On the Hydration of Portland Cement Author(s): J. D. Birchall, A. J. Howard, J. E.

Bailey Reviewed work(s): Source: Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, Vol. 360, No. 1702 (Apr. 4, 1978), pp. 445-453 Published by: The Royal Society Stable URL: http://www.jstor.org/stable/79592 . Accessed: 09/11/2011 10:46
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Proc. B. Soc. Lond. A. 360, 445-453 (1978) Printed in Great Britain

On the hydration of Portland cement

BY J. D. BIRCHALL,t A. J. HOWARDt AND J. E. BAILEY;

t Imperial Chemical Industries Limited, Mond Division, Runcorn, Cheshire, U.K.

t Departmnent Metallurgy and Materials Technology, of

University of Surrey, Guildford, U.K. by (Communicacted A. Kelly, F.R.S. - Received 11 May 1977 - Revised 10 November 1977)
[Plate 1]

When Portland cement is contacted with water, calcium ion is rapidly leached from the solid to form calcium hydroxide solution but only traces of silica are found in the aqueous phase. It is proposed that the hydrated, calcium-depleted surface of grains consists of low molecular mass silicic acids and that these interact with dissolved hydroxylated calcium species (principally Ca(OH)2) to produce a semi-permeable membraine of 'calcium silicate hydrate' at the hydrated grain surface. Osmotic pressure within this membrane causes its rupture and hence the growth of exerescences from the grain as the contents are extruded into the surrounding calcium hydroxide solution. The interstitial solid material is best regarded as a coagultum resulting from the combination of low molecular mass silicate anions with dissolved calcium hydroxide. It is proposed that the low tensile strength of Portland cement paste results from microstructural features consequent upon this mechanism of hydration and setting.
INTRODUCTION

The property of materials made from Portland cement that most restricts their use is a tensile strength that is low (5-15 MN/M2) in comparison with other structural materials such as wood (100 MN/M2) and steel (1000 MN/M2). Until comparatively recently few attempts have been made to relate this deficiency to the microstructure of cement and to the mechanism by which this microstructure develops during hydration and setting. The major constituents of Portland cement are alite (essentially tricalcium silicate, Ca3SiO5or C3A)at ca. 50 % (by mass) and belite (essentially ,-dicalcium silicate, P-Ca2Si04 or p-C2S) at ca. 25 %(by mass); smaller proportions of aluminate, ferrite and free lime etc. are also present (Taylor I 964). When cement clinker is exposed to water, the anhydrous components react to form hydrated products, principally calcium silicate hydrate (C-S-H) at ca. 70 % (by mass) and well crystallized calcium hydroxide (Portlandite) at ca. 20 % (by mass) (Diamond 1976).
[445]

446

J. D. Birchall, A. J. Howard and J. E. Bailey

Calcium silicate hydrate is of variable composition and its formation cannot be expressed by simple equilibria. When Portland cement powder is mixed with water the paste will typically contain 40 % solids and 60% water (Powers I964), and setting must involve a redistribution of the material of the clinker to fill the interstitial space occupied by water. The precise mechanism of this space-filling remains obscure; Taylor (i 964) says: 'An unsolved problem... concerns the relative importance of mechanisms involving dissoluLtionand reprecipitation and those taking place by conversion of solids in situ.' Cement products can be considered as dispersions of solid particles (unhydrated grain residues in cement pastes; sand, gravel, etc., in mortars and concretes) in a matrix of hydration products. Attempts to relate, by direct examination, the microstructure of cement paste of realistic water/cement ratio to its mode of formation prove confusing because of the density of packing of the interstitial material. However, cement hydrated at higher water/cement ratios in which the hydration of individual grains can be observed, shows a two-stage process. First, a shell of hydrous, gel-like material is formed around the grain and from this, fibrillar outgrowths are later seen to develop. In this paper an attempt is made to explain the mechanisms by which the morphology (observed most clearly in dilute pastes) arises and to relate this to the mechanical properties of dense, hydrated cement paste, an approach which has received only limited attention (see for example, Walsh, Otooni, Taylor & Marcinkowski I974). The work concentrates on the major interstitial material (C-S-H) since this is likely to play the dominant part in the hardening process and in the mechanical properties of the final material.

CHEMICAL

CHANGES

DURING

HYDRATION

Calcium and silicon are two of the major elements of cement and their appearance in the aqueous phase of a slurry was followed. Portland cement powder was stirred with water (at 1: 5 ratio), at 20 ?Cfor varying lengths of time, filtered and the filtrate analysed. Calcium is leached very rapidly from the cement grains reaching a concentration in the aqueous phase corresponding to 100 0 super-saturation with respect to Ca(OH)2 within 1 min, in agreement with the findings of other workers (see, for example, Ludwig 1974). The subsequent decrease in concentration at leaching times greater than 5 min is consistent with the relief of supersaturation by the nucleation and growth of Ca(OH)2 (Portlandite) and its subsequent removal by filtration. Filtrates were also analysed for Si02 (table 1) and it is evident that virtually no soluble silica is released to the bulk aqueous phase when cement is contacted with water. Leaching times from 30 s to 15 h failed to give SiO2 concentrations in excess of 3 jig/g. On contacting cement with water at ratios 1: 2-1: 10, the pH of the aqueous phase rises to 12.5-12.7 within 15s and remains at that level for as long as measurement is practicable. The effect of changing this 'equilibrium' pH on the leaching

On the hydration of Portland cement

447

of SiO2 was studied by stirring cement/water (1: 5) slurries for 15 h at 20 ?C using water of varying initial pH and analysing the filtrates for SiO2 (figure 1). The amount of SiO2 leached from cement grains increases progressively as the pH is reduced from the 'equilibrium' value and the concentration of SiO2 found at pH 8 (ca. 130 jg/g) accords well with the saturation concentration of low molecular mass silicic acid in water (Iler I955).
TABLE

1. APPEARANCE

OF SOLUBLE SILICA IN BULK

AQUEOUS PHASE AS A FUNCTION OF TIME soluble Si02 time of leaching 6s 30s 1 min 6 min 30 min 15 h pg/g 0.2 0.6,1.8 1.6 2.2 2.4 1.5

1 120 o\ . 80 _

pH of normal cement paste

*~40

E~~~~~
8
0 1

|
I I I

'

/
14

12 10 initial pH of aqueous phase

FIGURE 1. Leaching of silicon from Portland cement as a function of pH.

EFFECT

OF

pH

ON MORPHOLOGY

The increase in Si02 leached from Portland cement effected by a reduced initial pH, prompted an investigation of the morphological features produced by hydration in water at a pH lower than that of 'normal' cement paste. Scanning electron micrographs (s.e.m.) were produced of pastes prepared: (a) in pure water (figure 2, plate 1) and (b) in water at pH 8 (figure 3, plate 1), the pastes being mounted and cured (5 d; 100 % r.h.) directly on s.e.m. sample holders. The control shows the fibre-like morphology reported by other workers (see, for

448

J. D. Birchall, A. J. Howard and J. E. Bailey

example, Williamson I 972) but the low pH sample shows an absence of the normal hydration features and yet the grains, which did not agglomerate,could be dried only with difficulty implying a considerablepenetration by water. It is difficultto invoke a dissolution, nucleation and particle growth mechanism for the appearanceof C-S-Hin the interstitial space of cement paste when one constituent of C-S-H (Si02) does not appear in the bulk aqueous phase. Clearly any movement of SiO2is restricted to the vicinity of the original particle under normal conditions, a restriction which can be removed by reducing the pH of the aqueous phase; the Si02 level in the aqueous phase then rises to saturation level, but the normalformationof C-s-H is notobservedby electron microscopy. At pH values not exceeding 8.5 calcium will exist as Ca2+ (Britton I927) and silica species will be but weakly ionized (Iler I955) whereas at pH 12.6, calcium will be present as hydroxylated species (principallyCa(OH)2)and silica as silicate anions. This suggests that the principalinterstitial material (C-S-H)is formedat the grain surfaceby the combinationof dissolved calciumhydroxide and silicate anionDS. In an analogous system - the precipitation of 'hydrated calcium silicates' on mixing solutions of sodium silicate and calcium chloride- we have shown that no precipitate is formed when the solutions are adjusted to pH less than or equal to 8.5 before mixing.
ON
THE NATURE OF

C-S-H

The nature of the precipitates formed from silicate- and calcium-containing solutions at normalcement paste pH (ca. 12.6)was studied by X-ray diffractionand compared with materials related to cement and its hydration products. Dilute (0.025M) solutions of CaCl2and sodium silicate were mixed, both having been adjusted to pH 12.6 and filtered before mixing. Three sources of soluble silicate were used, namely sodium orthosilicate, sodium metasilicate and 'water glass' (I.C.I. P84 grade; SiO2:Na2Oratio = 3.3). The precipitates formed were allowed to settle, filtered, exhaustively washed and dried at 25 ?C and examined by X-ray diffraction(figure4). The figureincludes data on the constituents of cement and on cement hydration productsfor comparison,the data being presentedin a schematic form in which vertical lines representthe incidence of reflexionsas a function of the Bragg angle and the height of a line is proportionalto the intensity of the reflected beam. The reflexions from the hydrated products are somewhat diffuse compared to those of the anhydrous materials, and this is illustrated by broadening the reflexionlines. The data are presentedin decreasingorderof crystallinity (reducing number and sharpness of reflexions) and suggest that the C-S-H gel formed in hydrated cement is not unique and that hydrosilicates of similarly low degrees of long range order can be produced for example, by precipitation from solutions containingcalciumand siliconof non-cementitiousorigin.

Proc. R. Soc. Lond. A, volume 360

Birchall et al, plate I

_^~~~~~~~~~~~~~-

FIGURE

2. Scanning electron micrograph of Portland cement paste; water/cement ratio = 5: 1; with pure water. (Magn. x 2250.)

FIGURE

3. Scanning electron micrograph of Portland cement paste; water/cement ratio = 5: 1, with buffer solution at pH 8. (Magn. x 1500.) 5. The 'reversed silicate garden'; sodium orthosilicate solid immersed in calcium chloride solution (12.5 %O mass). Transmitted light. (Magn. x 15.) by
(Facing p. 448)

FIGURE

On the hydration of Portland cement

C3S anhydrous

449

anhydrous O-C2S

3A

P84 Afrom waterglassst

A\

eA
AL

A A

6
C-ge-em n paste . . . .

7 5 10 20 30
20/deg
FIGURE 4. X-ray diffraction

40

50

60

of cement and related materials. Data sources: 1, 2, Taylor (i

956);

3, 4, 5, precipitates formed by mixing CaCl2 and sodium silicates; 6, Diamond (I976);

7, Taylor (1 964).

THE

MODE

OF FORMATION MATERIAL

OF THE INTERSTITIAL IN CEMENT

The changes observed around cement grains during hydration have been described by several workers and recently the process has been observed directly under the electron microscope (Double & Hellawell I976). Initially, a gel-like layer forms around each grain which extends slowly into the core. After 1-3 h, fibre-like outgrowths are observed radiating from the grain, the resemblance of the process to that obtaining in the well known 'silicate garden' having been implied by Powers and recently emphasized by Double & Hellawell (1976). In the 'silicate (I96I) garden' tubiform growths emanate from a crystal of a soluble, polyvalent metal salt placed in a solution of sodium silicate. lt is significant that this process does not occur with a calcium salt if the silicate solution is at pH 8.5 or below, again supporting the view that precipitation of 'hydrated calcium silicates' results from the combination of silicate anions and calcium hydroxide. The 'silicate garden' process is not strictly analogous to that of cement hydration since in the latter, the aqueous phase is essentially a solution saturated or supersaturated with respect to Ca(OH)2, with silicate confined to the region of the grain. ln experiments to produce a system more akin to hydrating cement, crystals of a soluble silicate

450

J. D. Birchall, A. J. Howard and J. E. Bailey

(sodium orthosilicate) were immersed in calcium chloride solutions of various strengths. The crystals dissolved to produce NaOH and SiO4- ions and the formation of a membranous sheath around the crystal was observed to be followed by the appearance of outgrowths which may be tubiform (figure 5, plate 1). Similar experiments with sodium metasilicate, and solid produced by drying 'water glass' failed to produce such outgrowths.

DISCUSSION It now becomes possible to construct a model for the hydration and setting of Portland cement and this is shown schematically in figure 6. Both C38 and P-C2S have orthosilicate structures with isolated [5i04] tetrahedra joined through calcium

(Jeffrey

1952;

Midgley 1952)

and the removal of the latter by addition of water

will necessarily release orthosilicate species. Thus the early stage of hydration involves the rapid leaching of calcium into the bulk aqueous phase and the formation of a calcium depleted layer of orthosilicic species round the cement grains. This layer increases in depth as hydration progresses into the grain. The pH of the bulk aqueous phase (now a solution supersaturated with respect to Ca(OH)2) is ca. 12.6 and it is known that while the monomeric anion SiO4- iS stable above pH 13.6, the dimeric anion Si206- is the principal anion between pH 10.9 and 13.6 (Jander & Heukeshoven I 93 I) although its precise state of protonation is unknown. It seems likely then that the orthosilicic species will be converted to disilicate anions at the interface with the bulk aqueous phase at pH ca. 12.6. It is now proposed that combination occurs at the interface between dissolved Ca(OH)2 and the dimeric silicate anions. It has been shown that in dilute solution, combination between soluble silicates and metal salts occurs only at pH values slightly below and upwards of that at which the metal hydroxide is precipitated (Britton 1927). For calcium this occurs at pH 9-10 and the combination, according to Iler (I 955) may best be regarded as 'mutual coagulation' of a positively-charged metal hydroxide with silicate anion. Hence a membranous precipitate of C-S-H is formed at the interface through which water passes into the grain and calcium ions pass outwards to the bulk aqueous phase. Osmotic pressure rises within the membrane eventually causing its rupture at weak points and extruding the fluid contents (essentially a solution of orthosilicate and disilicate anions) into the bulk aqueous phase. Continuous precipitation of C-S-H at the stream periphery then gives rise to tubiform excrescences. It is significant that both sodium metasilicate (comprising an infinite chain structure) and sodium silicate solid derived from water glass (a three-dimensional polymeric structure) fail to produce a 'reversed silicate garden' effect, confirming the requirement for low molecular mass silicate anions in the vicinity of the solid. The view that early hydration products of cement contain mainly dimeiic silicate species is supported by the studies of Tamas, Sarkar & Roy (1976) and Lentz (1 966), by the technique of trimethylsilylation.

On the hydration of Portland cement

451

H20

anhydrous cement grains

supersaturated at Ca(OH)2 pH 12.7

Ca2+ rapidlyleached
t

,, Ca(OH)2 crystallizing

2+ Ca 2+ 0:Ca

anhydrous

core

Ca-depleted layer; [-

mass low molecular

silicic acids- swelling

and imbibingwater

mixedhydroxide membrane formed

fibrillar outgrowths > formedby osmotic ' of bursting membrane

FIGURE

6. Schematic model for the hydration and setting of Portland cement.

Thus as far as the formation of the major interstitial material is concerned the early hydration and setting of Portland cement may be represented by: cement clinker + water -? orthosilicate anions + calcium hydroxide
(surface) (dissolved)

orthosilicate anions P!-> disilicate anions

(surface) 12.6 (surface)
-?

disilicate anions + calcium hydroxide

(surface) (dissolved)

C-S-H
(formed outward from surface)

The present work confirms that crystallization (defined as the nucleation and growth of solids having long range order) is not involved in the early formation of

452

J. D. Birchall, A. J. Howard and J. E. Bailey

the major cementing phase in Portland cement - the hydrated calcium silicates; nor is a 'through solution' mechanism involved. C-S-H is a disordered material (best regarded as a mixed hydroxide), the morphology of which is determined not by crystallographic considerations, but by a curious mode of precipitation perhaps best described as 'membrane precipitation'. Crystalline material will necessarily be present in the hydrated mass, notably Portlandite, but this will have less effect on mechanical properties (particularly tensile strength) than is imposed by the nature of the major space-filling material, C-S-H. The generation of C-S-H morphology is most clearly seen when cement grains are hydrated in relative isolation from other grains. In realistic cement pastes (water/ cement ratios of say, 0.3-0.5) grains are much closer together, but there is no reason to suppose that the osmotic mechanism of space-filling does not occur, although the morphology will vary as packing alters the geometry of the interstitial space. Hence in hardened cement pastes, unhydrated grain residues are held together by a discontinuous but interpenetrating mass of C-S-H in forms that have arisen from osmotic bursting. Such a microstructure accords well with recent observations on the fracture behavxiour of hardened cement pastes. It has been shown (Higgins & Bailey 1976a) that the strength of such pastes is relatively insensitive to notch damage, the strength being reduced only by a factor of 3-4 whereas equivalent notch damage in glass results in a reduction factor of ca. 100. This difference in behaviour is attributable to inherent flaws in set cement. The observation of fine crack propagation in cement paste by a new technique (Higgins & Bailey I976b) has shown fine stable cracks to propagate before catastrophic failure. Close inspection shows the cracks to be tortuous at two levels; on a scale of some mnicronssuggesting the avoidance of dense regions (e.g. unhydrated grain residues, Portlandite, etc.) and at a finer level implying sub-micron inhomogeneity which is consistent with a model for cement paste in which the grains are held together by interpenetrating but discontinuous outgrowths (Higgins & Bailey
I 976a).

While the early processes of hydration and setting involve low molecular mass silicate species (mainly dimeric species), changes occur with time. The work of Lentz (I966) suggests that, for example, in 103 days, over 30 % of the silicate in the hydrated material is polymeric, there being a corresponding decrease in the proportion of dimer. Such changes probably involve the migration of calcium from C-S-H to such 'calcium sinks' as Portlandite crystals and may also involve morphological change in C-S-H. The inherent strength of cement paste as predicted from fracture studies (Higgins & Bailey I976 a) is of the order 15MN/M2 and this low value is thought to be a consequence of discontinuities in the microstructure of the paste. The importance of this present view of hydration and setting of Portland cement is that it may suggest novel ways for modifying the microstructure, reducing discontinuities, and realising considerable improvements in strength.

On the hydration of Portland cement

REFERENCES

453

Britton, H. T. S. I927 J. chem. Soc. pp. 425-436. Diamond, S. I976 Proceedings of the conferenceon hydraulic cementpastes; their structure and properties, Sheffield, 8-9 April, pp. 2-30. Cement and Concrete Association. Double, D. D. & Hellawell, A. I976 Nature, Lond. 261, 486-488. Higgins, D. D. & Bailey, J. E. I976 a J. Mater. Sci. 11, 1995-2003. Higgins, D. D. & Bailey, J. E. I976 b Proceedings of the conferenceon hydraulic cementpastes; their structure and properties, Sheffield, 8-9 April, pp. 283-296. Cement and Concrete Association. Iler, R. K. I955 The colloid chemistry of silica and silicates. Ithaca, New York: Cornell University Press. Jander, C. & Heukeshoven, W. I93I Z. anorg. allg. Chem. 201, 361-382. Jeffrey, J. W. I952 Acta Crystallogr. 5, 26-36. Lentz, C. W. I966 Highways Research Board. Washington D.C. Special Report 90, pp. 269-283. Ludwig, U. I974 Int. Congr. Chem. Cement., Moscow. Principal paper 6. Midgley, C. M. I952 Acta Crystallogr. 5, 307-312. Powers, T. C. I96I J. Portland Cem. Ass. Res. Dev. Labs 3, 47-56. Powers, T. C. i964 The chemistry of cements, vol. 1 (ed. H. F. W. Taylor). New York: Academic Press. Tamas, F. D., Sarkar, A. K. & Roy, D. M. I976 Proceedings of the conference on hydraulic cement pastes: their structure and properties, Sheffield, 8-9 April, Cement and Concrete Association. Taylor, H. F. W. I956 Crystallographic data for the calcium silicates. H.M.S.O. Taylor, H. F. W. i964 The chemistry of cements, vol. 1. (ed. H. F. W. Taylor). New York: Academic Press. Walsh, D., Otooni, M. A., Taylor, M. E. Jr & Marcinkowski, M. J. I974 J. Mater. Sci. 9, 423-429. Williamson, R. B. I972 Progr. Mater. Sci. 15, 189-286.