Available online at www.sciencedirect.

com

Cement and Concrete Research 38 (2008) 137 – 158

The calcium silicate hydrates

I.G. Richardson⁎
School of Civil Engineering, University of Leeds, Leeds LS2 9JT, United Kingdom

Received 16 November 2007; accepted 19 November 2007

Abstract

This article is concerned with the calcium silicate hydrates, including crystalline minerals and the extremely variable and poorly ordered phase (C-S-H)
that is the main binding phase in most concrete. Up-to-date composition and crystal-structure information is tabulated for the most important crystalline
calcium (alumino) silicate hydrates and related phases. A number of models for the nanostructure of C-S-H are summarized and compared and it is shown
that there is much more of a consensus than might seem apparent at first sight. The value of the recently solved structures of 1.4 nm tobermorite and
jennite, together with those of jaffeite and metajennite, for visualizing the nanostructural elements present in the models is demonstrated. The importance
of Hal Taylor's contribution to the solution of the structure of jennite is highlighted. The applicability of Richardson and Groves' model is demonstrated
using experimental composition-structure observations on the nature of C-S-H in a Portland cement-fly ash blend.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Cement; Calcium silicate hydrate (C-S-H); Crystal structure; TEM

1. Introduction sentence to the first paper read at that meeting in 1918, Cecil H.
Desch noted with regard to calcareous cements that ‘…our
Many naturally occurring crystalline calcium silicate hydrates or knowledge of the scientific nature of the materials and processes
calcium aluminosilicate hydrates are relevant to Cement Science, involved is even yet imperfect, in spite of many excellent
either because they are formed hydrothermally — as in deep oil- investigations covering various parts of the subject’. The same
well or geothermal cements — or in autoclaved or hot-pressed statement could be used today, but ninety additional years of
materials, or because their structures have proved to be very useful investigations — utilizing increasingly sophisticated experimental
in modeling the structure of the extremely variable and poorly techniques — have of course resulted in many significant advances
ordered phase that is essentially the ‘glue’ of the concrete part of the in our knowledge; the Proceedings of the international conferences
Built Environment. The nature of this phase was discussed [1–3] at in this series have to date been a valuable record of those advances,
the meeting in London in 1918 that later came to be considered to as is outlined by Francis Young elsewhere in this issue [4]. The
be the first in the series of international conferences on the purpose of this article is threefold: firstly, to tabulate up-to-date
chemistry of cement of which this is the twelfth.1 In the opening composition and crystal-structure information for the most
important calcium (alumino) silicate hydrates and related phases,
which should be a useful reference source for others interested in
⁎ Tel.: +44 113 343 2331; fax: +44 113 343 2265. these phases; secondly, to summarize and compare the various
E-mail address: [email protected].
1
The meeting of the Faraday Society to discuss ‘The Setting and Hardening of
models that exist for the nanostructure of the calcium silicate
Cements and Plasters’ was held on Monday, January 14, 1918, in the House of hydrate (C-S-H) phase in hardened C3S and Portland cements — or
the Royal Society of Arts, John Street, Adelphi, London, and was published in in blends of Portland cement with supplementary cementing
Volume 14 of the Transactions of the Faraday Society in January 1919. The materials —many of which are in fact much more similar to one
Faraday Society ‘...had intended to inaugurate a research into the question of another than might seem apparent at first sight; and thirdly, to
cements and setting generally, realizing its great importance, but there has been
great difficulty in this owing to the war, and the Council have considered the best
highlight the recent solutions to the structures of jaffeite, jennite,
thing they can do is to have a discussion such as we are going to have this metajennite (as yet unrefined) and 1.4 nm tobermorite, and to
evening’ (James Swinburne FRS, Past-President and Chair of the meeting). demonstrate how the structures of these phases are useful for
0008-8846/$ - see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cemconres.2007.11.005
 138
Table 1
Crystal-structure data for calcium silicate hydrates, calcium aluminosilicate hydrates and related phases
Name Formula Ca/Si References Sy SG Mr cell Z Mr V Dc a b c α β γ
g mol− 1 formula Å3 g cm− 3 Å
g mol− 1
(a). Wollastonite group
Foshagite Ca4(Si3O9)(OH)2 1.33 [6,7,8,9,10] Tc P 1̄ 845.17 2 422.59 513.0 2.736 10.32 7.36 7.04 90 106.4 90

Hillebrandite Ca2(SiO3)(OH)2 2.00 [11,12,9,10,13–17] O C m c 21 1141.53 6 190.25 702.1 2.700 3.6389 16.311 11.829 90 90 90

Nekoite Ca3Si6O15·7H2O 0.50 [18,19–21] Tc P1 654.85 1 654.85 490.3 2.217 7.588 9.793 7.339 111.77 103.5 86.53

Okenite [Ca8(Si6O16)(Si6O15)2 0.56 [22,23,10,16] Tc P 1̄ 1966.60 1 1966.60 1418.5 2.302 9.69 7.28 22.02 92.7 100.1 110.9
(H2O)6]4–[Ca2(H2O)9·3H2O]4+

I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

Pectolite Ca2NaHSi3O9 1.00 a [24,25–29,30] Tc P 1̄ 664.821 2 332.41 382.2 2.888 7.98 7.023 7.018 90.54 95.14 102.55

Wollastonite 1A Ca3Si3O9 1.00 [31,29,32,33,13,34] Tc P 1̄ 696.98 2 348.49 396.96 2.916 7.9258 7.3202 7.0653 90.055 95.217 103.43

Xonotlite b Ca6Si6O17(OH)2 1.00 [35,36,10,13,14,37–45] M P 1 2/a 1 1427.99 2 713.99 879.3 2.700 17.032 7.363 7.012 90 90.36 90

(b). Tobermorite group

Clinotobermorite c Ca5Si6O17·5H2O 0.83 [46,47,48–50,45,51] M C1c1 2923.93 4 730.98 1859.64 2.611 11.276 7.343 22.642 90 97.28 90
Clinotobermorite d Ca5Si6O17·5H2O 0.83 Tc C 1 1461.97 2 730.98 929.8 2.611 11.274 7.344 11.468 99.18 97.19 90.03

‘Clinotobermorite 9 Å’ c Ca5Si6O16(OH)2 0.83 [46,47,51] M C 12/ c 1 2635.68 4 658.92 1528.03 2.864 11.161 7.303 18.771 90 92.91 90
‘Clinotobermorite 9 Å’ d Ca5Si6O16(OH)2 0.83 Tc C1̄ 1317.84 2 658.92 763.9 2.865 11.156 7.303 9.566 101.08 92.83 89.98

Oyelite Ca10B2Si8O29·12.5H2O 1.25 [52,53] O n.d. 2672.52 2 1336.26 1668.77 2.659 11.25 7.25 20.46 90 90 90

9 Å tobermorite Ca5Si6O16(OH)2 0.83 [51,54,55] O Fd2d 5271.37 8 658.92 3055.25 2.865 11.16 7.32 37.40 90 90 90
(riversideite) c
9 Å tobermorite Ca5Si6O16(OH)2 0.83 M P 1 1 21/a 1317.84 2 658.92 764.78 2.861 6.7 7.32 18.70 90 90 123.5
(riversideite) d

Anomalous Ca4Si6O15(OH)2·5H2O 0.67 [50,56,50,54] O F2dd 5543.35 8 692.92 3741.65 2.460 11.265 7.386 44.970 90 90 90
11 Å tobermorite c
Anomalous 11 Å Ca4Si6O15(OH)2·5H2O 0.67 [56–60,9,10,14] M B 11m 1385.84 2 692.92 935.4 2.460 6.735 7.385 22.487 90 90 123.25
tobermorite d
Normal 11 Å Ca4.5Si6O16(OH)·5H2O 0.75 [34,41,44,45,51,61–65] M B 11m 1423.88 2 711.94 941.68 2.460 6.732 7.369 22.680 90 90 123.18
tobermorite d

14Å tobermorite Ca5Si6O16(OH)2·7H2O 0.83 [66,67–69] O F2dd 6280.23 8 785.03 4578.56 2.278 11.2 7.3 56.0 90 90 90
(plombierite) c
14Å tobermorite Ca5Si6O16(OH)2·7H2O 0.83 [44,51,63] M B 11 b 1570.06 2 785.03 1170.4 2.228 6.735 7.425 27.987 90 90 123.25
(plombierite) d

(c). Jennite group

Jennite Ca9Si6O18(OH)6·8H2O 1.50 [70,60,71–74,12] Tc P1̄ 1063.44 1 1063.44 759.5 2.325 10.576 7.265 10.931 101.30 96.98 109.65

Metajennite Ca9Si6O18(OH)6·8H2O 1.50 [75,70,72] M I 1 2/m 1 955.30 1 955.30 631.1 2.513 9.944 3.638 17.72 90 100.09 90
(d). Gyrolite Group
Fedorite (Na,K)2(Ca,Na)7(Si,Al)16O38 0.56 e [76,77,51] Tc P1̄ 1448.66 1 1448.66 961.24 2.503 9.645 9.6498 12.617 102.43 96.247 119.89
(F,OH)2·3.5H2O f

Gyrolite NaCa16Si23AlO60 0.71 e [78,79–81,9,10,16, Tc P1̄ 2685.47 1 2685.47 1824.1 2.445 9.74 9.74 22.40 95.7 91.5 120
(OH)8·14H2O 30,38,41–43,51,82,83]

K-phase Ca7Si16O38(OH)2 0.44 [51,9] Tc P1̄ 1371.91 1 1371.91 944.39 2.412 9.70 9.70 12.25 101.9 96.5 120

Reyerite Na2Ca14Si22Al2O58 0.67 e [84,80,81,85,86,51] Tg P3̄ 2451.07 1 2451.07 1574.6 2.585 9.765 9.765 19.067 90 90 120
(OH)8·6H2O

I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

Truscottite Ca14Si24O58 0.58 [81,87,88,9,43,51] Tg P 3̄ 2335.20 1 2335.20 1545.5 2.509 9.735 9.735 18.83 90 90 120
(OH)8·2H2O

Z-phase Ca9Si16O40 0.56 [78,81,42,51,82] Tc P1̄ 1736.27 1 1736.27 1238.3 2.328 9.70 9.70 15.24 90.94 93.19 120
(OH)2·14H2O

(e). γ-C2S group

Calcium chondrodite g Ca5[SiO4]2(OH)2 2.50 [89, 90–93,15,17] M P 1 1 21/b 837.16 2 418.58 492.1 2.825 8.9207 11.4481 5.0759 90 90 108.32

Kilchoanite Ca6(SiO4)(Si3O10) 1.50 [94,9,17,40] O I2cm 2307.21 4 576.80 1275.9 3.003 11.42 5.09 21.95 90 90 90

(f). Other calcium silicate phases

Afwillite Ca3(SiO3OH)2·2H2O 1.50 [95,96–100,9, M C1c1 1369.82 4 342.46 859.6 2.646 16.278 5.6321 13.236 90 134.90 90
10,14,44,64]

α-C2SH Ca2(HSiO4)(OH) 2.00 [101,102,103,9,13, O P 21/b 21/c 1522.07 8 190.26 928.8 2.721 9.487 9.179 10.666 90 90 90
15,17,38,40,42,43,104] 21/a

Cuspidine h Ca4(F1.5(OH)0.5)Si2O7 2.00 [105,106–108,13] M P 1 21/c 1 1461.96 4 365.49 814.2 2.982 7.518 10.521 10.906 90 70.7 90

Dellaite Ca6(Si2O7)(SiO4)(OH)2 2.00 [109,110,111,15,17] Tc P1̄ 1069.49 2 534.74 598.8 2.966 6.825 6.931 12.907 90.68 97.57 98.18

Jaffeite Ca6[Si2O7](OH)6 3.00 [112,113,15,17,38, Tg P 3 1021.38 2 510.69 654.0 2.593 10.035 10.035 7.499 90 90 120
40,41,70,104]

Killalaite Ca6.4(H0.6Si2O7)2(OH)2 1.60 [114,115] M P 1 21/m 1 1258.49 2 629.24 710.2 2.943 6.807 15.459 6.811 90 97.76 90

Poldervaartite i Ca(Ca0.67Mn0.33)(HSiO4)(OH) 2.00j [116] O P 21/b 21/c 1561.69 8 195.21 904.8 2.866 9.398 9.139 10.535 90 90 90
21/a

Rosenhahnite Ca3Si3O8(OH)2 1.00 [117,118–120] Tc P1̄ 733.02 2 366.51 420.2 2.897 6.955 9.484 6.812 108.64 94.84 95.89

Suolunite CaSiO2.5(OH)·0.5H2 O 1.00 [121,122–125] O Fd2d 2146.87 16 134.18 1317.1 2.707 19.776 5.99 11.119 90 90 90

Tilleyite Ca5Si2O7(CO3)2 2.50 [126,127,128] M P 1 2/a 1 1954.35 4 488.59 1131.8 2.867 15.108 10.241 7.579 90 105.17 90
(continued on next page)

139
 140
Table 1 (continued)
Name Formula Ca/Si References Sy SG Mr cell Z Mr V Dc a b c α β γ
g mol− 1 formula Å3 g cm− 3 Å
g mol− 1
(g). Other high temperature cement phases

I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

0.67 k [129,130,131,132]
P
Bicchulite Ca2(Al2SiO6)(OH)2 C I 4 3m 1168.86 4 292.22 688.9 2.818 8.8318 8.8318 8.8318 90 90 90

Fukalite Ca4(Si2O6)(CO3)(OH)2 2.00 [133,134] O P 21 21 21 1626.02 4 406.50 966.2 2.794 3.786 10.916 23.379 90 90 90

Katoite Hydrogarnet l 0.94k I41 =a 3 2=d 3211.72

P
Ca1.46AlSi0.55O6H3.78 [135,38,41,65, C 16 200.73 1847.3 2.887 12.27 12.27 12.27 90 90 90
136–139]

Rustumite Ca10(Si2O7)2(SiO4)Cl2(OH)2 2.00 [140,110] M C 1 2/c 1 3736.56 4 934.14 2124.1 2.921 7.620 18.550 15.510 90 104.33 90

Scawtite m Ca7(Si6O18)(CO3)·2H2O 1.17 [141,142–146,13,127] M C1m1 1666.21 2 833.11 1003.2 2.758 11.0394 15.1935 6.6344 90 115.645 90

0.62k
P
Strätlingite Ca2Al(AlSi)2.22O2 [147,148–150,151,152] Tg R 3 2=m 1334.65 3 444.88 1079.6 2.053 5.745 5.745 37.77 90 90 120
(OH)12·2.25H2O
References for data that are associated with a full crystal-structure solution are shown underlined; other selected relevant references are included (not underlined), with those published since the 11th International
Congress on the Chemistry of Cement shown in bold type. The crystal system (Sy) is indicated by: C = cubic; M = monoclinic; O = orthorhombic; Tg = trigonal; Tc = triclinic. SG = full international space group. Dc is the
calculated density.
a
(Na + Ca)/Si.
b
Ma2bc polytype (an MDO2 polytype).
c
MDO1 polytype.
d
MDO2 polytype.
e
(Na + K + Ca)/(Al + Si).
f
Actual composition: (Na1.29 K0.79)(Ca4.48Na2.52)Si16O38F2·3.47H2O.
g
Synthetic phase similar to the mineral reinhardbraunsite, Ca5[SiO4]2(OH,F)2.
h
Cuspidine: cell parameters given in the paper transformed by the following matrix (00-1/010/100).
i
Isostructural with α-C2SH; j(Ca+Mn)/Si.
k
Ca/(Si + Al).
l
Composition is variable.
m
Scawtite: cell parameter, a, given in the paper as 10.0394 is a mistake and has been corrected to 11.0394 Å.
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 141

visualizing the models for the nanostructure of C-S-H. The material mean length from 2 in young pastes, to about 5 in mature pastes,
in this article is extended in a companion paper [5] in which the whilst values of 20 or greater can be found in blended cements
cohesion forces that act between individual C-S-H layers or cured at elevated temperature (for example [156] ). As well as the
crystallites are considered, and two possible strategies are discussed mean length, a successful model must also account for the
for tuning the mechanical properties of cementitious materials experimentally observed sequence of chain lengths; i.e. 2, 5, 8, …
based on modifying the bonding scheme in C-S-H. (3n − 1) where n is integer (for individual structural units), and
that in Al-substituted C-S-H, Al3+ substitutes for Si4+ only in the
2. Crystalline calcium silicate hydrates central tetrahedron of pentamers — or in every third tetrahedron
in longer chains — which has now been observed by a number of
Crystal-structure data are given in Table 1 for the most workers [157–159]. It should also be remembered that there is
important calcium (alumino) silicate hydrates and related phases. some hydrated monomer to consider that forms during the
The references for the data that are associated with full crystal- induction period, some of which persists over long timescales
structure solutions are shown underlined; a selection of other (years) in some systems [160–162].
relevant references are included (not underlined), with those Unsurprisingly, given the importance of concrete to the Built
published since the 11th International Congress on the Chemistry Environment, a large number of models have been proposed for the
of Cement (ICCC) are shown in bold type. The arrangement of nanostructure of C-S-H, many of which are listed in Table 2.
the phases in the table is derived from Table II of Taylor and Roy Table 2 includes information on: the authors of each model; the
[153], which was the Principal Report at the 7th ICCC on the principal reference(s) with date(s) of publication; the main crys-
Structure and Composition of Hydrates. Whilst the information in talline phase from which the model is derived; the nature of the
Table 1 is much more comprehensive than that given by Taylor silicate anions; if given, the main formulation or structure-compo-
and Roy — and also more so than that given in a Plenary Paper at sition relationship; and some comments, including a brief note of
the 5th ICCC [154] — in contrast with those papers, no further links with other models. It is evident from the table that all the
discussion is provided in this article on the nature of the phases models fall into one of two categories: one where the silicate anions
other than 1.4 nm tobermorite, jennite, metajennite and jaffeite. are entirely monomeric, and the other where they are derived from
The reader is instead directed to the extensive list of references, the type of linear silicate chain that is present in 1.4 nm tobermorite
which includes an excellent review article by Bonaccorsi and (and a number of other minerals); i.e. dreierkette-based models.
Merlino [51] in which the tobermorite and gyrolite groups are
discussed in detail; Bonaccorsi and Merlino's determinations of 3.1. Models involving monomeric silicate anions
the crystal structures of 1.4 nm tobermorite and jennite are two of
the most significant advances in Cement Science since the 11th Bernal [164] considered that the greater part of the silica in the
ICCC. Table 1 is intended to be a useful reference point for hydration products of a set cement is in the form of two hydrated
anybody interested in crystalline calcium silicate hydrates. In calcium silicates, which were termed C2SH(II) and CSH(I). He
particular, the fact that the crystal structures have now been solved speculated that both these phases included the monomeric silicate
for so many of the phases means that calculated X-ray diffraction anion [SiO2(OH)2]2−, and proposed the general formula given as
(XRD) patterns can be used instead of experimentally-derived Formula 1 in Table 2. Shpynova et al. [169] and Grudemo [176]
patterns, which should enable more reliable indexing, checking of also proposed models that involve monomeric silicate anions.
peak intensities and easier recognition of peaks from impurities. Both were derived from the structure of Ca(OH)2 in an
attempt to explain anomalous XRD peak intensities observed
3. Models for the nanostructure of C-S-H in hardened C3S for Ca(OH)2 in hardened cements. For example, in Shpynova's
and Portland cements, or in blends of Portland cement with model (OH)4 in the triple formula Ca3(OH)6 is replaced by
supplementary cementing materials [SiO4] giving — with some additional molecular water — Ca3
[SiO4](OH)2·2H2O (Formula (3), Table 2). Whilst monomer is
Unfortunately, in contrast to the phases in Table 1, the C-S-H the only hydrated silicate species present during the induction
that is the principal binding phase in most concrete is nearly period of hydrating C3S, none of these monomer-based models
amorphous, and so X-ray diffraction techniques are of limited are consistent with the experimentally observed distribution of
value. Any model that is developed for its nanostructure must of silicate anions for the C-S-H that forms afterwards (see Section
course be consistent with experimental observations from other 3.3 in [189] for discussion).
techniques; most importantly, it must be compatible with the wide
ranges in chemical composition and silicate (or aluminosilicate) 3.2. Dreierkette-based models for C-S-H
anion structure that have been observed. The C-S-H present in
hardened pastes of C3S or neat Portland cements generally has a The first dreierkette-based model for C-S-H was due to
mean Ca/Si ratio of about 1.75, with a range of values within a Bernal et al. [163]. They performed X-ray studies on hydrated
given paste from around 1.2 to 2.1 [155]; if a paste contains a C3S pastes and considered that the C-S-H phase formed was
supplementary cementing material — such as silica fume, fly ash, similar to C-S-H phases produced in dilute suspensions, which
metakaolin or ground granulated blast-furnace slag — then the they called calcium silicate hydrates (I) and (II). Calcium
mean value is much reduced, in some cases to less than 1 [155]. In silicate hydrate (I) had a layer structure, with the layers
neat C3S or Portland cement pastes, the silicate anions vary in elongated in one direction that resulted in a fibrous structure,
 142
Table 2
Summary of models for the nanostructure of C-S-H in hardened cements

Year(s) Author(s) Ref Based on Silicate anion Formulation or structure-composition equation Comments
structure of: structure

1952 Bernal et al. [163] Tobermorite Infinite Infinite-chain models not consistent with experimentally observed
distribution of silicate anions; i.e. 3n − 1 where n is integer for
individual structural units.
1954 Bernal [164] Monomer Ca½SiO2 ðOHÞ2 ½CaðOHÞ2 x ½H2 Oy ð1Þ Monomeric models not consistent with experimentally observed
distribution of silicate anions; i.e. 3n − 1 where n is integer for
individual structural units.
x would be 1 for C2SH(II) and between 0 and 0.5 for CSH(I)
1956 Taylor and Howison [165] Tobermorite 3n − 1 Ca/Si ratio raised above 0.83 by the removal of some ‘bridging’
tetrahedra and replacement by interlayer Ca2+ ions
1960,1962 Kurczyk and Schwiete [166,167] Tobermorite Infinite Ca½Ca4 Si6 O16 ðOHÞ2 ½CaðOHÞ2 5→7 dmH2 O ð2Þ Ca2+ and OH− ions in an interlayer region, represented in their
formula as Ca(OH)2 groups, together with water molecules.
Formula is consistent with Kantro et al.'s [1962] model in

I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

which layers of tobermorite are sandwiched between layers of
calcium hydroxide.
1967 Shpynova et al. [169] Ca(OH)2 Monomer Ca3 ½SiO4 ðOHÞ2 d2H2 O ð3Þ As Bernal (1954) above.

h
i
1980–1987 Stade and co-workers [170–175] Tobermorite Dimer and polysilicate Extension of Kurczyk and Schwiete's model by allowing silicate
Ca4þy ðOHÞz H1þ2x Si2 O7 dmH2 O ð4Þ
2 chains that are not infinite, and in particular dimeric. Limits on y
simply correspond to the compositions studied.
1984 Grudemo et al. [176] Ca(OH)2 Monomer As Bernal (1954) above.
1986 Taylor [177] 1.4 nm tobermorite and jennite (3n-1) Structural elements based on 1.4 nm tobermorite and jennite
(i.e. so-called T/J model). Fixed degree of protonation of the
silicate chains.
1987 Glasser et al. [178] Tobermorite Dimer Cax H62x Si2 O7 dzCaðOHÞ2 dmH2 O ð5Þ Derived from Stade and co-workers dimeric model, Formula
(4) above (but z does not have the same definition as in
Formula (4)).

 
1992, 1993 Richardson and Groves [179,180] Tobermorite, jennite, Ca(OH)2 (3n-1) Includes both T/J and T/CH formulations; Formula (6)
CaX Hð6n2X Þ Si1a R½4
a Oð9n2Þ dIacþ
ð3n1Þ dzCa OHÞ2 dmH2 O ð6Þ
ð3n1Þ c (with no substitution) is the polysilicate equivalent of
Formula (5) (Glasser).
n o
Variable degree of protonation of silicate chains.
Ca2n Hw ðSi1a R½4
a Þð3n1Þ O9n2 Iað3n1Þ dðOHÞwþnðy2Þ dCa 2 dmH2 O
cþ ny ð7Þ
c

nð4 þ yÞ nð4 þ yÞ þ að3n  1Þ Incorporation of substituent ions, most importantly substitution

Ca=Si ¼ Ca=Si ¼ ð8Þandð9Þ of Si4+ by Al3+. Possibility that T-, J- and CH-based structural
2ð1  aÞð3n  1Þ 2ð1  aÞð3n  1Þ
elements co-exist.

1993 Taylor [181] Tobermorite and jennite 3n − 1 Ca4 ½ðSi6−Δ □Δ O18−2Δ ÞH2p Ca2p q dðOHÞ8ð1qÞ dmH2 O ð10Þ Formulation of 1986 model in response to Richardson and
Groves' model, but extended to incorporate some of their
modifications (variable protonation and substituents); as a
r 2
C=S ¼   QRT ¼  3  ð11Þandð12Þ consequence it is equivalent to Richardson and Groves'
1  m3 m1 T/J formulation.
1996 Cong and [182,183] Tobermorite 3n − 1 ‘Defect tobermorite’ model; Eqs. (11) and (12) are equivalent
Kirkpatrick to equations in Richardson and Groves' 1992 model; see
section 4.4.2 in Richardson (2004).
1997–1999 Grutzeck [184,185] Tobermorite, sorosilicate Long-chain, dimer Ca4(OH)2[SiO3.5]2·mH2O Long-chain T-based phase with low Ca/Si and a dimeric
sorosilicate-based phase with high Ca/Si.
1998 Nonat and Lecoq [186] Tobermorite 3n − 1 Two hypotheses: 1st equivalent to T units with w/n = 0 and
y = 2 in Richardson and Groves' model (Formula (7) above);
2nd involves Ca2+ and OH− ions in an
interlayer region, in which respect it is similar to Kurczyk
and Schwiete and Stade and co-workers.
2004 Chen, Thomas, Taylor, Jennings [187] Tobermorite and jennite 3n − 1 Chen et al. 's Table 5 presented formulae for Formulae equivalent to T units with w/n = 0 and y = 2 in
mean chain lengths of 2, 3, 4, 5 and ∞ Richardson and Groves' model (Formula (7) above).
2004 Nonat [188] Tobermorite; 3n − 1 Update of 1998 model; mentions jennite-based structure.
jennite.
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 143

from one another, they are in fact very similar. The similarities
between some of them have already been discussed recently
elsewhere [189], and those similarities will be only mentioned
briefly here; the reader is therefore directed to reference [189] for
the details. The models listed in Table 2 are considered in the
following discussion in chronological order.

3.2.1. Kurczyk and Schwiete [166,167]

Kurczyk and Schwiete reported results of studies on both C3S
Fig. 1. Schematic diagram showing dreierkette chains present in tobermorite and β-C2S pastes (water/cement = 0.5; 30 °C; hydrated 1, 2 and
(which in theory are of infinite length). The chains have a kinked pattern where 3 months). The studies involved transmission electron micro-
some silicate tetrahedra share O−O edges with the central Ca−O layer (called scopy (TEM) with selected area electron diffraction (SAED),
‘paired’ tetrahedra (P)), and others that do not (called ‘bridging’ tetrahedra (B)). thermal analysis, XRD and infrared spectroscopy. The Ca/Si
ratios calculated from the XRD and thermal analysis were
between 1.80 and 1.92. They suggested a hypothetical structure
and showed similarities to tobermorite, a rare crystalline formula for the C-S-H that formed in both systems (that they
calcium silicate hydrate that had been found in Northern referred to as a ‘tobermorite-like phase’) based on the same
Ireland (Ca4(Si6O18H2)·Ca·4H2O). Its structure — that was first structural elements as determined by Megaw and Kelsey [57] to
described by Megaw and Kelsey [57] — is considered in more be present in tobermorite (i.e. single chains of dreierketten
detail in Section 4. However, it is important to note here that it conformation). The tobermorite-like layers included ≡Si−OH
contains linear silicate chains of the ‘dreierkette’ form in which groups and, since they were the same as in crystalline tobermorite,
the silicate tetrahedra are co-ordinated to Ca2+ ions by linking in were presumably considered to be of infinite silicate chain length.
such a way as to repeat a kinked pattern after every three The observed Ca/Si ratios were accounted for by the inclusion of
tetrahedra. Two of the three tetrahedra share O−O edges with the Ca2+ and OH−ions in an interlayer region, represented in their
central Ca−O part of the layer; these are linked together and are formula as Ca(OH)2 groups, together with water molecules. Their
often referred to as ‘paired’ tetrahedra (P). The third tetrahedron, formula, modified with the inclusion of the interlayer water, is
which shares an oxygen atom at the pyramidal apex of a Ca given as Formula (2) in Table 2. This formula is consistent with
polyhedron, connects the two paired tetrahedra and so is termed Kantro et al.'s [168] model — which was proposed at around the
‘bridging’ (B). The dreierkette-type chain is illustrated in Fig. 1. same time —in which layers of tobermorite are sandwiched
As long ago as 1956, Taylor and Howison [165] made the between layers of calcium hydroxide.
significant suggestion that the Ca/Si ratio could be raised above
0.83 — the value for Megaw and Kelsey's tobermorite — by the 3.2.2. Stade and co-workers [170–175]
removal of some of the bridging tetrahedra and replacement by Like Kurczyk and Schwiete, Stade and Wieker [170] based
interlayer Ca2+ ions; this mechanism for raising the Ca/Si ratio is a their model on Megaw and Kelsey's proposal for the structure
central feature of most dreierkette-based models. The various of tobermorite [57]. They envisaged that poorly crystalline and
dreierkette-based models that have been proposed are listed in amorphous C-S-H phases are built up from CaOx polyhedra
Table 2. Whilst the models might at first sight seem quite different sandwiched between two silicate layers. Again, like Kurczyk

Fig. 2. Schematic representation of Stade and Wieker's model [170] illustrating the four-layer sequence (labelled as layers 1, 2, 3, and an intermediate layer, I).
144 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

Table 3 Fig. 2. Nevertheless, the formula given by Garbev et al. for

Calculated Ca/Si atom ratio and silicate chain length for the structural units Ca/Si ratio of 1.25 is useful in that it conveniently demonstrates
envisaged in Taylor's model [177]. Taylor assumed that each unit had n silanol
groups.
the close similarity of Stade and Wieker's model with others:
the formula is actually the same as that for Taylor's
Label Ca/Si atom ratio Chain length
(3n − 1)
tobermorite-based dimer (see Section 3.2.3), or, in terms of
Richardson and Groves' model [179] it corresponds to T-based
J2 2.25 2
units with w/n = 1 and y = 1.
J5 1.80 5
J8 1.69 8
J11 1.64 11 3.2.3. Taylor [177]
J¥ 1.50 ∞ Taylor's 1986 model, was a development of his earlier
T2 1.25 2 discussion, published 30 years earlier with Howison [165], that
T5 1.00 5
was mentioned above. The model envisages that C-S-H of high
T8 0.94 8
T11 0.91 11 Ca/Si is composed of structural units derived from jennite and to
T∞ 0.83 ∞ a lesser extent 1.4 nm tobermorite [177]. The silicate chains
present in jennite — which are in theory infinitely long — are
similar to those in tobermorite, i.e. both are of the ‘dreierkette’
and Schwiete, these three-layer sequences are separated by an form. However, whilst in tobermorite the main layer consists of
intermediate layer into which H2O, Ca2+, OH−, and other ions a central Ca−O part sandwiched between parallel silicate
may be incorporated to satisfy the observed composition. Their chains, in jennite half the oxygen atoms of the central
model extended Kurczyk and Schwiete's, however, in that it component are part of −OH groups. The structure of jennite is
allows for their experimental observation that the silicate chains discussed in Section 4.
in their C-S-H were not infinite and in certain circumstances The Ca/Si ratios of the structural units that result from the
entirely dimeric. They expressed their model in two forms, one omission of bridging tetrahedra from the structures of 1.4 nm
purely dimeric, and the other incorporating both dimer and tobermorite and jennite vary linearly with the reciprocal of the
polysilicate chains. The model is illustrated schematically in silicate chain length; the values for the units derived assuming
Fig. 2, which is based on figures in Stade [170]. The limits on y the level of protonation used by Taylor [177] are given in
simply correspond to the compositions studied. The formula for Table 3. To aid this discussion, the structural units derived from
purely dimeric C-S-H, as given by Stade and Wieker [170] is either jennite or 1.4-nm tobermorite are identified by the use of
given as Formula (4) in Table 2. Garbev et al. [190] used Stade ‘J’ or ‘T’ as labels [179]. Hence, J2 and T2 correspond to
and Wieker's dimeric model in a recent paper and stated that dimeric structural units that result from omission of all bridging
the maximum possible Ca/Si ratio is 1.25. It must be tetrahedra from jennite and tobermorite respectively, and J∞
emphasized that this is only the maximum because the dimeric and T∞ represent infinite chain lengths and so correspond to
silicate units in one of the layers in the model was fixed by the crystalline phases themselves. The removal of numbers
Stade and Wieker as being totally protonated, see layer 1 in of bridging tetrahedra intermediate between none (infinite

Fig. 3. Schematic diagram showing dreierkette chains present in 1.4 nm tobermorite projected along [210] (crystal structure data from [66] ). Note that the two sets of
chains in the central part of the figure are not linked, but are offset from one another by b/2.
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 145

Table 2), which allows greater flexibility in the degree of

protonation of the silicate chains; the close relationship between
the models is detailed in Section 4.4.1. of reference [189].

3.2.4. Glasser et al. [178]

Glasser et al. proposed a compositional model for dimeric
C-S-H that seems to have been derived from Stade and co-
workers' model. Whilst their thermodynamic treatment was
strictly only applicable to precipitated gels with Ca/Si ratio
between 1.0 and 1.4, they considered that the compositional
model itself could be applied equally well to young C-S-H
produced as a product of cement hydration. Glasser et al. referred
Fig. 4. Backscattered electron image of a region in a sample of 1.4 nm to Stade and Wieker's formula (i.e. Formula (4) in Table 2) but
tobermorite from Crestmore, California. The image was obtained using a Philips stated that it was ‘… difficult to write balanced equations based
XL-30 SEM operated at 20 kV. on this presentation for formation and dissolution equilibria of
C-S-H.’ They represented their model by Formula (5) in Table 2
(note that x and z do not have the same definitions as those in
length chains) and all (dimers) results in a sequence of finite Stade and Wieker's formula).
silicate chains containing 2, 5, 8, …3n − 1 tetrahedra (where n =
1, 2, 3, …), which is consistent with the silicate anion structure 3.2.5. Richardson and Groves [179,180]
observed in hardened C3S and OPC pastes (see [155,189] and Richardson and Groves [179] proposed a generalized
references therein). Taylor assumed that each bridging tetra- model that included formulations that could be interpreted
hedron carries only one H atom, and that when one of these from either the tobermorite-jennite (T/J) or tobermorite-‘solid
tetrahedra is missing only one of the broken ends of the chain is solution’ Ca(OH)2 (T/CH) viewpoints; indeed, it is possible
terminated by a H atom. Thus the net charge remains unchanged that structural elements based on tobermorite, jennite (or jaffeite;
and the omission of a tetrahedron requires no change in the see Section 4) and CH can all occur within the same system. The
amount of interlayer Ca. He stated that, ‘... there is no direct model includes maximum flexibility in the possible degree of
evidence for this assumption, but it is crystal-chemically reason- protonation of the silicate chains, and it accounts for the
able and leads to a number of results that agree with experimental substitution of Al3+ for Si 4+ ions only at bridging sites
data.’ Taylor's model can thus be considered a special case of [157,180], which is important for C-S-H present in cements
Richardson and Groves' T/J formulation (i.e. Formula (7) in containing fly ash, metakaolin or ground granulated blast-furnace

Fig. 5. High-resolution transmission electron micrograph of 1.4 nm tobermorite from Crestmore, California. The image was obtained using a Philips CM200 field
emission TEM equipped with light element EDX detector.
146 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

slag, but which is not included in other models. The two Richardson [189]. Glasser et al. 's [178] and Stade's [170] models
formulations are given in Table 2 (Formulae (6) and (7)); Eqs. (8) are also closely related. The special case of Formula (6) for dimer
and (9) are the composition–structure relationships where charge (n = 1) is the same as that given by Glasser et al. [178], Formula (5)
compensation of the substitution of Al3+ for Si4+ ions is entirely (i.e. Formula (6) is essentially the polysilicate version of Glasser's
by alkali cations or Ca2+ ions respectively. The close relationship compositional model for dimeric C-S-H) and Richardson and
between Richardson and Groves' formulations and the models Groves' alternative formulation, Formula (7), reduces to Stade's
due to Taylor [177], Cong and Kirkpatrick [182,183], Nonat and dimeric model (n = 1) if the number of silanol groups, w, is set
Lecoq [186] and Chen et al. [187] has been demonstrated in equal to (1 + x / 2) (like Taylor's model, Stade and Wieker's is less

Fig. 6. Schematic diagrams illustrating the steps taken by Taylor in deriving his model structures for metajennite and jennite; Bonaccorsi et al. 's refined structure for
jennite is shown in (g).
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 147

flexible than Richardson and Groves' in terms of the possible was due to the 1.4 nm tobermorite or oyelite (i.e. 1.0 nm
variation in the level of protonation of the silicate chains). tobermorite). TEM-EDX gave a mean Ca/Si of 0.85 (SD = 0.03,
Glasser's and Stade's models do not account for the 3n − 1 N = 28); the analyses ranged between 0.80 and 0.91. For
sequence of silicate chain lengths. Richardson and Groves' model comparison, another sample from Crestmore has been examined
is explained in detail with the extensive use of illustrative recently at the University of Leeds: the 1.4 nm tobermorite was
diagrams in reference [189]. intermixed with small amounts of oyelite and scawtite (on a host
rock containing grossular, calcite, wollastonite, Mg silicate
3.2.6. Models of Cong and Kirkpatrick [182,183], Nonat and hydrate and scawtite). TEM-EDX gave a significantly lower
Lecoq [186] and Chen et al. [187] mean Ca/Si of 0.80 (SD = 0.06, N = 19) with a broader range of
As noted above, the similarities in the models of Cong and composition — between 0.70 and 0.96 — which suggests
Kirkpatrick [182,183], Nonat and Lecoq [186] and Chen et al. significant variation in protonation of the silicate chains (which
29
[187] to the formulations of Richardson and Groves are Si NMR showed were essentially infinitely long (no Q1)).
discussed in detail in reference [189]; the reader is directed to Fig. 4 shows an illustrative backscattered electron micrograph
that article. of the tobermorite, which, together with bright field transmis-
sion electron micrographs (not shown) indicate that the
4. Tobermorite (1.4 nm), jaffeite, metajennite and jennite tobermorite has lath and platy morphologies. The layer structure
is illustrated in Fig. 5, which is a high-resolution transmission
It is evident from Table 2 and the discussion in Section 3 that electron micrograph. This particular micrograph was taken as
most models for the nanostructure of C-S-H in hardened the crystal lost interlayer water under the electron beam, which
Portland cement pastes involve elements of tobermorite-like resulted in a reduction in the layer spacing from 1.42 nm (e.g.
structure. In a number of cases, these are intermixed with others A) to 1.24 nm (e.g. C) to 1.13 nm (e.g. D); this was followed by
of jennite-like structure (or jaffeite-like; see Section 4.2): the so- decomposition of the tobermorite structure. This sequence of
called tobermorite-jennite, or T/J, viewpoint [177,179]. As a dehydration steps is direct confirmation of the thermal analysis
consequence, perhaps two of the most significant papers for and XRD results reported by Yu and Kirkpatrick [60], which
Cement Science that have been published since the 11th showed that upon heating water was lost in steps that
International Congress on the Chemistry of Cement are those by corresponded to decreases in layer spacing from 1.4 to 1.2,
Bonaccorsi et al. that report refined crystal structures for 1.4 nm 1.1 and 0.96 nm; the 1.2 nm stage was not noted by Bonaccorsi
tobermorite [66] and jennite [70], which were determined with et al. [51]. It is of interest to note that the intermediate spacing of
great skill using very small crystals. 1.24 nm is the same as the value typical of the basal spacing for
semi-crystalline C-S-H that is often observed in alkali-activated
4.1. Tobermorite (1.4 nm) hardened cements and in many synthetic C-S-H preparations,
i.e. phases that give XRD patterns that match C-S-H (I), ICDD
Bonaccorsi et al.'s determination of the structure of 1.4 nm data set No. 34-0002.
tobermorite followed very extensive studies on other forms of
tobermorite. The details of those structures have recently been 4.2. Jaffeite, jennite and metajennite
reviewed and need no further summary here, other than to note
that it includes a discussion of the reasons for so-called normal Jennite is another crystalline calcium silicate hydrate that
and anomalous behaviour and of the order–disorder (OD) has dreierkette silicate chains, but it has a much higher Ca/Si
character of phases in the tobermorite group [51]. The crystal ratio than tobermorite (formula Ca9Si6O18(OH)6·8H2O; Ca/Si
structure of 1.4 nm tobermorite consists of the same complex ratio of 1.5). Taylor suggested a tentative crystal structure for
layers that are present in 1.1 nm tobermorite: that is, it has a
central Ca-O sheet that has silicate chains on both sides, which
are kinked with a periodicity of three tetrahedra; these chains are Table 4
called dreierketten, or wollastonite-like chains. The chemical The positions of the atoms in the asymmetric unit of Taylor's model structure for
composition of the complex layer is [Ca4Si6O16(OH)2(H2O)4]2−. metajennite [75]
However, unlike 1.1 nm tobermorite, the silicate chains that Atom Position x/a y/b z/c Occ.
belong to adjacent layers are not condensed into double chains,
Ca1 (4i) 0.142 0 0.19 1
but are shifted by b/2 with respect to one another; the layers are Ca2 (4i) 0.788 0.5 0.165 1
also further apart, with the extra interlayer space occupied by H2O Ca3 (2b) 0 0.5 0 0.5
molecules and Ca2+ ions. The structure is illustrated in Fig. 3. Si1 (8j) 0.497 0.092 0.159 0.5
As well Bonaccorsi et al. 's determination of the crystal Si2 (4i) 0.33 0.5 0.068 0.5
O1 (4i) 0.206 0.5 0.11 1
structure of a sample of natural 1.4 nm tobermorite from
O2 (4i) 0.92 0 0.117 1
Crestmore, California, another sample has also been character- O3 (4i) 0.652 0 0.188 1
ized recently by analytical TEM and 29Si nuclear magnetic O4 (4i) 0.406 0 0.221 1
resonance spectroscopy (NMR) [63]. The single-pulse NMR O5 (8j) 0.425 0.125 0.081 0.5
spectrum was dominated by Q2, indicating very long silicate O6 (4i) 0.462 0.5 0.126 0.5
O7 (4i) 0.734 0.5 0.023 1
chains; the authors were uncertain as to whether a small Q1 peak
148 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

Fig. 7. The monoclinic structure of Taylor's metajennite projected along its b axis showing the positions of the atoms in the unit cell (data from [75] ). Co-ordinates (x y z)
and atom labels are given in the left and right figures respectively.

jennite 40 years ago at the 5th International Symposium on the crystals. As noted above, perhaps one of the most significant
Chemistry of Cement [154], which included a central papers for Cement Science that has been published since the
corrugated Ca−O sheet, but a full structure determination last Congress is Bonaccorsi et al. 's refined crystal structure
proved elusive because of the poor quality of available for jennite [70], which was determined using single crystal

Fig. 8. (a) Taylor's model structure for jennite (average structure) viewed along [010]; the dreierketten chains are seen end-on (data from [75] ). (b) Bonaccorsi et al. 's
refined structure for jennite (real structure) viewed along [010] (left) and [100] (data from [70] ).
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 149

X-ray diffraction data collected on a very thin crystal from [112] ), with its attached Si2O7 groups, and with the addition
Fuka, Japan. The paper includes a report of the development of of bridging tetrahedra [75]. The steps taken by Taylor in
a starting model for the structure, before describing the deriving his model structure are represented schematically in
experimental work and the structural refinement. Hal Taylor Fig. 6.
was included posthumously as a co-author on the paper and the The structure is monoclinic (space group I 1 2/m 1) with the
extent of his very significant contribution to the work was lattice parameters given in Table 1 (i.e. those reported in [72] ).
described by Bonaccorsi in an excellent presentation for the 1st Taylor located 9 Ca, 6 Si and 26 O atoms in the subcell; the
H.F.W. Taylor Memorial Lecture, which was held during the positions of the atoms in the asymmetric unit are given in
23rd Cement and Concrete Science conference, 8th–9th Table 4, and are illustrated in Fig. 7, which is projected along
September 2003, University of Leeds. In fact, Taylor had its b axis. He noted that O3, O4, O5, and O6, and in 50% of
progressed much further than his tentative structure of 1968: cases, O1 and O7, are parts of silicate chains; that O2 is
by the summer of 2000 he had determined trial substructures probably always OH, attached only to Ca; that where O1 is not
for both metajennite (Ca9Si6O18(OH)6·2H2O) — which is in a silicate chain, it may be OH; and that where O7 is not in a
formed on heating jennite to 70–90 °C — and jennite itself. silicate chain it may be water. The subcell contents and ionic
Taylor developed his model for the substructure of metajennite constitution would therefore be Ca9Si6O18(OH)6·2H2O. Taylor
by assuming that it has a Ca\O structure similar to one of the also derived a model for the substructure of jennite, again
three symmetry-related layers in jaffeite (Ca6[Si2O7](OH)6 using the parameters given in [72], essentially by the insertion

Fig. 9. Diagrams illustrating tobermorite-based dimer (n = 1) that has the minimum (a), intermediate (b), and maximum (c) degree of protonation of the silicate chains.
The purpose of the highly schematic diagrams on the left-hand-side of the figure is to demonstrate chemical accounting; the values of the variables in Richardson and
Groves' model [179] are indicated. The diagrams on the right-hand-side are more realistic structural representations that were derived from crystal-structure data for
tobermorite [66] (the silicate chains are aligned along the plane of the page).
150 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

Table 5 have w/n = 1 and y = 1 for T-based units and y = 5 for J-based;
Mean Ca/Si, Ca/(Al + Si) and Al/Si atom ratios for both Op and Ip C-S-H in the the T-based units are illustrated on Fig. 9(b), which have a Ca/Si
4-year-old water-activated 70% WPC-30% fly ash blended cement paste
obtained using TEM-EDX, and the Al/Si ratio determined by deconvolution of
ratio of 1.25. The similarity of the two models is easily
the single-pulse 29Si MAS NMR spectrum demonstrated: substitution of y = 1 or 5 and n = 1, 2, 3, etc. into
Ca/Si Ca/(Al+Si) Al/Si
Formula (8) in Table 2 (and a = 0, since there is no aluminium in
Taylor's units) gives the Ca/Si ratios given in Table 3 (i.e. the
N Mean S.D. Mean S.D. Mean S.D. NMR
values given in Taylor's paper). As noted above, the maximum
Wpfa30 Op 20 1.40 0.18 1.19 0.10 0.18 0.07 0.18 Ca/Si ratio possible for dimer in Stade and co-workers' model
Ip 17 1.36 0.06 1.16 0.06 0.17 0.03
also corresponds to w/n = 1 and y = 1.
All 37 1.38 0.10 1.18 0.09 0.18 0.05
(N = number of EDX analysis; S.D. = standard deviation). 5.3. Example of similarity of models: T-based structural units
with maximum degree of protonation (w/n = 2)

of a layer of water molecules between metajennite-like layers, Nonat updated his and Lecoq's 1998 model in 2004 [188].
as illustrated in Fig. 6. Whilst the full solution and refinement The formula Ca2H2Si2O7 given by Nonat [188] on p1525
of the structure of jennite was achieved with great experi- corresponds to T units with w/n = 2 and y = 0 in Formula (7)
mental skill by Bonaccorsi — and is described in detail in (illustrated in Fig. 9(c)). For Ca/Si ratios ≥ 1.5 Nonat incorpo-
[70] — it is apparent that the model structure derived by rated what are essentially T/CH and T/J formulations. The
Taylor in 2000 was substantially correct, which is clearly paper includes the following on page 1526: ‘Ca3H2Si2O7(OH)2
apparent from Fig. 8. (Ca/Si = 1.5, one silicate bridging tetrahedron is be replaced by
Ca(OH)2 (tobermorite-like structure) or a non-bridging tetra-
5. Visualization of models for the nanostructure of C-S-H. hedron is replaced by 2OH− (jennite-like part)’; on the T/J
model this formula corresponds to w/n = 2 and y = 2; i.e. an
A consequence of the publication of the crystal structures of equal mixture of T-based structure (represented by Fig. 9 (c),
jaffeite [112], jennite [70], and 1.4 nm tobermorite [66] is that it y = 0) and J-based structure (represented by Fig. 29 in
is now much easier to build, display and manipulate the type of Richardson [189], y = 4) that have maximum degree of
nanostructural units that are proposed in the various models for
C-S-H. The result is that the similarities between the models are
more readily apparent. An extensive set of illustrative figures is
given in Richardson [189], which were derived from these
structures, together with Taylor's trial structure for metajennite;
three examples are given here, which are tobermorite-based
(T-based) dimer (i.e. n = 1) with different levels of protonation
of the silicate chains (i.e. different values of w/n in Richardson
and Groves' model).

5.1. Example of similarity of models: T-based structural units

with minimum degree of protonation (w/n = 0)

Fig. 9(a) shows T-based dimeric structural units that have the
minimum degree of protonation; the Ca/Si ratio is 1.50 and in
terms of Richardson and Groves' model w/n = 0 and y = 2. This
unit is the same as:

(i) The formula for dimer in Chen et al. 's Table 5 [187],
which was the result of their charge-balance arguments Fig. 10. Single-pulse 29Si (middle) and 1H-29Si cross polarization (CP) (top)
for the minimum Ca/Si ratios above which Ca-OH groups MAS NMR spectra for a water-activated 70% WPC-30% fly ash blend hydrated
must be present; for 4 years at 25 °C. The spectra are scaled to their tallest peak. The result of the
(ii) Cong and Kirkpatrick's [182,183] model when 2C/S − deconvolution of the single-pulse spectrum is shown at the bottom: the C-S-H
peaks have chemical shifts of − 79.1 ppm (Q1), −81.1 ppm (Q2(1Al)), and
NBO = 0; −84.6 ppm (Q2(0Al)); there is a small Q0H peak at − 75.0 ppm. The NMR
(iii) Nonat and Lecoq's ‘first hypothesis’ [186,188]. spectra were acquired using a Varian InfinityPlus 300 spectrometer (magnetic
field 7.05T; operating frequencies of 59.5 MHz for 29Si and 78.2 MHz for 27Al).
5.2. Example of similarity of models: T-based structural units The sample was freshly ground and packed into a 6 mm zirconia rotor sealed at
with intermediate degree of protonation (w/n = 1) either end with Teflon end plugs, and spun at 6 kHz in a Chemagnetics-style
probe. The single-pulse spectrum was acquired over 27616 scans using a pulse
recycle delay of 2 s, a pulse width of 4 μs and an acquisition time of 20 ms. The
The structural units present in Taylor's 1986 model CP spectrum was acquired over 9440 scans with a contact time of 1 ms and a
correspond to units in Richardson and Groves' model that recycle delay of 2 s.
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 151

specifically regarding C-S-H present in hardened pastes of C3S,

β-C2S, neat Portland cement and blends of Portland cement
with blast-furnace slag, metakaolin, or silica fume. Additional
examples have also recently been published for C-S-H in a 80%
white Portland cement (WPC)-20% metakaolin blend hydrated
at 25 °C [191], for neat Portland cement hydrated at 55 °C
[192], a 70% WPC-30% fly ash blend hydrated at 85 °C [156],
and in 20-year-old neat Portland cement and 10% WPC-90%
blast-furnace slag pastes [193]. Another example is given here
for C-S-H present in a 70% WPC-30% fly ash blend hydrated at
25 °C for 4 years.
Fig. 10 shows single-pulse 29Si (middle) and 1H-29Si cross
polarization (top) MAS NMR spectra for the paste; experi-
mental details are given in the Figure caption. Deconvolution of
Fig. 11. TEM image from a water-activated 70% WPC-30% fly ash blend the single-pulse spectrum gave a mean aluminosilicate chain
hydrated for 4 years at 25 °C. The outer product C-S-H has fine fibrillar
morphology and the inner product has a fine homogeneous morphology. The
length (MCL) of 11.3, the proportion of occupied bridging
region also contains CH crystals and AFt relicts. tetrahedra occupied by Al (rather than Si) was 57%, and the
Al/Si ratio was 0.18.
protonation (w/n = 2), and on the T/CH viewpoint it corresponds Part of the sample was examined by TEM. The TEM
to X = 2 and z = 1 (i.e. substitution of n = 1, a = 0 (no micrograph in Fig. 11 shows a region with both fibrillar outer
aluminium), X = 2 and z = 1 into Formula (6) in Table 2 gives product (Op) C-S-H and fine and dense inner product (Ip) C-S-H.
Ca2H2Si2O7·Ca(OH)2). Large crystals of CH were also identified together with relicts
of AFt; the hexagonal outline of an AFt relict near to the
6. Example of the applicability of the models to C-S-H in bottom left corner of the micrograph is particularly striking as
hardened cements it supports the view that the morphology of outer product C-S-H is
not overly affected by the preparation procedure and high vacuum
A number of examples of the applicability of the models to of the microscope (see discussion in [194] ). Areas of Ip and Op
C-S-H in hardened cements are given in Richardson [189], C-S-H were analysed by EDX (∼200 nm in diameter). The data

Fig. 12. (a) Al/Ca against Si/Ca atom ratio plot of TEM-EDX analyses of Ip (□) and Op (◯) C-S-H present in the water-activated 70% WPC-30% fly ash blend
hydrated for 4 years. The other symbols represent the compositions of tobermorite-(T) or jennite-/jaffeite-based (J) structural units with different levels of protonation
◇
of the silicate chains: the minimum level ( ; w/n = 0), an intermediate level (+; w/n = 1), and the maximum level (×; w/n = 2). Points are included on the figures that
represent tobermorite-based units with chain lengths of 2, 5, 8, 11, 14, 17 and ∞. Most of the units are saturated with Al (i.e. all the occupied bridging sites are occupied
by Al rather than Si). The only exceptions are units with 11 tetrahedra, which in addition to those saturated with Al (i.e. Al/(Al + Si) = 3/11, which are labelled simply as
T11), are also represented with one or two of the three bridging sites occupied by Al (i.e. Al/(Al + Si) = 1/11or 2/11): units with one or two Al ions are labelled as T11
(1Al) and T11(2Al) respectively. T11 units with the same degree of protonation but different content of Al are joined by dotted lines. The dashed tie lines join points for
T11 structural units with points on the Si/Ca axis that represent jennite-based dimer (with different degrees of protonation). (b) As (a) except that the dashed tie lines
now join points for structural units of the same length but different degrees of protonation with CH (at the origin).
152 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

are plotted as Al/Ca against Si/Ca scatter graphs in Fig. 12. The compatible with the data from the deconvolution of the NMR
full line on Fig. 12(a) corresponds to the compositional relation- spectrum.
ship established in previous studies for C-S-H present in blast-
furnace slag-Portland cement blends [195–200]: it is interesting 7. Size of particles of C-S-H in hardened C3S and neat
to note that the compositions measured for this mature blend Portland cement pastes
containing fly ash follows the same relationship. Mean values of
Ca/Si, Ca/(Al + Si) and Al/Si ratios for C-S-H are given in Table 5. It was noted in the Introduction that a companion paper in
The Al/Si ratio measured in the TEM is in good agreement with this issue is concerned with the cohesion forces that act between
that determined by deconvolution of the NMR spectrum. individual layers or crystallites of C-S-H [5]; the purpose of this
The NMR and TEM-EDX data in Table 5 can be used to section is to lead into that paper by considering the size of
establish formulae for average structural units in the C-S-H in individual particles of C-S-H. The example that is used to
terms of the two alternative formulations for the nanostructure illustrate a small particle — which employs J-based (i.e.
of C-S-H given by Richardson and Groves [179,180]; i.e. in jaffeite- or jennite-based) type of structure for the C-S-H — also
terms of either the tobermorite-jennite (T/J) or tobermorite- demonstrates possible reasons for the persistence of hydrated
calcium hydroxide (T/CH) structural viewpoints. The procedure monomer in C-S-H and the fact that the extent of silicate
to establish the structural formulae is straightforward: it simply polymerization is limited in systems with high Ca/(Si + Al)
involves calculation of the models' variables by inserting the ratio.
experimentally determined mean values of Ca/Si and Al/Si In hardened cements there is a clear distinction between the
ratios and aluminosilicate chain length into Formulae (6) and (7) morphology of C-S-H that forms in the originally water-filled
given in Table 2. So, for example, an average structural unit space (outer product (Op) C-S-H) and the C-S-H that forms
with minimum degree of protonation of the aluminosilicate within the volume of the original particles (inner product (Ip)
chains and assuming that the substitution of Si4+ by Al3+ is C-S-H). The Ip C-S-H generally has a very fine particulate
balanced entirely by Ca2+ ions (i.e. using Eq. (9) to calculate y') morphology; the morphology of Op C-S-H is strongly
can be represented by Eq. (13): dependent on chemical composition: at high Ca/(Si + Al) ratio
it has a fibrillar morphology whereas with lower Ca/(Si + Al) it
VCa8:2 ðSi0:85 Al0:15 Þ11:3 O34:9 tdðOHÞ0:25 dCa5:07 dmH2 O ð13Þ is foil- or sheet-like; many examples of TEM micrographs are
given in Richardson [189,194] and references therein. Particles
The presence of hydroxyl groups outside the braces indicates of C-S-H in water-activated C3S, β-C2S and PC pastes appear
that in terms of the T/J viewpoint, there must be some J-like to be very small. Ip C-S-H particles appear to be globular,
structure. In terms of the T/CH viewpoint, the average structural around 3 to 8 nm in diameter. Op C-S-H particles appear to be
unit is represented by (14): long and thin, say 3 nm by some tens of nm; the fibrils of C-S-H
consist of agglomerations of these thin particles. Particles of Ip
Ca12:3 ðSi0:85 Al0:15 Þ11:3 O34:9 dCa0:85 d0:12CaðOHÞ2 dmH2 O ð14Þ C-S-H are smaller when formed at elevated temperature, which

It is evident from Formulae (13) and (14) that — if the

aluminosilicate chains did indeed have a minimum degree of
protonation — the C-S-H in this paste would consist mostly of T-
based structure with little J- or CH-like structure necessary.
Nevertheless, it is instructive to compare the distribution of the
TEM-EDX analyses with the compositions of different units in
Richardson and Groves' structural models: points that represent
various structural units are included on Fig. 12; an explanation of
the different symbols and tie lines on the figures is given in the
caption. Each TEM-EDX data point corresponds to an analysis
of C-S-H that had been checked by selected area electron
diffraction to not be intermixed with a crystalline phase. The
mean aluminosilicate chain length for the C-S-H was 11, with
57% of the occupied bridging sites occupied by Al; that is, an
average structural unit would be a dreierkette chain with 11
tetrahedra with an Al3+ ion at approximately two of the three
bridging sites and Si4+ at the other one. Consideration of the
positions of the EDX data points with those of the structural units
on Fig. 12 indicates that the C-S-H is likely to consist of
structural units that are unprotonated, but it is not possible to
Fig. 13. Schematic diagram showing a view of an approximately 3-nm-sized
decide whether there is a small amount of J- or CH-like structure. particle, consisting entirely of J dimer with the minimum degree of protonation
Nevertheless, it is clear that the relative positions of the TEM- (w/n = 0). The silicate chains are aligned across the page; a monomer is evident
EDX analyses and the theoretical T-based structural units are at the extreme right of the top row of silicate tetrahedra.
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 153

is illustrated in Figs. 7(b) and 9(b) of reference [189]. An likely to be significant edge effects with such small particles of
approximately 3 nm-sized particle is shown in Fig. 13; the C-S-H: a monomer can be seen at the extreme right of the top
dimeric silicate chains are aligned along the plane of the page. row of silicate tetrahedra; this would seem to offer a reasonable
The 3 nm size of the particle requires only two layers, which is explanation for the persistence of hydrated monomeric species.
more clearly apparent in Fig. 14(a), which shows the same Certainly, it would explain why there is more hydrated
particle as in Fig. 13 but rotated horizontally through 80°. In monomer at elevated temperatures, where the particles seem
reality the adjacent layers are quite possibly not as close or to be smaller and apparently less in systems where the Op C-S-
aligned as shown; in this case they are as close as they can get to H has a foil-like morphology, which presumably has fewer
one another and well-ordered, betraying the model's origin chain-end edges than the particles in the fibrils present in water-
(Ca-deficient jaffeite). Fig. 13 nicely illustrates that there is activated C3S or PC pastes.
Further consideration of this schematic representation of a C-
S-H particle highlights an interesting point regarding the nature
of polymerization in J-based structure. The same projection as
in Fig. 14(a) is shown in Fig. 14(b) but this time with bridging
tetrahedra replacing Ca2+ ions, which have been displaced. This
figure is derived from the model structure for metajennite
(unrefined) produced by Taylor [75], who, as explained earlier,
used jaffeite as a starting point; the relationship between the two
structures is again clear from these two figures. It is equally
clear that the displacement of Ca2+ ions and the insertion of
silicate tetrahedra would be easier at the surfaces of the particle
than within its interior. This point is reinforced in reference
[189], which has similar figures together with one derived from
jennite itself (Fig. 38); in that case the main layers are much
further apart. The point was made in that paper that it seems
quite plausible that in an early-age particle that consists entirely
of J dimer (with some associated monomer due to chain-end
edge effects) the main layers would be closer together than in
crystalline jennite, and that the subsequent insertion of bridging
tetrahedra would therefore be much easier at the particle's
surfaces (those that are not chain-end surfaces). It was noted that
this is perhaps one reason why mean silicate chain lengths do
not get above five in C3S pastes hydrated at ambient
temperatures, but can get longer at higher temperatures where
a smaller proportion of the silicate chains are in the interior of
particles (because the particles are smaller).

8. Summary

This article is concerned with the calcium silicate hydrates,

including crystalline minerals and the extremely variable and
poorly ordered phase (C-S-H) that is essentially the ‘glue’ of the
concrete part of the Built Environment. Up-to-date composition
and crystal-structure information is tabulated for the most
important crystalline calcium (alumino) silicate hydrates and
related phases, which should be a useful reference source for
others interested in these phases. A number of models for the
nanostructure of C-S-H in hardened C3S and Portland cements
— or in blends of Portland cement with supplementary
cementing materials — have been published over the past
55 years. These models are summarized and compared and it is
shown that many of them are in fact very similar to one another;
i.e. there is much more of a consensus than might seem apparent
at first sight. Illustrative examples are used to demonstrate the
Fig. 14. (a) Schematic diagram showing the same J dimer-based particle as in similarities. Most of the models involve elements of tobermorite-
Fig. 13, but rotated horizontally by 80°. (b) Essentially the same particle as in (a), but like structure. In a number of cases, these are intermixed with
with silicate bridging tetrahedra now in place; i.e. the chains are fully polymerized. others of jennite-like structure. As a consequence, perhaps two
154 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

of the most significant papers for Cement Science that have been [16] Y. Okada, T. Masuda, H. Ishida, H. Nishido, Silicate anion structure and
published since the 11th International Congress on the dehydration processes in okenite, J. Ceram. Soc. Jpn. 102 (1994)
919–924.
Chemistry of Cement are those by Bonaccorsi and co-workers [17] K. Yanagisawa, X. Hu, A. Onda, K. Kajiyoshi, Hydration of β-dicalcium
that report refined crystal structures for 1.4 nm tobermorite and silicate at high temperatures under hydrothermal conditions, Cem. Concr.
jennite. The value of these structures, together with those of Res. 36 (2006) 810–816.
jaffeite and metajennite, for visualizing the nanostructural [18] A. Alberti, E. Galli, The structure of nekoite, Ca3Si6O15·7H2O, a new
type of sheet silicate, Am. Mineral. 65 (1980) 1270–1276.
elements present in the models is demonstrated. The importance
[19] J.A. Gard, H.F.W. Taylor, Okenite and nekoite (a new mineral), Mineral.
of Hal Taylor's contribution to the solution of the structure of Mag. 31 (1956) 5–20.
jennite is highlighted. The applicability of Richardson and [20] R.A. Chalmers, A.W. Nicol, H.F.W. Taylor, The composition of nekoite,
Groves' model is demonstrated using experimental composi- Mineral. Mag. 33 (1962) 70–71.
tion-structure observations on the nature of C-S-H present in a [21] R. Cerny, Powder pattern decomposition with the aid of preferred
blended cement paste containing 30% fly ash, and attention is orientation — experimental test, Mat. Sci. Forum 321 (3) (2000) 22–27.
[22] S. Merlino, Okenite, Ca10Si18O46·18H2O: the first example of a chain and
drawn to other examples published recently for C-S-H present in sheet silicate, Am. Mineral. 68 (1983) 614–622.
a range of systems. The stages in the dehydration of 1.4 nm [23] J.A. Gard, H.F.W. Taylor, Okenite and nekoite (a new mineral), Mineral.
tobermorite are illustrated using high-resolution transmission Mag. 31 (1956) 5–20.
electron microscopy. [24] Y. Takeuchi, Y. Kudoh, Hydrogen bonding and cation ordering in Magnet
Cove pectolite, Z. Kristallog., Kristallg., Kristallp., Kristallch. 146 (1977)
281–292.
Acknowledgements [25] M.J. Buerger, The determination of the crystal structure of pectolite,
Ca2NaHSi3O9, Z. Kristallogr. 108 (1956) 248–262.
Thanks are due to the Engineering and Physical Sciences [26] C.T. Prewitt, M.J. Buerger, Comparison of the crystal structures of
Research Council for funding under Grant No. GR/S45874/01, wollastonite and pectolite, Mineral. Soc. Amer. Spec. Paper 1, 3rd
to Dr. Andrew Brown for taking the HRTEM image and to General Meeting Int. Mineral. Ass., 1963, pp. 293–302.
[27] C.T. Prewitt, Refinement of the structure of pectolite, Ca2NaHSi3O9, Z.
Castle Cement, UK Nirex Ltd., and Lafarge Cements for the Kristallogr. 125 (1967) 298–316.
additional technical and financial support. [28] W.F. Müller, On stacking disorder and polytypism in pectolite and
serandite. Z. Kristallogr., 144 (1976) 401–408.
References [29] A. Sebald, L.H. Merwin, W.A. Dollase, F. Seifert, A multinuclear, high–
resolution solid-state NMR study of sorensenite (NaSnBe2(Si3O9)·2H2O) and
[1] C.H. Desch, The mechanism of the setting process in plaster and cement, comparison with wollastonite and pectolite, Phys. Chem. Miner. 17 (1990)
Trans. Faraday Soc. 14 (1–2) (1919) 1–7. 9–16.
[2] H. Le Chatelier, Crystalloids against colloids in the theory of cements, [30] K. Baltakys, R. Siauciunas, The influence of γ-Al2O3 and Na2O on the
Trans. Faraday Soc. 14 (1–2) (1919) 8–11. formation of gyrolite in the stirring suspension, J. Mater. Sci. 41 (2006)
[3] G.A. Rankin, The setting and hardening of Portland cement, Trans. 4799–4805.
Faraday Soc. 14 (1–2) (1919) 23–28. [31] Y. Ohashi, Polysynthetically-twinned structures of enstatite and wollas-
[4] J.F. Young, Looking ahead from the past: The heritage pf cement chemistry, tonite, Phys. Chem. Miner. 10 (1984) 217–229.
Cem. Concr. Res., this issue, doi:10.1016/j.cemconres.2007.09.011. [32] M.J. Buerger, C.T. Prewitt, The crystal structure of wollastonite and
[5] R.J.-M. Pellenq, N. Lequeux, H. van Damme, Engineering the bonding pectolite, Proc. Nat. Acad. Sci., 47 (1961) 1884–1888.
scheme in C-S-H: the iono-covalent framework, Cem. Concr. Res., this issue, [33] C.T. Prewitt, M.J. Buerger, Comparison of the crystal structures of
doi:10.1016/j.cemconres.2007.09.026. wollastonite and pectolite, Min. Soc. Am. Sp. Paper 1 (1963) 293–302.
[6] J.A. Gard, H.F.W. Taylor, The crystal structure of foshagite, Acta [34] K. Lin, J. Chang, J. Lu, Synthesis of wollastonite nanowires via
Crystallogr. 13 (1960) 785–793. hydrothermal microemulsion methods, Mater. Lett. 60 (2006)
[7] A.S. Eakle, Foshagite, a new silicate from Crestmore, California, Am. 3007–3010.
Mineral. 10 (1925) 97–99. [35] C. Hejny, T. Armbruster, Polytypism in xonotlite Ca6Si6O17(OH)2, Z.
[8] J.A. Gard, H.F.W. Taylor, Foshagite: composition, unit cell and Kristallogr. 216 (2001) 396–408 polytype derived from structure in
dehydration, Am. Mineral. 43 (1958) 1–15. Kudoh and Takeuchi (1979).
[9] L. Black, K. Garbev, P. Stemmermann, K.R. Hallam, G.C. Allen, [36] Y. Kudoh, Y. Takeuchi, Polytypism in xonotlite: (I) Structure of an A-1
Characterisation of crystalline C-S-H phases by X-ray photoelectron polytype, Mineral. J. 9 (1979) 349–373.
spectroscopy, Cem. Concr. Res. 33 (2003) 899–911. [37] X. Li, J. Chang, A novel hydrothermal route to the synthesis of xonotlite
[10] C.L. Dickson, D.R.M. Brew, F.P. Glasser, Solubilities of CaO–SiO2– nanofibres and investigation on their bioactivity, J. Mater. Sci. 41 (2006)
H2O phases at 25, 55, 85 °C, Adv. Cem. Res 16 (2004) 35–43. 4944–4947.
[11] Y.-S. Dai, J.E. Post, Crystal structure of hillebrandite: a natural analogue [38] N. Meller, C. Hall, K. Kyritsis, G. Giriat, Synthesis of cement based on
of calcium 5 silicate hydrate (CSH) phases in Portland cement, Am. CaO–Al2O3–SiO2–H2O (CASH) hydroceramics at 200 and 250 °C: Ex-
Mineral., 80 (1995) 841–844. situ and in-situ diffraction, Cem. Concr. Res. 37 (2007) 823–833.
[12] K.H. Mamedov, N.V. Belov, Crystal structure of hillebrandite, Dokl. [39] A. Hamilton, C. Hall, Physicochemical characterization of a hydrated
Akad. Nauk SSSR, 123 (1958) 741–743 (in Russian). calcium silicate board material, J. Building Phys. 29 (2005) 9–19.
[13] M.R. Hansen, H.J. Jakobsen, J. Skibsted, 29Si chemical shift anisotropies [40] F. Meducin, B. Bresson, N. Lequeux, N. de Noirfontaine, H. Zanni, Calcium
in calcium silicates from high-field 29Si NMR spectroscopy, Inorg. Chem. silicate hydrates investigated by solid-state high resolution 1H and 29Si
42 (2003) 2368–2377. nuclear magnetic resonance, Cem. Concr. Res. 37 (2007) 631–638.
[14] S.Y. Hong, F.P. Glasser, Phase relations in the CaO–SiO2–H2O system [41] N. Meller, C. Hall, J. Phipps, A new phase diagram for the CaO–Al2O3–
to 200 °C at saturated steam pressure, Cem. Concr. Res. 34 (2004) SiO2–H2O hydroceramic system at 200 °C, Mater. Res. Bull. 40 (2005)
1529–1534. 715–723.
[15] X. Hu, K. Yanagisawa, A. Onda, K. Kajiyoshi, Stability and phase [42] R. Siauciunas, K. Baltakys, Formation of gyrolite during hydrothermal
relations of dicalcium silicate hydrates under hydrothermal conditions, synthesis in the mixtures of CaO and amorphous SiO2 or quartz, Cem.
J. Ceram. Soc. Jpn. 114 (2006) 174–179. Concr. Res. 34 (2004) 2029–2036.
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 155

[43] K. Luke, Phase studies of pozzolanic stabilized calcium silicate hydrates [69] S. Gross, The mineralogy of the Hatrurim Formation, Israel. Geol. Sur.
at 180 °C, Cem. Concr. Res. 34 (2004) 1725–1732. Israel Bull., 70 (1977) 47.
[44] F.P. Glasser, S.Y. Hong, Thermal treatment of C-S-H gel at 1 bar H2O [70] E. Bonaccorsi, S. Merlino, H.F.W. Taylor, The crystal structure of jennite,
pressure up to 200 °C, Cem. Concr. Res. 33 (2003) 271–279. Ca9Si6O18(OH)6·8H2O, Cem. Concr. Res. 34 (2004) 1481–1488.
[45] S. Shaw, S.M. Clark, C.M.B. Henderson, Hydrothermal formation of [71] A.B. Carpenter, R.A. Chalmers, J.A. Gard, K. Speakman, H.F.W. Taylor,
calcium silicate hydrates, Chem. Geol. 167 (2000) 129–140. Jennite, a new mineral, Am. Mineral. 51 (1966) 56–74.
[46] S. Merlino, E. Bonaccorsi, T. Armbruster, The real structures of [72] J.A. Gard, H.F.W. Taylor, G. Cliff, G.W. Lorimer, A re-examination of
clinotobermorite and tobermorite 9 Å: OD character, polytypes, and jennite, Am. Mineral. 62 (1977) 365–368.
structural relationships, Eur. J. Mineral. 12 (2000) 411–429. [73] I. Kusachi, C. Henmi, K. Henmi, Afwillite and jennite from Fuka,
[47] C. Henmi, I. Kusachi, Monoclinic tobermorite from Fuka, Bitchu-cho, Okayama Province, Japan, Mineral. J. (Japan) 14 (1989) 279–292.
Okayama Prefecture, Japan, J. Min. Petr. Econ. Geol. 84 (1989) 374–379 [74] E. Bonaccorsi, S. Merlino, H.F.W. Taylor, Crystal structures of jennite
(In Japanese). and tobermorites: New data for understanding the nanostructure of
[48] C. Henmi, I. Kusachi, Clinotobermorite, Ca5Si6(O,OH)18·5H2O, a new Portland cement. Paper presented at Congress of the Italian Association
mineral from Fuka, Okayama Prefecture, Japan, Mineral. Mag. 56 (1992) of Crystallography, 2002.
353–358. [75] H.F.W. Taylor, Personal communication, 2000.
[49] C. Hoffmann, T. Armbruster, Clinotobermorite, Ca5[Si3O8(OH)]2·4H2O– [76] R.H. Mitchell, P.C. Burns, The structure of fedorite: a reappraisal,
Ca5[Si6O17]·5H2O, a natural C-S-H(I) type cement mineral: determina- Canadian Mineral. 39 (2001) 769–777.
tion of the substructure, Z. Kristallogr. 212 (1997) 864–873. [77] G.V. Sokolova, A.A. Kashayev, V.A. Drits, V.V. Ilyukhin, The crystal
[50] S. Merlino, E. Bonaccorsi, T. Armbruster, Tobermorites: their real structure of fedorite, Krisallografiya 28 (1983) 170–172.
structure and order-disorder (OD) character, Am. Mineral. 84 (1999) [78] S. Merlino, Gyrolite: its crystal structure and crystal chemistry, Mineral.
1613–1621. Mag., 52 (1988) 377–387.
[51] E. Bonaccorsi, S. Merlino, Modular microporous minerals: cancrinite- [79] A.L. Mackay, H.F.W. Taylor, Gyrolite, Mineral. Mag. 30 (1953) 80–91.
davyne group and C-S-H phases, Rev. Min. Geochem., 57 (2005) [80] J.W. Meyer, K.L. Jaunarajs, Synthesis and chemistry of gyrolite and
241–290. reyerite, Am. Mineral. 46 (1961) 913–933.
[52] L. Heller, H.F.W. Taylor, Crystallographic Data for the Calcium Silicates, [81] J.A. Gard, T. Mitsuda, H.F.W. Taylor, Some observations on Assarsson's
H.M. Stationary Office, London, 1956, pp. 37–38, (10 Å tobermorite). Z-phase and its structural relations to gyrolite, truscottite, and reyerite,
[53] I. Kusachi, C. Henmi, K. Henmi, An oyelite-bearing vein at Fuka, the Mineral. Mag. 40 (1975) 325–333.
town of Bitchu, Okayama Prefecture, Japan, J. Japan. Assoc. Min. Petr. [82] S. Shaw, C.M.B. Henderson, S.M. Clark, In situ synchrotron study of the
Econ. Geol. 79 (1984) 267–275. kinetics, thermodynamics, and reaction mechanisms of the hydrothermal
[54] J.D.C. McConnell, The hydrated calcium silicates riversideite, tobermor- characterization of gyrolite, Am. Mineral. 87 (2002) 533–541.
ite, and plombierite, Mineral. Mag., 30 (1954) 293–305. [83] A. Stumm, K. Garbev, G. Beuchle, L. Black, P. Stemmermann, R.
[55] H.F.W. Taylor, Crestmoreite and riversideite, Mineral. Mag. 30 (1953) Nuesch, Incorporation of zinc into calcium silicate hydrates, Part I:
155–165. formation of C-S-H(I) with C/S = 2/3 and its isochemical counterpart
[56] E. Bonaccorsi, S. Merlino, T. Armbruster, The real structure of gyrolite, Cem. Concr. Res. 35 (2005) 1665–1675.
tobermorite 11 Å: normal and anomalous forms, OD character and [84] S. Merlino, The structure of reyerite, (Na,K) 2 Ca 14 Si 22 Al 2 O 58
polytypic modifications, Eur. J. Mineral., 13 (2001) 577–590. (OH)8·6H2O, Mineral. Mag. 52 (1988) 247–256.
[57] H.D. Megaw, C.H. Kelsey, Crystal structure of tobermorite, Nature, 177 [85] R.A. Chalmers, V.C. Farmer, R.I. Harker, S. Kelly, H.F.W. Taylor,
(1956) 390–391. Reyerite, Mineral. Mag. 33 (1964) 821–840.
[58] T. Mitsuda, H.F.W. Taylor, Normal and anomalous tobermorites, Mineral. [86] S.C. Clement, P.H. Ribbe, New locality, formula, and proposed structure
Mag., 42 (1978) 229–235. for reyerite, Am. Mineral. 58 (1973) 517–522.
[59] S.A. Hamid, The crystal structure of 11 Å natural tobermorite Ca2.25 [87] A.L. Mackay, H.F.W. Taylor, Truscottite, Mineral. Mag. 30 (1954)
[Si3O7.5(OH)1.5]·1H2O, Z. Kristallogr. 154 (1981) 189–198. 450–457.
[60] P. Yu, R.J. Kirkpatrick, Thermal dehydration of tobermorite and jennite, [88] E.E. Lachowski, L.W. Murray, H.F.W. Taylor, Truscottite: composition
Concr. Sci. Eng., 1 (1999) 185–191. and ionic substitutions, Mineral. Mag. 43 (1979) 333–336.
[61] L. Black, A. Stumm, K. Garbev, P. Stemmermann, K.R. Hallam, G.C. [89] T.P. Kuznetsova, N.N. Nevskii, V.V. Ilyukhin, N.V. Belov, Refinement of
Allen, X-ray photoelectron spectroscopy of aluminium-substituted the crystal structure of calcium chondrodite, Ca5[SiO4]2(OH)2=Ca
tobermorite, Cem. Concr. Res. 35 (2005) 51–55. (OH)2·Ca2SiO4, Soviet Physics Crystallography, 25 (1980) 91–92
[62] N.J. Coleman, Synthesis, structure and ion exchange properties of 11 Å (translation of Kristallografiya, 25 (1980) 159–160).
tobermorites from newsprint recycling residue, Mater. Res. Bull. 40 [90] E.R. Buckle, H.F.W. Taylor, A calcium analogue of chondrodite, Am.
(2005) 2000–2013. Min. 43 (1958) 818–823.
[63] T. Maeshima, H. Noma, M. Sakiyama, T. Mitsuda, Natural 1.1 and [91] R.M. Ganiev, Yu.A. Kharitonov, V.V. Ilyukhin, N.V. Belov, Crystal
1.4 nm tobermorites from Fuka, Okayama, Japan: Chemical analysis, cell structure of calcium chondrodite, Ca5[SiO4]2(OH)2=Ca(OH)2·Ca2SiO4,
dimensions, 29Si NMR and thermal behaviour, Cem. Concr. Res. 33 Soviet Physics – Doklady, 14 (1970) 946–948 (translation of Dokl. Acad.
(2003) 1515–1523. Nauk SSSR, 188 (1969) 1281).
[64] F. Sato, G. Mi, M. Hanada, Mechanochemical synthesis of hydrated [92] H.-M. Hamm, G. Hentschel, Reinhardbraunsite, Ca5(SiO4)2(OH,F)2, a
calcium silicates by room temperature grinding, Solid State Ion. 101–103 new mineral equivalent of synthetic ‘calcio-chondrodite’, Neues Jahrb.
(1997) 37–43. Mineral., Monatsh. (1983) 119–129.
[65] R. Siauciunas, A. Baltusnikas, Influence of SiO2 modification on [93] A. Kirfel, H.-M. Hamm, G. Will, The crystal structure of reinhard-
hydrogarnets formation during hydrothermal synthesis, Cem. Concr. braunsite, Ca5(SiO4)2(OH,F)2; a new mineral of the calcio-chondrodite
Res. 33 (2003) 1789–1793. type, Tschermaks Mineral. Petrogr. Mitt. 31 (1983) 137–150.
[66] E. Bonaccorsi, S. Merlino, A.R. Kampf, The crystal structure of [94] H.F.W. Taylor, The crystal structure of Kilchoanite, Ca6(SiO4)
tobermorite 14 Å (plombierite), a C-S-H phase, J. Am. Ceram. Soc. 88 (Si3O10), with some comments on related phases, Mineral. Mag. 38
(2005) 505–512. (1971) 26–31.
[67] J.D.C. McConnell, The hydrated calcium silicates riversideite, tobermor- [95] K.M.A. Malik, J.W. Jeffrey, A re-investigation of the structure of
ite, and plombierite, Mineral. Mag. 30 (1954) 293–305. afwillite, Acta Crystallogr. 32 (1976) 475–480.
[68] J.D.C. McConnell, The hydration of larnite (b-Ca2SiO4) and bredigite [96] J. Parry, F.E. Wright, Afwillite, a new hydrous calcium silicate from
(a1-Ca2SiO4) and the properties of the resulting gelatinous mineral Dutoitspan Mine, Kimberley, South Africa, Mineral. Mag. 20 (1925)
plombierite, Mineral. Mag., 30 (1955) 672–680. 277–285.
156 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

[97] H.D. Megaw, The structure of afwillite, Ca3(SiO3OH)2(H2O)2, Acta [125] G. Stanger, C. Neal, A new occurrence of suolunite, from Oman, Mineral.
Crystallogr. 5 (1952) 477–491. Mag. 48 (346) (1984) 143–146.
[98] G. Switzer, E.H. Bailey, Afwillite from Crestmore, California, Am. [126] S.J. Louisnathan, J.V. Smith, Crystal structure of tilleyite: refinement and
Mineral. 38 (1953) 629–633. coordination, Z. Kristallogr. 132 (1970) 288–306.
[99] L. Heller, H.F.W. Taylor, Crystallographic Data for the Calcium Silicates, [127] J.D. Grice, The structure of spurrite, tilleyite and scawtite, and
H.M. Stationary Office, London, 1956, pp. 50–53. relationships to other silicate-carbonate minerals, Canadian Mineral. 43
[100] I. Kusachi, C. Henmi, K. Henmi, Afwillite and jennite from Fuka, (2005) 1489–1500.
Okayama Prefecture, Japan, Mineral. J. (Japan) 14 (1989) 279–292. [128] S. Medvescek, R. Gabrovsek, V. Kaucic, A. Meden, Hydration products
[101] R.E. Marsh, A revised structure for a-dicalcium silicate hydrate, Acta in water suspension of Portland cement containing carbonates of various
Crystallogr. C50 (1994) 996–997. solubility, Acta Chim. Slov. 53 (2006) 172–179.
[102] H. Heller, The structure of dicalcium silicate a-hydrate, Acta Crystallogr. [129] S.E. Dann, P.J. Mead, M.T. Weller, Lowenstein's rule extended to an
5 (1952) 724–728. aluminium rich framework. The structure of bicchulite, Ca8(Al2SiO6)4
[103] T. Yano, K. Urabe, H. Ikawa, T. Teraushi, N. Ishizawa, S. Udagawa, (OH)8, by MASNMR and neutron diffraction, Inorg. Chem. 35 (1996)
Structure of a-dicalcium silicate hydrate, Acta Crystallogr. C49 (1993) 1427–1428.
1555–1559. [130] K. Sahl, N.D. Chaterjee, Crystal structure of bicchulite Ca2(Al2Si O6)
[104] B. Bresson, F. Meducin, H. Zanni, C. Noik, Hydration of tricalcium (OH)2, Z. Kristallogr. 146 (1977) 35–41.
silicate (C3S) at high temperature and high pressure, J. Mater. Sci. 37 [131] K. Sahl, Refinement of the crystal structure of bicchulite Ca2(Al2Si O6)
(2002) 5355–5365. (OH)2, Z. Kristallogr. 152 (1980) 13–21.
[105] S. Saburi, A. Kawahara, C. Henmi, I. Kusachi, K. Kihara, The refinement [132] B. Winkler, V. Milman, C.J. Pickard, Quantum mechanical study of Al/Si
of the crystal structure of cuspidine, Mineral. J. (Japan), 8 (1977) disorder in leucite and bicchulite, Mineral. Mag. 68 (2004) 819–824.
286–298. [133] R.K. Rastsvetaeva, N.B. Bolotina, A.E. Zadov, N.V. Chukanov, Crystal
[106] C.E. Tilley, Cuspidine from dolomite contact skarns, Broadford, Skye. structure of fukalite dimorph Ca4(Si2O6)(CO3)(OH)2 from the Gume-
Mineral. Mag. 28 (1947) 90–95. shevsk deposit, the Urals, Dokl. Earth Sci. 405 (2005) 1347–1351.
[107] R.F. Smirnova, I.M. Rumanova, N.V. Belov, The crystal structure of [134] C. Henmi, I. Kusachi, A. Kawahara, K. Henmi, Fukalite, a new calcium
cuspidine, Zap. Vses. Mineral. Obsestva 84 (1955) 159–169. carbonate silicate hydrate mineral, Mineral. J. 8 (1977) 374–381 (Japan).
[108] A. Van Valkenberg, G.F. Rynders, Synthetic cuspidine, Am. Mineral. 43 [135] O. Ferro, E. Galli, G. Papp, S. Quartieri, S. Szakáll, G. Vezzalini, A new
(1958) 1195–1202. occurrence of katoite and re-examination of the hydrogrossular group,
[109] A.N. Safronov, N.N. Nevsky, V.V. Ilyukhin, N.V. Belov, The refinement Eur. J. Mineral. 15 (2003) 419–426.
of the crystal structure of the cement phase gamma-C6S3H, Dokl. Akad. [136] G.A. Lager, W.G. Marshall, Z. Liu, R.T. Downs, Re-examination of the
Nauk SSSR 256 (1981) 1387–1389. hydrogarnet structure at high pressure using neutron powder diffraction
[110] S.O. Agrell, Polythermal metamorphism of limestones at Kilchoan, and infrared spectroscopy, Am. Mineral. 90 (2005) 639–644.
Ardnamurchan. Mineral. Mag. 34 (1965) 1–15. [137] G. Le Saout, E. Lecolier, A. Rivereau, H. Zanni, Chemical structure of
[111] R.M. Ganiev, V.V. Ilyukhin, N.V. Belov, Crystal structure of cement cement aged at normal and elevated temperatures and pressures Part I.
phase Y = Ca6(Si2O7)(SiO4)(OH)2, Dokl. Akad. Nauk SSSR 190 (1970) Class G oilwell cement, Cem. Concr. Res. 36 (2006) 71–78.
831–834. [138] G. Le Saout, E. Lecolier, A. Rivereau, H. Zanni, Chemical structure of
[112] N.A. Yamnova, Kh. Sarp, Yu. K. Egorov-Tismenko, D.Yu. Pushchar- cement aged at normal and elevated temperatures and pressures, Part II:
ovskii, Crystal structure of jaffeite, Crystallogr. Rep 38 (1993) 464–466 Low permeability class G oilwell cement, Cem. Concr. Res. 36 (2006)
(c/c of Kristallografiia). 428–433.
[113] H. Sarp, D.R. Peacor, Jaffeite, a new hydrated calcium silicate from the [139] J.M.R. Mercury, P. Pena, A.H. De Aza, X. Turrillas, I. Sobrados, J. Sanz,
Kombat mine, Namibia. Am. Mineral. 74 (1989) 1203–1206. Solid-state Al-27 and Si-29 NMR investigations on Si-substituted
[114] H.F.W. Taylor, The crystal structure of killalaite, Mineral. Mag. 41 (1977) hydrogarnets, Acta Mater. 55 (2007) 1183–1191.
363–369. [140] R.A. Howie, V.V. Ilyukhin, Crystal structure of rustumite, Nature
[115] R. Nawaz, Killalaite, a new mineral from Co. Sligo, Ireland, Mineral. 269 (1977) 231.
Mag. 39 (1974) 544–548. [141] L. Zhang, P. Fu, H. Yang, K. Yu, Z. Zhou, Crystal structure of scawtite,
[116] Y.-S. Dai, G.E. Harlow, A.R. McGhie, Poldervaartite, Ca(Ca0.5Mn0.5)(SiO3 Chin. Sci. Bull. 37 (1992) 930–934.
(OH))(OH), a new acid nesosilicate from the Kalahari manganese field, [142] C.E. Tilley, Scawtite, a new mineral from Scawt Hill, Co. Antrim,
South Africa: crystal structure and description, Am. Mineral. 78 (1993) Mineral. Mag. 22 (1930) 222–224.
1082–1087. [143] J. Murdoch, Scawtite from Crestmore, California, Am. Mineral. 40 (1955)
[117] C. Wan, S. Ghose, G.V. Gibbs, Rosenhahnite, Ca3Si3O8(OH)2:crystal 505–509.
structure and the stereochemical configuration of the hydroxylated [144] J.D.C. McConnell, A chemical, optical and X-ray study of scawtite from
trisilicate group, [Si3O8(OH)2, Am. Mineral. 62 (1977) 503–512. Ballycraigy, Larne, N. Ireland, Am. Mineral. 40 (1955) 510–514.
[118] A. Pabst, E.B. Gross, J.T. Alfors, ‘Rosenhahnite, a new hydrous calcium [145] D. McConnell, J. Murdoch, The crystal chemistry of scawtite, Am.
silicate from Mendocino County, California', Am. Mineral. 52 (1967) Mineral. 43 (1958) 498–502.
336–351. [146] J.J. Pluth, J.V. Smith, The crystal structure of scawtite, Ca7(Si6O18)(CO3)
[119] J.W. Jeffery, P.F. Lindley, Remarkable new structure, Nature 241 (1973) 22H2O, Acta Crystallogr. (B29) (1973) 73–80.
42–43. [147] R. Rinaldi, M. Sacerdoti, E. Passadlia, Strätlingite: crystal structure,
[120] J.V. Oglesby, J.F. Stebbins, 29Si CPMAS NMR investigations of silano- chemistry, and a reexamination of its polytype vertumnite, Eur. J.
group minerals and hydrous aluminosilicate glasses, Am. Mineral. 85 Mineral. 2 (1990) 841–849.
(2000) 722–731. [148] W. Gessner, D. Müller, Solid-state NMR investigations of gehlenite
[121] Z. Ma, N. Shi, G. Mou, L. Liau, Crystal structure refinement of suolunite hydrate 2CaO×Al2O3×SiO2×8H2O, Z. Chem. 29 (1989) 344–345.
and its significance to the cement techniques, Chin. Sci. Bull. 44 (1999) [149] S. Kwan, J. Larosa, M.W. Grutzeck, Si-29 and Al-27 MAS NMR study of
2125–2130. strätlingite, J. Am. Ceram. Soc. 78 (1995) 1921–1926.
[122] Y. Huang, Suolunite — a new mineral, The Geological Review 23 (1965) [150] M. Frias, J.G. Cabrera, Influence of MK on the reaction kinetics in MK/lime
7 (in Chinese). and MK-blended cement systems at 20 °C, Cem. Concr. Res. 31 (2001)
[123] J. Tseng, C. Hsueh, C. Peng, The crystal structure of suolunite, Kexue 519–527.
Tongbao 17 (1966) 45–48. [151] A. Setiadi, N.B. Milestone, J. Hill, M. Hayes, Corrosion of aluminium and
[124] Anon, The X-ray Laboratory of Hubei Geological Institute), the crystal magnesium in BFS composite cements, Adv. Appl. Ceram. 105 (2006)
structure of suolunite, Sci. Geol. Sin. 2 (1974) 117–132 (in Chinese). 191–196.
 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158 157

[152] M. Frias, The effect of metakaolin on the reaction products and [173] H. Stade, D. Müller, G. Scheler, On the structure of ill-crystallized
microporosity in blended cement pastes submitted to long hydration calcium hydrogen silicates. V. Studies on the coordination of Al in CSH
time and high curing temperature, Cem. Concr. Res. 36 (2006) 1–6. (di,poly) by 27Al NMR spectroscopy, Z. Anorg. Allg. Chem. 510 (1984)
[153] H.F.W. Taylor, D.M. Roy, Structure and composition of hydrates, 16–24.
Principal Report, Sub-Theme II-2, Proc. 7th Int. Cong. Chem. Cem., [174] H. Stade, A.-R. Grimmer, G. Engelhardt, M. Magi, E. Lipmaa, On the
Paris, I, Editions Septima, Paris, 1980, II-2/1-II-2/13. structure of ill-crystallized calcium hydrogen silicates. VII. Solid state
[154] H.F.W. Taylor, Crystal structures and properties of cement hydration silicon-29 NMR studies on C-S-H (Di,Poly), Z. Anorg. Allg. Chem. 528
products (calcium silicate hydrates), Proc. 5th Int. Symp. Chem. Cem., (1985) 147–151 (in German).
Tokyo, 2 (1968) 1–26. [175] H. Stade, D. Müller, On the coordination of Al in ill-crystallized C-SH
[155] I.G. Richardson, The nature of C-S-H in hardened cements, Cem. Concr. phases formed by hydration of tricalcium silicate and by precipitation
Res. 29 (1999) 1131–1147. reactions at ambient temperature, Cem. Concr. Res. 17 (1987) 553–561.
[156] A.V. Girão, I.G. Richardson, C.B. Porteneuve, R.M.D. Brydson, [176] Å. Grudemo, The crystal structures of cement hydration—A review and a
Composition, morphology and nanostructure of C-S-H in white Portland new gel structure model, CBI (Cement och Betong Institutet [Swedish
cement-fly ash blends hydrated at 85 °C, Adv. Appl. Ceram. 106 (2007) Cement and Concrete Research Institute]) Report ra 1 86 (1986) 3 –16.
283–293. (Reprinted from Nordic Concrete Research, 1984).
[157] I.G. Richardson, A.R. Brough, R.M.D. Brydson, G.W. Groves, C.M. [177] H.F.W. Taylor, Proposed structure for calcium silicate hydrate gel, J. Am.
Dobson, The location of aluminium in substituted calcium silicate hydrate Ceram. Soc. 69 (6) (1986) 464–467.
(C-S-H) gels as determined by 29Si and 27Al NMR and EELS, J. Am. [178] F.P. Glasser, E.E. Lachowski, D.E. Macphee, Compositional model for
Ceram. Soc. 76 (1993) 2285–2288. calcium silicate hydrate (C-S-H) gels, their solubilities and free energies
[158] M.D. Andersen, H.J. Jakobsen, J. Skibsted, Incorporation of aluminum in of formation, J. Am. Ceram. Soc. 70 (7) (1987) 481–485.
the calcium silicate hydrate (C-S-H) of hydrated Portland cements: a [179] I.G. Richardson, G.W. Groves, Models for the composition and structure
high-field Al-27 and Si-29 MAS NMR Investigation, Inorg. Chem. 42 of calcium silicate hydrate (C-S-H) gel in hardened tricalcium silicate
(2003) 2280–2287. pastes, Cem. Concr. Res. 22 (1992) 1001–1010.
[159] G.K. Sun, J.F. Young, R.J. Kirkpatrick, The role of Al in C-S-H: NMR, [180] I.G. Richardson, G.W. Groves, The incorporation of minor and trace
XRD, and compositional results for precipitated samples, Cem. Concr. elements into calcium silicate hydrate (C-S-H) gel in hardened cement
Res. 36 (2006) 18–29. pastes, Cem. Concr. Res. 23 (1993) 131–138.
[160] S.A. Rodger, G.W. Groves, N.J. Clayden, C.M. Dobson, Hydration of [181] H.F.W. Taylor, Nanostructure of C-S-H: current status, Adv. Cem. Based
tricalcium silicate followed by 29Si NMR with cross-polarization, J. Am. Mater. 1 (1993) 38–46.
Ceram. Soc. 71 (2) (1988) 91–96. [182] X. Cong, R.J. Kirkpatrick, 29Si MAS NMR study of the structure of
[161] A.R. Brough, C.M. Dobson, I.G. Richardson, G.W. Groves, In situ solid- calcium silicate hydrate, Adv. Cem. Based Mater. 3 (1996) 144–156.
state NMR studies of Ca3SiO5: hydration at room temperature using 29Si [183] X. Cong, R.J. Kirkpatrick, 17O MAS NMR investigation of the structure
enrichment, J. Mater. Sci. 29 (1994) 3926. of calcium silicate hydrate gel, J. Am. Ceram. Soc. 79 (1996)
[162] I.G. Richardson, G.W. Groves, The structure of the calcium silicate 1585–1592.
hydrate phases present in hardened pastes of white Portland cement/blast- [184] M.W. Grutzeck, A new model for the formation of calcium silicate
furnace slag blends, J. Mater. Sci. 32 (1997) 4793–4802. hydrate (C-S-H), Mater. Res. Innov. 3 (1999) 160–170.
[163] J.D. Bernal, J.W. Jeffery, H.F.W. Taylor, Crystallographic research on the [185] M.W. Grutzeck, S. Kwan, J.L. Thompson, A. Benesi, A sorosilicate
hydration of Portland cement. A first report on investigations in progress, model for calcium silicate hydrate (C-S-H), J. Mater. Sci. Lett. 18 (1999)
Mag. Concr. Res. 4 (11) (1952) 49–54. 217–220.
[164] J.D. Bernal, The structure of cement hydration compounds, Proc. 3rd Int. [186] A. Nonat, X. Lecoq, The structure, stoichiometry and properties of CS-H
Symp. Chem. Cem., London, 1952, Cement and Concrete Association, prepared by C3S hydration under controlled conditions, in: P. Grimmer,
London, 1954, pp. 216–236. A.-R. Grimmer, H. Zanni, P. Sozzani (Eds.), Nuclear Magnetic
[165] H.F.W. Taylor, J.W. Howison, Relationships between calcium silicates Resonance Spectroscopy of Cement-Based Materials, Springer, Berlin,
and clay minerals, Clay Miner. Bull. 3 (1956) 98–111. 1998, pp. 197–207.
[166] H.G. Kurczyk, H.E. Schwiete, Electronenmikroskopische und thermo- [187] J.J. Chen, J.J. Thomas, H.F.W. Taylor, H.M. Jennings, Solubility and
chemische Untersuchungen über die Hydratation der Calciumsilikate structure of calcium silicate hydrate, Cem. Concr. Res. 34 (2004)
3CaO·SiO2 und β-2CaO·SiO2 und den Einfluß von Calciumchlorid und 1499–1519.
Gips auf den Hydratationsvorgang, Tonind.-Ztg. Keram. Rundsch. 84 [188] A. Nonat, The structure and stoichiometry of C-S-H, Cem. Concr. Res. 34
(1960) 585–598. (2004) 1521–1528.
[167] H.G. Kurczyk, H.E. Schwiete, Concerning the hydration products [189] I.G. Richardson, Tobermorite/jennite-and tobermorite/calcium hydro-
of C3S and β-C2S, Proc 4th Int. Symp. Chem. Cem., vol. 1, 1962, xide-based models for the structure of C-S-H: applicability to hardened
pp. 349–358. pastes of tricalcium silicate, beta-dicalcium silicate, Portland cement, and
[168] D.L. Kantro, S. Brunauer, C.H. Weise, Development of surface in the blends of Portland cement with blast-furnace slag, metakaolin, or silica
hydration of calcium silicates. II. Extension of investigations to earlier fume, Cem. Concr. Res. 34 (2004) 1733–1777.
and later stages of hydration, J. Phys. Chem. 66 (1962) 1804–1809. [190] K. Garbev, P. Stemmermann, L. Black, C. Breen, J. Yarwood, B.
[169] L.G. Shpynova, I.D. Nabitovich, N.V. Belov, Microstructure of alite Gasharova, Structural features of C-S-H(I) and its Carbonation in air— a
cement stone (hydrated tricalcium silicate), Sov. Phys. Crystallogr. 11 (6) Raman spectroscopic study. Part I: Fresh phases, J. Am. Ceram. Soc. 90
(1967) 747–751 (English translation of Krystallografiya). (2007) 900–907.
[170] H. Stade, On the structure of ill-crystallized calcium hydrogen silicates.II. [191] C.A. Love, I.G. Richardson, A.R. Brough, Composition and structure of
A phase consisting of poly-and disilicate, Z. Anorg. Allg. Chem. 470 C-S-H in white Portland cement-20% metakaolin pastes hydrated at 25 °
(1980) 69–83 (in German). C, Cem. Concr. Res. 37 (2007) 109–117.
[171] H. Stade, W. Wieker, On the structure of ill-crystallized calcium hydrogen [192] A.V. Girão, I.G. Richardson, C.B. Porteneuve, R.M.D. Brydson,
silicates. I. Formation and properties of an ill-crystallized calcium Composition, morphology and nanostructure of C-S-H in white
hydrogen disilicate phase, Z. Anorg. Allg. Chem. 466 (1980) 55–70 Portland cement pastes hydrated at 55 ·C, Cem. Concr. Res. 37
(in German). (2007) 1571–1582.
[172] H. Stade, W. Wieker, G. Garzo, On the structure of ill-crystallized [193] R. Taylor, I.G. Richardson, R.M.D. Brydson, Nature of C-S-H in 20 year
calcium hydrogen silicates. IV. Anion composition of the hydration old neat ordinary Portland cement and 10% Portland cement—90%
products of tricalcium silicate, Z. Anorg. Allg. Chem. 500 (1983) ground granulated blast furnace slag pastes, Adv. Appl. Ceram. 106
123–131. (2007) 294–301.
158 I.G. Richardson / Cement and Concrete Research 38 (2008) 137–158

[194] I.G. Richardson, Electron microscopy of cements, in: P. Barnes, J. [198] I.G. Richardson, A.R. Brough, G.W. Groves, C.M. Dobson, The
Bensted (Eds.), Chapter 22 in Structure and Performance of Cements, 2nd characterization of hardened alkali-activated blast-furnace slag pastes
ed., Spon Press, London, 2002, pp. 500–556. and the nature of the calcium silicate hydrate (C-S-H) phase, Cem. Concr.
[195] I.G. Richardson, G.W. Groves, The microstructure and microanalysis of Res. 24 (1994) 813–829.
hardened cement pastes involving ground granulated blast-furnace slag, [199] I.G. Richardson, The structure of C-S-H in hardened slag cement pastes,
J. Mater. Sci. 27 (1992) 6204–6212. Proc. 10th Int. Cong. Chem. Cem., Göteborg, vol. 2, 1997, 2ii068, 8pp.
[196] I.G. Richardson, G.W. Groves, The composition and structure of C-S-H [200] I.G. Richardson, The nature of the hydration products in hardened cement
gels in cement pastes containing blast-furnace slags, Proc. 9th Int. Cong. pastes, Cem. Concr. Compos. 22 (2000) 97–113.
Chem. Cem., New Delhi, IV, 1992, pp. 350–356.
[197] I.G. Richardson, G.W. Groves, The microstructure and microanalysis
of hardened ordinary Portland cement pastes, J. Mat. Sci. 28 (1993)
265–277.