GypsuminCement

Introduction
Gypsum, CaSO4.2H2Oa dihydrate of calcium sulphate, is a nonhydraulic binder occurring naturally as a soft crystalline rock. It has long been recognized as an important and essential component of Portland cement.Itisthesetretarderforcements.Withoutgypsum,groundclinkerexhibitsflashsettinginafew minutes, due to the rapid hydration of calcium aluminates to from calcium aluminate hydrates (CAH).The CAH, thus formed, does not contribute for strength of matrix and moreover, hampers the hydrationofcalciumsilicates.Additionofsmallamountsofgypsum(35%)toclinkerduringthegrinding process changed the reaction course of C3A owing to its affinity with SO3, which in turn, resulted in betterworkabilityforalongerduration.Itisnowadaysgenerallyknownthatgypsumnotonlyaffectsthe setting of cement, but it also influences other characteristics of cement such as grindability, storage, compressivestrengthandvolumestability. Gypsum that occurs in nature is called mineral gypsum. In addition to mineral gypsum, seawater and some chemical plants are sources of byproduct marine gypsum and byproduct chemical gypsum, respectively. Marine gypsum is recovered from salt pans during production of common salt whereas later is obtained as byproduct phosphogypsum or fluorogypsum, depending upon the source. The recovery of marine gypsum and byproduct gypsums together is substantial and is comparable with the production of mineral gypsum. Both, mineral and byproduct gypsum are used in cement manufacture. Large quantities of gypsum are produced by flue gas desulphurization at coalfired power stations and areincreasinglybeingutilizedinPortlandcementmanufacture.

FormsofGypsum
The CaSO4H2O system is composed of five solid phases: dihydrate (CaSO4.2H2O), hemihydrate (CaSO4.0.5H2O), anhydrite I (CaSO4), anhydrite II (CaSO4), and anhydrite III (CaSO4) and thus the effects of calcium sulphate on the behavior of cement depends on the forms in which it is present in the system. Table 1 shows the different forms of gypsum with their corresponding properties and their occurrence. Table1:DifferentformsofGypsum,theirproperties&occurrence

Designation Dihydrate Hemihydrate AnhydriteIII AnhydriteII AnhydriteI Formula CaSO4.2H2O CaSO4.0.5H2O CaSO4 CaSO4 CaSO4 Stability Crystal Density Water 0 g/cm3 C % 20.92 2.32 40 6.21 2.70 Metastable 0 2.50 Metastable 0 2.98 401180 0 ~ >1180 Solubility@200C % 0.20 0.95 0.95 0.20 ~ Occurrence In In nature cement Yes No No Yes No Yes Yes Yes No Clinker

The stable forms existing in nature are the dihydrate and anhydrite II and the metastable forms are hemihydrate and anhydrite III, which do not exist in nature but are formed during grinding and storage

of cement. Anhydrite I, a variety which is formed during calcinations of clinker, is seldom found in cement. During communition, in general and/or grinding of clinker and gypsum, the greater part of the mechanical energy is converted into thermic energy (temperature). Only a small part of the energy is usedfor: Breakingupcohesiveforces(physicalbindings) Breakingupchemicalbindings Deformingparticles(activationenergy) Thethermicenergycausesthedehydrationofgypsumespeciallyduringthegrindingwhiletheactivation energy, released days later as thermic energy, likewise affects the dehydration of the gypsum.It is undoubtedly the dehydration of the gypsum, a product of both the temperature and the period of exposure, which plays an important part as regards to the properties of the cement. The different influences exercised by calcium sulfates on the properties of cement are due mainly to their different degreeofsolubility. Optimumgypsumcontent The optimum SO3 content required to obtain the best strength at 28 days depends on the fineness, the alkalis and the C3A content. With increase in the specific area of cement, the amount of gypsum required for proper retardation increases since there is an acceleration in the initial reactions which mainly involves the sulphates and which determine the subsequent behavior of the hardened cement. Alkalies in Portland clinker, in general, are combined as easily soluble sulphates if sulphates are readily available or in absence of a sulphate source they are incorporated in the clinker minerals. Thus, in the calcium hydroxidealkali sulphatewater system, as the alkali content increases, the solubility of gypsum increases and the solubility of Ca(OH)2 decreases, thus affecting the aluminate and silicate phase hydration. Optimum gypsum content is related to the C3A content in a way such that the hydrating portionoftheC3Aiscombinedexclusivelyasettringite.IftheSO3 contentistoolow,thenthecementis inadequately regulated for smooth setting owing to monosulphate formation but if unnecessarily high, thentheprobabilityoffalsesetisincreasedduetoformationofsecondarygypsum.Ingeneral,itcanbe broadlystatedthatforanormalPortlandcementwithmoderateC3A(<10%)anoptimumSO3contentis about2.3%whereasforhigherC3Alevelsitisabout2.6%. The effect of gypsum upon strength in Portland cement is differently pronounced at various ages. It seems likely that the effects are the result of different influences which develop in different ways even with reference to presence of alkali sulphates. In terms of strength the addition of gypsum accelerates the rate of hydration of medium high C3S content Portland cement when added below the optimum SO3 content. When the SO3 content exceeds the optimum, it significantly retards the hydration of cement. Variations of the hydration degree thus cause variations of the total porosity of cement matrix andaccordinglyaffectthestrength. .