Journal

J. Am. Ceram. Soc., 94 [4] 12501255 (2011) DOI: 10.1111/j.1551-2916.2010.04207.x r 2010 The American Ceramic Society

Evidence of Solid Water Bridges Found in Hydrating Tricalcium Silicate Paste

Bernie OHare,z,z Rachel A. Steinle,z Hayden Black,z,J Pearl Kaplan,z,** Michael W. Grutzeck,y and Alan J. Benesiw,z
z y

Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802

Materials Research Laboratory, The Pennsylvania State University, University Park, Pennsylvania 16802

The D2O hydration of pure tricalcium silicate (Ca3SiO5) was examined at 231C with parallel measurements using deuterium NMR spectral analysis, deuterium NMR T1 relaxation measurements at several magnetic elds, isothermal calorimetry, scanning electron microscopy, and Vicat needle tests. The results show that the maximum rate of decrease in the deuterium T1 relaxation time of the D2O resonance, the maximum rate of increase in heat production, and the maximum rate of decrease in Vicat needle penetration occur simultaneously within experimental error. Together with results from other recent deuterium NMR studies in our laboratory, these observations support the new hypothesis that the formation of solid water bridges between closely adjacent developing hydrate surfaces causes initial setting. As a conrmatory experiment, it was found that microwave heating immediately after setting, i.e. immediately after zero Vicat needle penetration, softened the paste sufciently to once again allow some needle penetration, and furthermore, that upon cooling, the paste reset. This process could be repeated several times. I. Introduction
RICALCIUM silicate (Ca3SiO5), often abbreviated in cement science as C3S, is the main clinker phase found in anhydrous Portland cement as well as the primary source of calcium and silica needed to form calcium silicate hydrate (CSH), the major strength-producing phase that forms in hydrating Portland cement and concrete. The addition of water to C3S initiates a number of kinetically complex and still poorly understood hydration reactions that ultimately result in the production of two hydrated solid phases, i.e. high compressive strength calcium silicate hydrate (CSH) and calcium hydroxide (Ca(OH)2) (CH). Because CSH is the primary source of compressive strength in hardened cement,1 it seems logical to propose that the intergrowth and entanglement of developing CSH foils is responsible for both the initial setting and the long-term hardening of cement. Conventional tools including Vicat needle, X-ray diffraction, isothermal calorimetry, microwave heating, and scanning electron microscopy (SEM) were used to study the kinetics of setting and hardening of pure C3S hydrated with either H2O or D2O at 231711C. In parallel with these measurements, deuterium NMR was used to obtain static 2H NMR quadrupole echo powder

spectra and T1 relaxation times at three different magnetic elds for the same preparation of D2O-hydrated C3S in sealed capsules as a function of time after the addition of D2O. Our experimental data indicate that the initial setting of hydrating C3S may not be caused by intergrowth and entanglement of CSH. Instead, our data support the hypothesis that the solid surfaces are covered with two or three layers of solid-state water throughout the hydration reactions, and that when the adjacent surfaces grow to within four to six water layers, the solid water layers fuse to form a solid water bridge between them. After a sufcient number of solid water bridges form between closely adjacent CSH foils, the cement sets.

II. Background and Theory

The aim of this work was to focus on the nature and role of water and its products during the setting and hardening process. We have developed programs that can be used to quantitatively calculate deuterium quadrupolar dynamic powder lineshapes, T1, and T2 values for specic jump geometries, jump rates, or rotational diffusion coefcients.2,3 Using these programs, it has been possible to devise reasonable models of O2H bond motion that match the experimental deuterum NMR data over a wide range of temperatures and magnetic elds for 2H2O in porous solids. The match between experimental and theoretical spectra and relaxation times was used to show that the O2H bond motion consists of a mixture of C2 and tetrahedral symmetry jumps in 2H2O-synthesized kanemite and in 2H2O-hydrated Zeolite A, and that the 2H2O in these materials was therefore solid even well above ambient temperatures.2 We have also proposed in earlier work that solid-state water was present in hydrated cement.4 The objective in the work presented here was to measure deuterium NMR T1 relaxation times as a means of tracking the development of solid-state water in the system C3SD2O and correlate it with corresponding Vicat needle, calorimetric, and morphological data. 2 H NMR offers distinct advantages in comparison with 1H NMR for the characterization of angular dynamics because it is dominated by the single nucleus 2H quadrupolar interaction. The electric eld gradient tensor in 2H2O has nearly axial symmetry (Z 5 0.1) about the O2H covalent bond axis and yields a qcc of 215 kHz.5 The spectrum and relaxation times for 2H2O can therefore be used to monitor the time dependence of the angle made by the molecular O2H covalent bond with the magnetic eld.6 The situation for 1H NMR, where the intramolecular 1H1H dipolar interactions, intermolecular 1H1H dipolar interactions, and heteronuclear (X1H) dipolar interactions must be considered, is much more complicated, and for this reason was not used in these studies.ww A repertoire of deuterium NMR techniques are sensitive to O2H motions with frequenww H NMR relaxation studies, including eld cycling NMR measurements, yield useful information about motion of water, but the information is more difcult to connect to specic types of motion because of the large number of pairwise dipolar interactions that must be considered.

L. Strublecontributing editor

Manuscript No. 28210. Received June 18, 2010; approved September 24, 2010 Based in part on the thesis submitted by Bernie OHare for the Ph.D. degree in Chemistry, The Pennsylvania State University, University Park, PA, 2009. z Present address: Bruker-Biospin Corporation, Billerica, MA 01821, U.S.A. J Present address: Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, U.S.A. **Present address: Department of Environmental Sciences and Engineering, The University of North Carolina at Chapel Hill, Chapel Hill, NC 27599, U.S.A. w Author to whom correspondence should be addressed. e-mail: alan@chem.psu.edu

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Evidence of Solid Water Bridges in Hydrating Tricalcium Silicate

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cies (nmotion) of 1 102onmotiono1 1015 s1.7,8 These encompass most of the range of frequencies of reorientational and translational motions of water and other molecules in condensed phases. Almost all experimentally based knowledge about the detailed angular dynamics of water has been derived from deuterium NMR experiments. For bulk liquid and supercooled liquid water, the 2H T1 and T2 relaxation times show that the O2H bonds experience isotropic rotational diffusion. At 292 K and atmospheric pressure, the rotational rate constant for liquid 2 H2O is 2.8 1011 s1 ( 5 6 Drot, where Drot is the rotational diffusion coefcient),9 while for supercooled liquid water at pressures 42000 atm and temperatures between 188 and 210 K, the rotational rate constants are on the order of 108109 s1.8,10 Although it occurs in some solids with spherically symmetric molecules,11 isotropic rotational diffusion is typical of liquids composed of small molecules. In contrast, for pure solid Ice Ih at atmospheric pressure, 2H NMR lineshape analysis and stimulated echo experiments show that the O2H bonds experience tetrahedral jumps (jump rate B104 s1 several 1C below freezing) due to the diffusion of Bjerrum defects through the ice lattice.12 On a slower time scale, there is also a seven-site reorientation mediated by proton transfer and interstitial translational diffusion.5 For most crystalline hydrates (CaSO4 2H2O for example), variable temperature 2H NMR lineshape analysis shows that the O2H bonds experience rapid C2 symmetry jumps around the bisector of the HOH bond angle with jump rates ! 106 s1 at ambient temperatures.13,14 In a few cases, spectral analysis for crystalline hydrates shows that the water molecules are rigid on the NMR timescale (njumps ( qcc), except for librations that reduce the effective 2H qcc. 2H NMR stimulated echo experiments on tetrahydrofuran clathrate hydrate show that the O2H bonds of the water molecules experience tetrahedral jumps (ascribed to Bjerrum defects) on a distorted tetrahedral lattice as well as a slower randomization process ascribed to a combination of Bjerrum and ionic defects.15 Dynamics characterized by rigidity or jumps rather than rotational diffusion provides atomic-level evidence of the solid state. Recent 2H NMR studies in our laboratories have found that solid-state water exhibits both tetrahedral jumps (like ice Ih) and C2 symmetry jumps (like crystalline hydrates) at room temperature and higher in the layered silicate kanemite (NaHSi2O5 3H2O) synthesized with 2H2O and in the nearly spherical porous cavities of 2H2O-hydrated Na1-Zeolite A (Na12Al12Si12O48 27H2O).2,16 In these samples, where the interlayer spacing and maximum pore diameter are 10.3 and 14.3 A, respectively, all of the internal water was shown to be in the solid state, hydrogen bonded to and extending several layers away from the negatively charged silicate or aluminosilicate solid surfaces, or coordinated to Na1 cations adjacent to the negative surface. In both of these hydrated solids, at ambient and higher temperatures, there is fast exchange between the solid-state water molecules that experience tetrahedral jumps of their O2H covalent bonds and the solid-state water molecules coordinated to Na1 that experience C2 symmetry jumps of their O2H bonds about the 2HO2H bond angle bisector. C2 symmetry jump rates were below 109 s1, far below the isotropic diffusion rotational rate constants observed for liquid water at ambient temperature and pressure. The tetrahedral jump rates were several orders of magnitude slower than the C2 jumps in both cases. The mixture by fast exchange of these two populations of OD deuterium atoms causes an exceptionally broad temperature minimum in the T1 vs jump rate and T1 vs temperature data. This model was found to match the unusual temperature dependence of the experimental deuterium relaxation times as well as the low-temperature powder spectra for these hydrated minerals over a very wide range of temperatures. The presence of solid-state water adjacent to silicate surfaces has also been shown previously with other experimental techniques1719 Attenuated total reection infrared spectroscopy studies by Asay and Kim indicate that the rst three layers of water on fresh silicate surfaces are in the solid state.20

The adsorbed water in CSH is often referred to as interlayer or interstitial water. The surfaces of the CSH foils in contact with the aqueous phase consist of silicate units similar in atomic arrangement to those in kanemite. 29Si solid-state NMR shows that the silicate units are primarily Q2, i.e. that most silicate tetrahedra are covalently bonded to two silicate units, yielding linear (or cyclic) oligomers and polymers. The silicate chains form a sheet-like tobermorite structure sandwiching CaOx polyhedra.21 The oxygen atoms of the silicate units provide hydrogen bonding sites for water, while Ca21 cations provide coordination sites for water in a manner similar to Na1 ions in kanemite and Zeolite A. Oxygen atoms in water, hydroxide ions, silicate SiOSi, and silicate SiO ions are all expected to coordinate to the Ca21 ions in an aqueous solution (i.e., those that are not in the solid Ca(OH)2 phase). The similarity to kanemite is supported by the observation that C2 symmetry jumps are known to dominate the deuterium NMR spectrum of D2O-synthesized gypsum, CaSO4 2D2O (where, for convenience, we have introduced D to represent 2H).13,14 The other nonaqueous solid phase is Ca(OH)2, and strong hydrogen bonds augmented by residual ion dipole forces are also expected. Strong hydrogen bonds to the solid CSH and Ca(OH)2 surfaces and the coordination of water to cationic Ca21 would therefore be expected to stabilize solid-state water structures in their vicinities. We assume that the extent of solidstate water is comparable to what we observed for Zeolite A and kanemite, and to what was observed by Asay and Kim for water on fresh silicate surfaces.2,21 Beyond three water diameters from a nonaqueous solid surface or Ca21 ion, the water molecules would therefore be expected to be in the liquid state at ambient temperatures, although we speculate that solid-state water may be able to extend even farther than three layers in some cases. As relatively large pores are known to exist in hydrated cement, a signicant fraction of the water would be expected to remain in the liquid state. The presence of both solid-and liquid-state water is conrmed in the experiments described below.

III. Experimental Methods

Tricalcium silicate was synthesized from reagent-grade silicic acid and CaCO3 (r0.002% Fe by weight). These reagents were heated to 10001C in a Pt crucible to dehydrate and decarboxylate them, and then mixed in stoichiometric proportions and ball milled in absolute ethyl alcohol with alumina/zirconium balls until homogeneous (typically 24 h). The mixture was poured into a Pyrex dish, allowing the alcohol to evaporate at room temperature. The resulting powder was pressed into 1-in.-diameter pellets, stacked on a zirconia plate, and red repeatedly (after grinding between rings) in a SiC furnace at 15001C or above. The sample was X-rayed and found to be single-phase tricalcium silicate (M1 polymorph). No evidence of CaO was observed. The sample was ground by hand in an agate mortar and then ball milled dry with zirconium balls. The Blaine surface area of the powder was measured as 3400 cm2/g, similar to that of Portland cement. The powder served as the C3S starting material. It was mixed with D2O to yield a D2O/C3S ratio of 0.40 by weight. Part of the well-mixed paste was used for calorimetry, part for Vicat needle testing, and part was placed in NMR sample tubes and sealed with epoxy for deuterium NMR analysis as a function of hydration time. The spectrometers used for deuterium NMR experiments were a Chemagnetics CMX-300 (Varian NMR Systems, Fort Collins, CO) (6.98 T, 45.65 MHz), a Chemagnetics Innity 500 (11.74 T, 76.73 MHz), a Bruker DRX-400 (Bruker-Biospin Corporation, Billerica, MA) (9.41 T, 61.50 MHz), a Bruker DPX-300 (7.05 T, 46.08 MHz), a Bruker AMX2-500 (11.75 T, 76.77 MHz), and a Bruker DRX-600 (14.10 T, 92.15 MHz). The T1 value of the sharp D2O peak was determined on the liquidstate spectrometers using the inversion recovery pulse sequence, pxtvariable(p/2)f1Acquirefref, with f1 5 x, y, x, y and

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fref 5 x, y, x, y (p/2% 90 ms and p% 180 ms) at 46.08 MHz, 61.50 MHz, and 76.77 MHz at 231711C. Deuterium solid-state powder spectra were obtained at 231711C on a solid-state spectrometer at 45.65 MHz with the quadrupole echo pulse sequence, (p/2)xt1(p/2)7yt2Acquirex with Cyclops phase cycling added to all pulse phases and the receiver phase (p/2 5 2.0 ms, t1 5 30 ms, t2 5 25 ms, spectral width 5 1 MHz). This is the standard phase cycling for the quadrupole echo experiment and eliminates artifacts from FID breakthrough. The inversion recovery quadrupole echo experiment, pxtvari(with Cyclops phase able(p/2)xt1(p/2)7yt2Acquirex cycling added), was used to obtain T1 values on the solid-state spectrometers. T1 values obtained at the same magnetic eld for the sharp central peak were the same within experimental error (ca. 75%) whether they were obtained on the liquid-state spectrometers with the inversion recovery sequence and soft pulses or with the quadrupole echo inversion recovery sequence on the solid-state spectrometers with hard pulses. Corresponding paste samples made from the same preparation of C3S with D2O (H2O/C3S 5 0.40 by weight) were tested using a modied Vicat needle procedure that penetrated into a small paste-lled mold (2 in. smallest diameter and 2 in. tall). The mold was covered with plastic wrap to prevent evaporation between measurements to simulate the sealed NMR samples. Vicat needle tests were also carried out on paste samples made with H2O (H2O/C3S 5 0.36 by weight). The heat evolution from 1.85 g of the same D2O hydrated paste was monitored continuously using a Thermonetics isothermal conduction calorimeter in a thermally isolated Styrofoam enclosure placed in a room with a well-regulated temperature of 231711C. After thorough mixing, paste samples were placed in a sealed 1 in.2 cubic stainless-steel sample holder that t snugly into the calorimeter cup. Data were collected using a computer data logger. Calorimetric tests were also carried out on paste samples made with H2O. In addition, small subsamples of H2O-hydrated C3S were allowed to hydrate at 231C as a function of time in tightly sealed glass vials. Using Vicat needle penetration to monitor the setting, samples (w/s 5 0.36, which is the same stoichiometric ratio as that used for the D2O-hydrated samples) were freeze dried (rst immersed in liquid N2 and then freeze dried at low pressure) at various stages of hydration and used to examine microstructural characteristics with SEM.

IV. Results
The Vicat needle tests (Fig. 1) for H2O-hydrated and D2O-hydrated C3S show that setting takes approximately three times longer for D2O-hydrated C3S than for H2O-hydrated C3S. The same phenomenon has been reported previously.22 This is a
Vicat Needle Penetration (mm) 40 35
Vicat Penetration (mm)

large kinetic isotope effect with a signicance that remains to be elucidated, but clearly demonstrates a major role of water in setting. Figure 2 shows the Vicat needle data for H2O-hydrated C3S along with the times (indicated with stars) when samples of the paste were removed for freeze drying in preparation for SEM. For both H2O- and D2O-hydrated C3S samples, Vicat needle penetration decreased as the sample set. Setting is considered complete when the needle no longer penetrates the sample. For example, it took B400 min for the sample in Fig. 2 to set. In samples that had only just achieved complete setting, full or partial penetration could be reestablished easily by heating the paste in a microwave oven for 3060 s. Cooling the sample for a few minutes stopped needle penetration as setting again occurred, reproducibly. This process could be repeated several times for samples that had not been set completely for more than about an hour, suggesting that the freezing and melting of water bridges plays a crucial role in initial setting. It is proposed that the microwave heating of the sample introduced enough local energy to melt the solid-state water bridges sufciently to allow the sample to become soft enough for needle penetration. Scanning electron micrographs of some of the selected H2Ohydrated C3S samples described earlier were examined in order to observe the progressive development of surface features that could be correlated with the other kinetic data. In summary, the images did conrm a sharp increase in the production of foil-like CSH hydrate after about 280 min. The production of hydrate foils and the corresponding increase in surface area accelerates very rapidly thereafter. The deuterium T1 relaxation times of the D2O resonance and heat evolution of the D2O-hydrated C3S are shown as a function of time along with the Vicat needle data in Fig. 3. The data in Fig. 3 show that the maximum rate of increase in heat output occurs when the Vicat needle penetration is decreasing rapidly and the needle penetrates about halfway through the sample. Recalling that the paste is rst mixed externally and then placed in the calorimeter cavity, it is suggested that the initial decrease in the heat ux observed in Fig. 3 (1015 min) is an artifact of placing the paste-lled calorimeter cup in the slightly warmer insulated calorimeter cavity. It is noteworthy that the maximum heat evolution rate is observed after the cement has set completely (B1200 min). After reaching its apex at B2000 min, the rate of heat evolution asymptotically decreases toward zero, as hydration continues to occur for weeks, months, and even years thereafter. The heat output rate data shown in Fig. 3 start at 50 min after mixing and end 10 045 min after mixing. Integration of the entire heat output
Vicat H2O 23 C Vicat H2O

40 35 Vicat Penetration (mm) 30 25 20 15 10 5 0 0 50

30 25 20 15 10 5 0 0 200 400

Vicat D2O (mm) Vicat H2O (mm)

100 150 200 250 300 350 400 450 500 Time (min)

600 800 1000 1200 1400 1600 Time (min)

Fig. 1. Vicat needle penetration vs time at 231C for C3S/H2O (w/s 5 0.36) vs C3S/D2O (w/s 5 0.40).

Fig. 2. Vicat needle penetration at 231C as a function of time for H2Ohydrated C3S with sampling points indicated by open stars, when samples were removed into glass vials and were immersed in liquid N2 to stop hydration. The samples were subsequently freeze dried for examination by scanning electron microscopy. Note: the rst sample was taken from the starting C3S before the addition of water.

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Evidence of Solid Water Bridges in Hydrating Tricalcium Silicate

400 350 300 20 15 10

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V. Discussion
The accumulation of solid-state water with time is indicated by the decreasing deuterium T1 value of the central D2O peak, Fig. 4, and by its magnetic eld dependent deuterium T1 values, Fig. 3. In bulk liquid D2O at 231C, the deuterium T1liquid 5 400 ms and is independent of the magnetic eld.23 In D2O-synthesized kanemite and D2O-hydrated Zeolite A at 231C, where all of the D2O is solid state, the T1solid values are slightly different for the two materials and are also magnetic eld dependent: at 46 MHz, T1solid 5 4.6 ms for kanemite and T1solid 5 7.3 ms for Zeolite-A and at 76.8 MHz, T1solid 5 6.4 ms for kanemite and T1solid 5 9.7 ms for Zeolite A.zz These values correspond to jump rates ranging from 103 to 106 s1 for tetrahedral and 106109 s1 for C2 symmetry jumps, many orders of magnitude below the rotational rate constants observed for liquid water at atmospheric pressure (10111012 s1). We propose that the solidwater interfaces of hydrating C3S are similar to those that were observed for D2O in kanemite and Zeolite-A (Table I), with solid-state water extending two to three layers away from Ca21 ions, silicate oxygen atoms, and Ca(OH)2 surfaces. Some of the experimental inversion recovery data used to calculate the T1 values shown in Fig. 3 were t with the Kohlrausch b stretched exponential function, It a b et=T1 . These analyses yield b4.95 in all cases, consistent with a nearly monoexponential relaxation process and a narrow range of T1 relaxation times within the sample throughout the setting process.24 This nding is consistent with the well-known biphasic fast exchange model.25 Invoking the fast exchange model and our solid water hypothesis, the experimentally observed T1observed values from Fig. 3 represent the fast exchange between residual liquid water and solid-state water T1 values2:  1 T1  fliquid
observed

Depression (mm)

30 25 20 15 10 5 0 0 2000

200 150 100 50 0 4000 6000 8000 10000 12000 Time (min)

T1 (ms)

250

5 0 5 10

Fig. 3. Vicat needle penetration (solid triangles), heat output (open squares), and deuterium NMR T1 values at three magnetic elds (11.75 T, 76.77 MHz: x, 9.41 T, 61.50 MHz: solid squares, and 7.05 T, 46.08 MHz T: solid diamonds) for sealed samples held at 231C as a function of time after mixing Ca3SiO5 with D2O (0.40 g D2O per g Ca3SiO5).

rate with time yields the heat evolved over this period: 1624 J (this value includes the negative contribution of the initial apparent heat absorption). The deuterium T1 values (Fig. 3) start to decline immediately after mixing, and precede any observable setting by the Vicat needle method. The deuterium T1 values, like the heat output, continue to decrease long after setting is complete. Also, there is an increasing and reproducible effect of the magnetic eld strength on the deuterium T1 values, with the shortest T1s observed at the lowest eld and the longest at the highest eld. An interesting empirical observation is that setting is about halfway complete when the deuterium T1 value declines to about 200 ms at this temperature. The deuterium quadrupole echo spectrum of D2O-hydrated C3S 3 months after mixing is shown in Fig. 4. In Fig. 4, the broad Pake powder pattern with outer horns at 798.3 kHz (qcc 5 262 kHz, Z 5 0) is assigned to rigid (on the D time scale) solid Ca(OD)2 (CH) or Portlandite.4 The slow angular dynamics of this rigid solid also produce long deuterium T1 values, hence the necessity for the long relaxation delay for the spectrum shown in Fig. 4. The sharp central peak represents D2O. It is the T1observed of the sharp D2O resonance that is plotted in Fig. 3 for the hydrating paste. At 231C, the deuterium T1observed for the 3-month-old sample shown in Fig. 4 is 16.7 ms at 46 MHz.

Heat Output (mW)

1 T1

 fsolid
liquid

1 T1

 (1)
solid

where fliquid1fsolid 5 1. The experimental deuterium T1observed values obtained at 231C at all magnetic elds were then t to Eq. (1) using the assumptions that the total fraction of water must be 1, that the T1liquid at all magnetic elds is 400 ms, and that at any given time of hydration, the fliquid and fsolid values must be xed and independent of the magnetic eld. With the additional relationship fliquid 5 (1fsolid), each experimental T1 value at a specic magnetic eld requires the calculation of two unknowns: T1solid and fsolid. This is underdetermined. However, our ndings for T1solid in a variety of D2O-hydrated materials, namely kanemite, Zeolite A, freeze dried D2O-hydrated starch, and freeze dried D2Ohydrated cellulose at room temperature, all have very similar values (Table I).yy Assuming that similar values occur in D2Ohydrated C3S, one can estimate the fraction of solid water as a function of time, Fig. 5. For example, if we assume that the T1solid 5 4.6 ms at 231C as is observed for kanemite at 45.65 MHz, the fsolid value for the D2O in Fig. 4 (T1observed 5 16.7 ms) is 0.266. Using the same assumption for the eld-dependent data from Fig. 3 yields Fig. 5. If this assumption holds, Fig. 5 shows that even after 3 months of hydration, more than 70% of the water in the hardened cement is still in the liquid state. There are apparently many waterlled pores with dimensions greater than six layers of water ( 15 B A). It should be kept in mind, however, that none of the loosely
zz In both of these hydrated solids, the dynamics of the OD bond vector is limited to slower tetrahedral jumps on an ice-like lattice of hydrogen-bonding sites in addition to faster C2 symmetry jumps for those water molecules directly coordinated to Na1. Fast exchange between the water molecules experiencing the two types of solid-state jump motion yields the observed T1solid using the fast exchange model.

300

200

100

0 KHz

100

200

300

Fig. 4. 2H (D) quadrupole echo spectrum of D2O-hydrated C3S at 231C 3 months after mixing ((p/2)xt1(p/2)7yt2Acquirex, with additional Cyclops phase cycling of all pulses and the receiver), with p/2 5 2.0 ms, t1 5 30 ms, t1 5 25 ms, relaxation delay of 60 s, full spectral width 5 1 MHz, phased FIDs left shifted to the echo maximum, 3 kHz of exponential apodization).

1=T1 solid fC2 1=T1 C2 ftet 1=T1 tet

yy Table I includes unpublished results for D2O hydrated, freeze-dried starch, and cellulose.

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Table I. Room-Temperature Deuterium T1 Values for the Water Resonance in D2O-Hydrated Materials
Deuterium T1 value, 46 MHz (ms) Deuterium T1 value, 77 MHz (ms)

Material

D2O-synthesized kanemite D2O-hydrated zeolite A Freeze-dried D2O-hydrated starch Freeze-dried D2O-hydrated cellulose D2O

4.6 7.3 5 5 400

6.4 9.7 10 10 400

bound liquid-state water can evaporate because the samples are sealed. Unsealed samples would be expected to lose much of their loosely bound liquid-state water by evaporation. Overall, the picture that emerges is that the surfaces of the nonaqueous solid phases in hydrated tricalcium silicate pastes are coated with a solid-state aqueous phase (water) two to three water layers thick. Water farther than about three layers from a CSH or CH surface is in the liquid state. As CSH and CH phases grow into the liquid-lled spaces between the C3S grains, their solid water-covered surfaces grow close enough together that they are eventually separated by only four to six water layers. At this point, the solid water regions make contact and fuse to form solid water bridges that glue the grains together. The solid-state water glue is created by hydrogen bonding between water molecules, by hydrogen bonding between water molecules and silicate oxygen atoms, by iondipole forces between Ca21 and water oxygen lone pair electrons, and by the electric eld gradient created by the negative surface charge and the positive Ca21 ions. When the number of interparticle solid-state water contacts is sufciently large that all of the particles are connected, the cement is said to be completely set, i.e. the Vicat needle can no longer penetrate the sample. At zero Vicat needle penetration (i.e., complete setting), the sample appears to contain roughly 10% solid water and 90% liquid water (assuming the T1solid values in Table I). The alternative hypothesis ascribes setting to intergrowth and interpenetration of nonaqueous solid phases, particularly CS H. Although the latter hypothesis is not refuted by the data presented here, it is troublesome for several reasons. First, liquid-state D2O has a eld-independent T1 of 400 ms corresponding to a rotational rate constant of 2.8 1011 s1, whereas our data show eld-dependent T1 values indicating rotational rate
1.2
Fraction Solid Fraction Liquid

constants or jump rates below 109 s1. Only solid-state D2O experiencing jumps or supercooled liquid D2O at pressures above 2000 atm and temperatures on the order of 200 K could explain these observations. As the experiments were carried out at 1 atm and 296 K, the latter explanation is improbable. Moreover, the ability of a paste to go through repeated cycles of rheological measurements and each time exhibit Bingham behavior: a nearly consistent yield stress, followed by near Newtonian behavior, argues against the intergrowth and interpenetration hypothesis (M. W. Grutzeck, unpublished results). Struble and Lei26 presented rheological data for the setting of cement paste, which led them to conclude The failure strain increased abruptly at the initial set, indicating a change in the nature of the forces that hold the particles together. Based on this abrupt increase in failure strain and on the SEM evidence of hydration during the induction period, it is concluded that the increase in yield stress was due to the accumulation of gel between cement grains, which increases the force by which the grains are held together. From this point of view, the solid water bridges of our hypothesis t well because they are based on noncovalent, relatively weak hydrogen and ion dipole bonds that do not hold the paste together strongly. The solid water bridges provide some rigidity, but are not of high strength and would be expected to break above a certain yield stress, beyond which the paste would exhibit uid behavior. Further support for the solid water bridge hypothesis is provided by the observation that just set pastes revert to uid behavior with microwave heating. Although arguments to explain these observations can also be made to t the intergrowth/interpenetration model of setting, the simpler explanation is provided by the solid water bridge hypothesis. Therefore, we would now interpret Struble and Leits ndings as evidence of increasing solid water bridges with the reduction in interparticle spaces as hydration proceeds. Initial set occurs when a critical number of bridges have formed to confer rigidity deemed as initial set. The amount of heat given off during setting is much greater (1624 J for the 1.85 g calorimetry sample between 50 and 10 045 min) than the heat of fusion from the approximately 10% of the D2O that becomes solid during setting (ca. 19 J).27 Heat is also evolved during the formation of the CSH and Ca(OH)2 solid phases; hence, the assignment of the respective enthalpy changes is ambiguous. Stadelmann et al.28 used krypton adsorption measurements to study the surface area of hydrating C3S with time. They observed a rapid increase in the surface area of the CSH during the acceleratory period (the period of rapidly decreasing Vicat penetration, rapidly increasing heat output, and rapidly decreasing deuterium T1 values). This nding lends substance to the idea that the heat evolution curve is due in large part to CS H formation. The accumulation of solid-state water occurs as more solid silicate surfaces are formed, and the molecular lms of water on their fresh surfaces are converted to the solid state.

Fraction Solid and Liquid

1 0.8 0.6 0.4 0.2 0 0 20000 40000 60000 80000 100000 120000 Time (min)

VI. Conclusions
Systematic analysis of tricalcium silicate hydration shows that setting, the maximum rate of change in heat evolution, and the maximum rate of change in D2O T1 relaxation times occur simultaneously within experimental error. The data are consistent with the hypothesis that solid surfaces are covered with two or three layers of solid-state water throughout the hydration reactions, and that when the adjacent surfaces grow to within four to six water layers, the solid water layers fuse to form solid water bridges. As very high surface area CSH and lower surface area Ca(OH)2 phases grow into the water-lled spaces between the reacting C3S grains, the distances separating the CSH foils decrease. Because they are immersed in an aqueous solution throughout the setting process, rst contacts between growing hydrated particles must be preceded by water contact. The solid water bridges comprise the initial network contacts that form during and after the setting process. When there are sufcient solid-state water bridges, the cement begins to exhibit what

Fig. 5. Fractions of liquid- and solid-state water in D2O-hydrated C3S as a function of time at 231C after mixing obtained from the experimental deuterium T1 data and Eq. (1), assuming T1liquid 5 400 ms, T1solid 5 4.6 ms at 46 MHz and 6.4 ms at 77 MHz (as observed for kanemite at room temperature).

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Evidence of Solid Water Bridges in Hydrating Tricalcium Silicate

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one refers to as setting as measured by Vicat needle penetration. The heat evolved during the setting process is primarily due to the formation of stable CSH and Ca(OH)2 hydrates, but there is also a small contribution from the heat of fusion of the solid-state water on CSH and Ca(OH)2 surfaces. Even after complete hardening for sealed samples, a signicant amount of liquid-state water remains in pores larger than 15 A due to the weaker forces farther from the solid surfaces. In solid water bridges, the water molecules are hydrogen bonded to other water molecules in the adjacent layer or via their H atoms to oxygen in SiOSi, SiO, Ca(OH)2, and/ or via their O atoms to Ca21 cations, Ca(OH)2, and perhaps Si OH groups. The dynamic solid water network and residual liquid-state water more than three layers from the nonaqueous solid surface allow for Ca21 and SiO4 to diffuse, and provide 4 these reactants access for the formation of more CSH foils and brils with time. Finally, it is important to note that solid water bridges are not likely to be the source of strength for fully cured and hardened cement. They may contribute, but it is more likely that interpenetration, fusion, and entanglement of nonaqueous solid phases provide most of the strength in fully hardened cement.

Acknowledgments
We thank Ed Rakiewicz for suggesting investigations of cement with deuterium NMR, John Phair for insights about kanemite, Burkhard Geil for his generous help with our jump dynamics model, Seong Kim for insightful discussions about solid-state water at interfaces, and Shoshanna Pokras for assisting with some of the experiments.

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