Sample 1 2.8 6.4 5.2 10.8 such rapid chemistry would not contribute Microstructure, Properties, and Materials, The
McGraw Hills Companies Inc, New York, 1993.
for strength gain. This explains the rationale
Sample 2 7.7 11.9 11.9 19.3
behind the increase of gypsum for rapid
Sample 3 9.1 15.9 17.7 21.7 hardening cements vide European code,
keeping an eye on the threshold limits.
Dr N Bhanumathidas is the
Conclusions director general of Institute
Durability aspects for Solid Waste Research and
Gypsum works as a double-edged sword
Chloride permeability with in cement chemistry. One needs to have com- Ecological Balance
change in dose of gypsum prehensive understanding of the cement (INSWAREB), the research
mineralogy and hydration chemistry before body dedicated to the utilisa-
When gypsum is added as a third compo- tion of industrial wastes to-
nent in lime reactivity studies, the LR value deciding on the dosage of gypsum. As
wards building material. After obtaining
improves strikingly that indicates forma- much one can get optimum results by judi-
her postgraduate degree in physics from
tion of quite cohesive matrix associated with cious input of gypsum, so much so one Andhra University, she did her doctoral
improved strength as shown in Table 5. may get disastrous results too by improper studies in chemical engineering (inter-dis-
dosing. This is where the holistic knowl- ciplinary). Dr Bhanumathidas has authored
Studies on blended concretes using edge on cement chemistry is of significance. several technical papers in collaboration with
Sample 3 have brought in interesting her associate, Mr N Kalidas, and presented
phenomena towards improved durability Acknowledgements at several national and international semi-
despite higher workability as shown in The authors acknowledge the guidance of nars. FaL-G is the outcome of this team-
Table 6. Prof P.K. Mehta and his wealth of library work. She is currently focussing on ad-
made available. The authors also record vanced concrete technology, use of indus-
trial byproducts as complementary cemen-
The rationale of gypsum in their gratefulness to Madras Cements Ltd.,
titious material and promotion of blended
European codes: for making available the laboratories to this
cements.
research.
Studies were conducted on OPC at differ- Mr N Kalidas is engaged in
ent doses of gypsum mentioned in terms of References the pursuit of waste utilisa-
SO3. The heat of hydration diminishes up tion technologies for the last
1. ______Cement part I : Composition, specifications
to a particular level beyond which, it is noted and conformity criteria for common cement, ENV,
18 years as a technocrat and
that, increase of SO3 the increases heat of 197-1 : 1995, European Committee for by virtue of his assignment
Standardisation, Brussels. with certain overseas compa-
nies. In order to consolidate
his work on waste utilisation, he along with
his associate, Dr N Bhanumathidas,
Table 6: Reduction in permeability upon addition of gypsum
founded the research body, INSWAREB. He
Cementitious Slump, mm Compressive strength, MPa Chloride permeability is the director of INSWAREB. His field of
Content, percent 3-day 7-day 28-day 90-day 180-day 360-day material, Coulombs interest includes: advanced concrete tech-
OPC Sample 3 28-day 90-day 180-day 360-day nology, use of industrial byproducts as
complementary cementitious material, pro-
100 — 14 21.6 31.2 43.3 47.2 51.4 54.7 3852 2451 2251 1912 motion of blended cements. Along with Dr
65 35 80 12.2 17.7 35.1 53.7 58.4 65.9 2529 313 166 155 N Bhanumathidas, he has authored sev-
eral technical papers and presented at vari-
65 35* 139 13.1 18.8 35.7 54.9 61.3 63.7 2107 234 130 151
ous national and international seminars.
*Added with 2.76 as SO3. •••

4 The Indian Concrete Journal * March 2004