Research and Development of the

Laboratories

Portland Cement Association

RESEARCH

DEPARTMENT

Bulletin 138

Tobermorite Gel The Heart of Concrete

By Stephen Brunauei

Authorized reprint from Amerieao Scientist Voi. 50, No. 1, 210-229 (March 1962)

TOBERMORITE THE HEART

GEL

OF CONCRETE
By

Stephen Brunauer

PORTLAND CEMENT ASSOCIATION RESEARCH AND DEVELOPM 13NT LABORATORIES 5420 Old Orchard Road Skokie, Illinois

TOBERMORITE THE HEART

By STEPHEN

GEL

OF CONCRETE
BRUNAUER

HEN PORTLAND cement is mixed with a limited amount of water, the resulting paste sets, i.e., it becomes reasonably firm in a few hours. The paste then continues hardening for months or even years. This hardened paste is the matrix in which the aggregate is embedded in concretethe grains of sand, the pieces of gravel or crushed stone are held together by the cementing action of hardened paste. Hardened paste and aggregate together form the artificial rock called concrete. Most of the important engineering properties of concrete, such as strength, dimensional stability, and permeability to water, are determined primarily by the properties of the hardened portland cement paste matrix w. Portland cement is a mixture of several compounds, among which the most important ones are two calcium silicates: tricalcium silicate, Ca$i05, and &dicalcium silicate, &CaJ3iO+ These two silicates constitute about 75~o of a portland cement by weight. In the hydration reaction, the two silicates produce similar calcium silicate hydrates and different amounts of calcium hydroxide. The calcium silicate hydrate, because of its similarity to the natural mineral tobermorite [21,has been called tobermorite gel, and this gel is the most important constituent of hardened portland cement paste and, consequently, also of concrete. Tobermorite gel plays a vital role in determining the theological properties of fresh portland cement paste, which properties in turn determine the consistency and workability of fresh concrete. Tobermorite gel plays a dominant role in the setting and hardening of the paste and in determining the strength and dimensional stability of hardened paste and concrete. It is, therefore, no exaggeration to say that tobermorite gel is the heart of concrete.
Hydration of the Calcium Silicates

1. Pastes of tricalcium silicate and dicalcium silicate set and harden, qualitatively, in the same manner as do pastes of portland cements. (There are four crystalline varieties of calcium silicate, but only one occurs in portland cements, the p-form. Whenever reference is made to dicalcium silicate, the ~-form is to be understood.) If one mixes tricalcium silicate with a limited amount (e.g., 0.7 of its own weight) of water at room temperature, and allows the mixture to stand, the reaction goes to completion in about a year. Examination of the hardened paste [31leads to the following stoichiometry of the reaction 2Ca&3i0, + 6Hi0 = Ca&i207.3Hz0 + 3Ca(OH), (1)

210

TOBERMORITE GEL--THE HEARTOF CONCRETE

211

The tricalcium silicate was ground to the fineness of portland cement, which has an average grain size of the order of 10P. This is a very fine powder from the point of view of a chemical engineer, yet the surface of the unhydrated material is negligible compared to the surface of the hydrated material. The specific surface area of the calcium silicate hydrate produced in the hydration is of the order of 300 m2/g, which is about 1000 times the specific surface of the tricalcium silicate. The calcium hydroxide appears in relatively large crystals, making a negligible contribution to the surface of the hardened paste. The surface of the calcium silicate hydrate will be discussed in detail later. The calcium silicate hydrate produced in the hydration of tricalcium silicate (and, as will be seen, of dicalcium silicate also) is a gel. It is called tobermorite gel or tobermorite (G). 2. There were two difficulties encountered in the determination of the stoichiometry of the hydration of the above reaction: one was in the determination of the calcium hydroxide produced in the reaction, the other in the determination of the combined water content of the tobermorite gel. Uncombined calcium oxide and calcium hydroxide can be quantitatively extracted by mpans of a number of organic solvents or solvent mixtures. The method found most suitable by us was proposed by lranke L41, and it employs a mixture of acetoacetic ester and isobutyl alcohol. The trouble was, however, that whether we used the Franke solvent or any other, a part of the lime was extracted also from the calcium silicate hydrate. It seemed, therefore, that the calcium hydroxide should be determined in situ. A method of quantitative analysis by means of X-ray diffraction, developed by Copeland and Bragg M, appeared well-suited for this purpose. It was tried, but it led to variable results, averaging about S5% of the value indicated by equation (1). This meant, we thought, that either the CaO/SiOz ratio in the calcium silicate hydrate was greater than 1.5 or some of the calcium hydroxide was adsorbed on the tremendous surface of the tobermorite gel. X-ray analysis determines only the amount of crystalline calcium hydroxide. We returned, therefore, to the chemical method of extraction. It was true that the Franke solvent extracted some of the lime from the tobermorite, but the rate of extraction was much slower than the rate of extraction of the uncombined calcium hydroxide. We utilized this difference between the rates of extraction to determine the lime contents of both hydration products, tobermorite (G) and calcium hydroxide. Actually, we developed three different modifications of -the Franke method [6,71,and each led to the result shown in equation (1). We found also that the non-crystalline calcium hydroxide was not adsorbed on the surface of the tobermorite. The adsorption of calcium hydroxide was

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AMERICAN SCIENTIST

slight, doubtless because, in t,he competition between calcium hydroxide and water for the surface, water prevailed. The non-crystalline calcium hydroxide, i.e., that undetected by X-ray analysis, was amorphous or very poorly crystallized material 18I. 3. The second difficulty was encountered in the determination of the combined water content of tobermorite (G). The large surface of the gel adsorbed large amounts of water. The question was how much of the water in the hydrate was chemically combined water and how much was adsorbed water. A complete physical separation of the two types of water by methods known at present was impossible. If one equilibrates the hydration products at a water vapor pressure of 5 X 104 mm, which is the vapor pressure of ice at 78C, the tobermorite contains just a little more than two molecules of water. Probably less than l~o of this is adsorbed water. If one equilibrates at a water vapor pressure of 8 X 103 mm, which is the equilibrium pressure of Mg(CIOJz o2Hz0 and Mg(CIOJr 4Hz0, the tobermorite contains 2.8 molecules of water per molecule. Adsorption experiments revealed that 0.3 moles of water per mole of tobermorite was adsorbed water, and 2.5 moles of water was chemically combined. We have called the first method of d~ying dry-ice drying or D-drying, the second, perchlorate drying or P-drying. Tobermorite (G) is a colloid and, like other colloidal hydrates, it loses water from its structure continuously when equilibrated at lower and lower vapor pressures of water. The free energy of binding of the adsorbed water to the surface is variable, as in most adsorbent-adsorbate systems. Although the average free energy of binding of the combined water in the structure is greater than the average free energy of binding of the adsorbed water to the surface, the most firmly bound adsorbed water is held more strongly than the most loosely bound combined water. As a result, at lower vapor pressures some of the combined water is removed, while some of the adsorbed water is held by the hydrate. At higher vapor pressures, tobermorite (G) would contain more than 2.5 moles of combined water and more than 0.3 moles of adsorbed water. Such experiments have not been performed to date, so the three molecules of water indicated in equation (1) are somewhat conjectural. Bernal [91proposed the structural formula Ca2[SiOz(OH)&[C a(OH)zl, which is equivalent to three molecules of water in tobermorite (G), Our experiments are consistent with Bernals formula, except that CaO oHJI should be written in place of Ca(OH)z. After P-drying, the formula is Caz [SiOJOH)z]2Ca0. %HZO, and after D-drying the formula becomes Cat[SiOJOH)z]z CaO. 4. Dicalcium silicate reacts with water much more slowly than tricalcium silicate. The ions are densely packed in CaiSiOA, whereas the structure of Cad3i06 has holes in it [101,which may explain why the

TOBERMORITE GE-THE

HEARTOF CONCRETE

213

latter is more easily attacked by water. Also, Ca@i06 is thermodynamically unstable with respect to CaJ3iOl plus CaO w. When dicalcium silicate is mixed with 0.7 of its own weight of water at room temperature and the mixture is allowed to stand, the reaction does not go to completion even in several years. Examination of a more than four years old hardened paste, which still contained about 15% unhydrated Ca2,SiOl, has indicated the following stoichiometry of the reaction
2Ca,Si04 + 4H,0 = Cat.8iz0,.S .3.3Hz0 + 0.7Ca(OH), (2)

The tobermorite gel in this paste is somewhat different chemically from the one that appears in equation (1); for example, the molar CaO/SiOz ratio in this gel is 1.65 as against 1.50. Nevertheless, the two gels are very similar; their X-ray diffraction patterns are the same, and electronmicroscopical examination reveals the same morphology. The specific surface areas are somewhat different, as will be discussed later. Tobermorite (G) is, thus, not a single compound, nor is it merely the two compounds shown in equations (1) and (2). It is a series of hydrates of continuously varying compositions. The lowest CaO/SiOZ ratio observed by us for a stable tobermorite (G) was 1.39, the highest was 1.75 uu. In the early stages of the hydration reactions, even lower ratios were observed for CaZSiOl and even higher ratios for Ca&3iOs. The word stable does not intend to imply thermodynamic stability. It is probable that only one member of the series is stable thermodynamically, that with the highest CaO/SiOZ ratio.
The Tobermorite Group

1. The tobermorite (G) series of hydrates constitutes a subgroup in the group of hydrates called tobermorites. The natural mineral tobermorite itself is, strictly speaking, not a single hydrate but a subgroup, because samples found in different localities have slightly different chemical compositions and X-ray diffraction patterns [121. All tobermorites, natural or synthetic, are layer crystals. The natural mineral that was found in Northern Ireland had the formula Cal(Si6018HJ . Ca. 4Hz0. Its crystal structure was determined by Megaw and Kelsey [131,who found that the layers were actually triple sheets, with some similarities to vermiculite, Taylor and Howison [141 described the structure as follows.
The central part of each layer, equivalent to the octahedral layer in a clay mineral, could be described as a distorted calcium hydroxide sheet divested of all its hydrogen atoms. This sheet is flanked on both sides by parallel rows of wollastonite-type chains, which are kinked in a plane perpendicular b that of the sheets. Only two-thirds of the tetrahedralin each chain are linked directly to the central CaOzsheet by sharing of oxygen atoms. The other thhd, which are held away from the CaO, sheet, will be called [bridging tetrahedral.The composite 2:1 sheets so

214

AMERICAN SC!IENTIST

far described, have the composition C~Si&&. Between them are the remaining or interlayer calcium atoms, and water molecules. The distribution of the hydrogen i~uncertain. There may be more SiOH than ie implied by the formula Cad(Si&H! ) o Ca. 4H20, with corresponding replacement of interlayer water by hydroxyl. TO a good approximation, tobermorite from the above localities is orthorhombic with a 11,23, b - 7.37, c 22.6 & Z = 4. The crystals are laths with length b (parallel to the chains) and cleavage (001) (the plane of the layers); a and b are both strongly pseudo-halved, and for many purposes a pseudo-cell with Z = 1 may be used. This pseudo-cell is body centered. The longest observed basal ~), and corresponds to the thickness of a single spacing is therefore 002 (d = 11.3 2:1 layer.

The molar CaO/SiO, ratio in this tobermorite is 0.83. Probably this is the lowest limit for any tobermorite; the upper limit found in our laboratory was 1.75, but others reported even higher values [15, 161. 2. When a tricalcium silicate paste is prepared, the water becomes saturated with calcium hydroxide within minutes. The same happens when a dicalcium silicate paste is prepared, except more slowly. The final hydration products, as we have seen, are calcium hydroxide and a member of the tobermorite (G) subgroup. If, however, the silicates are hydrated in a large excess of water, so that the concentration of the lime in the solution is below saturation, the calcium silicate hydrate that forms is not a member of the tobermorite (G) series and, of course, no calcium hydroxide is produced in the reaction. The CaO/SiOz ratio in the calcium silicate hydrate depends on the final concentration of lime in the solution. The lower limit of the ratio (at a low lime concentration) is somewhere around 0.8, the upper limit is in the vicinity of 1.5 (at or near lime saturation). The same series of hydrates can be produced by other reactions, the most widely used among which is the reaction between lime and silica in water. Taylor, who investigated these hydrates most thoroughly, has named the series calcium silicate hydrate (1) or, briefly, CSH (I) 1171. Other names have been used by others (including myself), but in this paper the designation CSH (I) will be used for this tobermorite subgroup. The subgroups tobermorite (G) and CSH (I) differ from each other not only in chemical composition but in morphology, degree of crystallinity and some other properties as well. The CSH (I) hydrate system was studied by many investigators. In a review paper, in 1947 Steinour UN reported the results of sixteen investigations. Although there is a vague general agreement between most of these results, they differ considerably in detail. The differences were probably caused, at least in part, by lack of adequate experimental techniques and lack of complete equilibration but, as will be seen later, there are some more subtle reasons also. Since 1947 other investigations have been published, the results of two of which are reproduced in Figure 1. The molar CaO/SiOZ in the tobermorite is plotted against the lime concentration in the solution,

TOBERMORITEGELTHE HEART OF CONCRETE

215

The curve of Taylor 1171 and the curve of Kalousek 1191 are in broad general agreement, butthey do not agree in detail. Forexample, both curves show that there is a sharp rise in the CaO/SiOz ratio of the solid at or near lime saturation, but Taylors curve indicates an upper limit of 1.5 for the CSH (I) series, whereas Kalousek drew his curve to indicate the upper limit of 1.33. The tobermorites corresponding to the sharply rising portion of the curve do not belong to the CSH (I) subgroup. They belong either to the tobermorite (G) subgroup or to another subgroup to be discussed later. The highest CaO/SiOz ratio for a CSH (I) hydrate obtained in this ,6I
,4 . a, = 2

g 2.0 . j .E 0 ~ a .8 6 .4 . .2 ,

ON 6I.0 .
\

o 01 234

I
56789
Calcium Ion

10

II

12

13
(moles

14

15

16
x )03

17

18

19

20

21 22

Concentration

I 1)

Fm. 1.

Variation of the molar CaO/SiOl ratio in tobermorites with the calcium ion concentration in the solution.

laboratory was 1.44, but others obtained higher values; for example, Grudemo 1201 reported 1.56. The lowest value for the tobermorite (G) series, as stated earlier, was 1.39. It seems, therefore, that the ratios overlap for the two subgroups. This, however, is not certain. It is possible, as Kalousek has pointed out, that the highest lime preparations of CSH (I) contain some tobermorite (G), or the lowest lime preparations of tobermorite (G) contain some CSH (I), or both. 3. The increase in the CaO/SiOZ ratios of the tobermorites is accompanied by an equimolar increase in the HzO/SiOZ ratios [81. lt is a remarkable fact that while the CaO/SiOz and HzO/SiOz ratios in the hydrates of the CSH (I) subgroup, from one end of the series to the other, almost double, the dimensions of the unit cell and the density remain practically constant. When water is removed from tobermorites, the a and b dimensions of the unit cell, i.e., the dimensions within the 2:1 layers described before,

216

AMERICAN SCIENTIST

show a very slight shrinkage, but the shrinkage is so small that these dimensions can be considered constant. The c dimension, however, i.e., the distance between the layers, shows a considerable shrinkage upon removal of water 1171. Removal of lime from the structure results in an increase in the c dimension 1201. Simultaneous removal of a molecule of lime and a molecule of water leaves the c dimension practically unchanged [211.Thus, large changes in composition cause almost no change in the unit cell dimensions. Taylor and Howison 1141 measured the densities of CSH (I) hydrates ranging in CaO/SiOz ratio from 0.81 to 1.50, and found no systematic trend Lo increase with ratio. They have also advanced a hypothesis for the explanation of constant density together with constant unit cell dimension, They have suggested that as the CaO/SiOZ ratio increases, calcium replaces silicon in the lattice. The (bridging SiOl tetrahedral, which are not attached to the central CaOZ sheet, are gradually removed or, more correctly, only SiOj is removed because two of the oxygen ions in each tetrahedron are common to adj scent groups. The calcium ion enters the lattice, but not directly into the place of SiOz, i.e., not into the layer, but between layers. Because the calcium ion has two positive charges and SiOZ is neutral, to preserve charge balance two hydrogen ions must also be removed. The over-all replacement is SiOzHz by Ca, Such a replacement would have a relatively small effect on the cell weight. It would also explain the very slow equilibration between CSH (I) hydrates and calcium hydroxide solutions. If increasing the lime content would involve merely uptake of lime between the layers, one would not expect such a slow equilibration. Finally, the hypothesis predicts that the upper limit of the CaO/SiOZ ratio would be 1.75, corresponding to the removal of all bridging tetrahedral. Although the upper limit of the ratio for the CSH (I) subgroup is around 1.5, the upper limit for the tobermorite (G) subgroup is 1.75, as was stated before, and the upper limit for another subgroup, CSH (11), which will be discussed later, is also 1.75. It is possible that either tobermorite (G) or CSH (II) or both of these subgroups form a continuous series with CSH (I). Brunauer and Greenberg m have modified the Taylor-Howison hypothesis with the suggestion that SiOzHz is replaced not by Ca alone, but by Ca plus a water molecule. Such a substitution would lead to a far better constancy of the cell weight than the Taylor-Howison substitution; it would explain the actually found compositions of tobermorites better; and it would also explain the constancy of the c spacing, mentioned earlier. The modified Taylor-Howison hypothesis accounts quite well for the compositions, structures, densities, and some other properties of the hydrates of the CSH (I) subgroup, possibly even of the entire tobermorite group, 4. While it is true that CSH (I) hydrates of widely different compo-

TOBERMORITEGEk

THE HEART OF CONcRETE

217

(a)

(b)

(c)

(d)

FIGS,2a to 2dCSH(I) hydrates.

sitions can exhibit almost identical X-ray diffraction patterns, it is also true that tobermorites of identical compositions can ex~bit widely different X-ray patterns. The hydrates first of all differ in degree of crystallinity. Heller and Taylor [121 list 46 diffraction lines for the natural

218

AMERICAN SCIENTIST

(e)

(f)

(!?3)

:11)

FIGS.2e and 2hFm. ,2e-CSH(I) hydrate. FIcJ, 2f,-2g.-CSH(II) FIG. 2htobermorite (G) hydrates

hydrates.

mineral from Ballycraigy; a hydrothermal preparation from lime and silica may give almost as many diffraction lines, but a room temperature preparation by the same reaction may give less than a dozen diffraction lines. In addition, the lines may appear at slightly different d-spacings,

TOBERMORITEGEI.r THE HEART OF CONCRETE

219

(i)

(j)

(k)

(1)

FIGS.2i to 21tobermorite (G) hydrates. and

their relative intensities may show great clifferences, Actually, no two investigators report identical X-ray patterns for tobermorite preparations as yet; nor can the same investigator obtain identical patterns if he uses different starting materials, or if he employs slightly different experimental conditions.

220

AMERICAN SCIENTIST

Besides structural variations, the CSH (I) hydrates exhibit a wide range of specific surface areas. The samples prepared in our laboratory had surface areas between 135 and 380 mz/g. Such differences in structure and surface area are, doubtless, responsible for the differences between the two curves of Figure 1 and for the greater differences obtained by earlier investigators UN. Two preparations of a hydrate of a given composition with differences in structure and specific surface area would have different free energy contents and solubilities, Thus, it may happen, as Figure 1 shows, that Taylors tobermorite, with a CaO/SiOa ratio of 1.1, is in equilibrium with a calcium ion concentration of about 3 millimoles per liter, whereas Kalouseks is in equilibrium with a concentration of about 6 millimoles per liter. 5. Figures 2a to 2e are electron micrographs of CSH (I) hydrates prepared by the reaction of lime and silica gel. The reaction products were suspended in an organic liquid and the suspension was subjected to ultrasonic vibrations for a short time to disperse the particles. Figure 2a is a micrograph of a hydrate with CaO/SiOa ratio of 0.98all particles are very thin crumpled sheets, frequently showing rolling up at the edges. As the CaO/SiOz ratio in the CSH (I) hydrate increases, one observes fibrous structures. Figures 2b to 2d are micrographs of a hydrate with CaO/SiOa ratio of 1.29. Particles of different morphologies can be detected: Figure 2b shows crumpled sheets, Figures 2C and 2d show the types of fibrous structure that we shall observe later in the hydration products of CaJ3iOs and Ca$i04. Figure 2e is a micrograph of a hydrate with CaO/SiOs ratio of 1.44; here the particles are predominantly fibers. The fibers may possibly be rolled up sheets, but there is no clear evidence of this in the micrographs of CSH (I) hydrates. The magnification is indicated in each micrograph. The length of the line is 0.5M,except in Figure 2f, in which it is 2p, 6. Figures 2f and 2g show electron micrographs of dicalcium silicate hydrated in excess water, with a water to solid ratio of 9.0. The slurry was placed into a polyethylene bottle, and the bottle was rotated on a wheel for more than two years. Almost all of the preparation was dispersed by ultrasonic vibrations, and all dispersed material consisted of such cigar-shaped particles. The particles show some resemblance to those seen in Figure 2d. The hydrate that exhibits the cigar-shaped particles is a member of another tobermorite subgroup, the CSH (II) subgroup. The CSH (I) subgroup is intermediate in properties between the natural minerals and the CSH (II) subgroup; the CSH (H) subgroup is intermediate in properties between the CSH (I) subgroup and the tobermorite (G) subgroup. Hydrates of the CSH (II) subgroup were first reported by Taylor 1171, and Grudemo obtained electron micrographs for Taylors hydrates similar to those shown in Figures 2f and 2g [201.

TOBERMORITEGEMHE

HEART OF CONCRETE

221

The X-ray diffraction patterns of CSH (II) hydrates are quite similar to those of the CSH (I) hydrates, though there are some differences ma. Both subgroups exhibit many diffraction lines, whereas tobermorite (G) hydrates Avayss howonly three diffraction lines. Onthe other hand, in composition CSH (II) resembles tobermorite (G); the CaO/SiOZ ratios obtained in this laboratory for CSH (II) hydrates range from 1.50 to 1.75,
The Tobermorite (G) Subgroup

1, The tobermorite (G) hydrates are very poorly crystallized. Their X-ray diffraction patterns consist of thre~ lines: a very strong and very broad reflection, with ~ maximum at 3.05 A, and two much weaker broad lines at 2.79 and 1.82 A. These spacings were obtained on samples dried at a vapor pressure of 5 X 10-4 mm (iiD-drying). Heller and Taylor 1221 found that these spacings have indices of (110), (200), and (020), respectively, and they reported the same spacings at 3.07,2.81, and 1.83 & for less strongly dried CSH (I) samples prepared hydrothermally. The three lines of tobermorite (G) hydrates correspond to three of the strongest lines of all tobermorites. All three are (hkO) spacings, i.e., spacings within the layers. The (020) spacing represents half the distance between neighboring Si atoms in the chains of the SiO* tetrahedral of the 2:1 layers described earlier. Twice this distance, 3.64 & is the ~ length of the orthorhombic pseudocell. Twice the (200) spacing, 5.59 A, is the a length of the pseudocell. However, tobermorite (G) exhibits no basal spacing, so the c length can be obtained only by indirect means. The density of D-dried tobermorite (G) preparations, having the formula CaJ3i,0T .2Hz0, was found to be 2.86 g/cc [211.From the molecular weight and the density, one obtains the volume of a molecule. Knowing the a and b lengths, the c length canobe calculated for a pseudocell containing one molecule, and it is 9.3 A. Numerous investigators found this value in X-ray patterns of very strongly dried CSH (1) hydrates; it appears to be the distance of closest approach of two layers. The tobermorite (G) preparations discussed above, when dried at 8 )( 10-3 mm pressure (P-drying), have the formula Ca$iZOT2. 8H20 and the density of 2.73 g/cc. If one assumes that the 0.3 mole of adsorbed water in this hydrate has the density of liquid water, then the density of C@izOT. 2. 5Hz0 is 2.76 g/cc. This gives an interlayer distance of 9.9 A. The extrapolated density of the CaSSizOy 3H1O of equation (1) is 2,70 g/ccj which gives a c spacing of 10.3 & Although the tobermorite (G) hydrates do not exhibit basal spacings, the closely allied CSH (II) hydrates do, and the reported values range between 9,8 and 10.5 ~ (12)(24). Even the three broad diffraction lines of the tobermorite (G) hydrates do not represent the lowest limit in the degree of crystallinity of tober-

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AMERIC!AN SCIENTIST

morites. When tricalcium silicate is hydrated in a small steel ball-mill, an unstable tobermorite is obtained which exhibits only a single broad diffraction band with the maximum in the vicinity of 3 ~ rm. Gard, Howison and Taylor EMIhave advanced a hypothesis for the structures of high-lime tobermorites (tobermorite (G) and CSH (II)), according to which the basic layer is not the triple (2:1) layer of Megaw and Kelsey. 1131 but a double (1:1) layer, one of which is a lime, the other is a silica layer. Our results disagree with this hypothesis. However, Gard, Howison, and Taylor rather suggested than developed their model, so it is possible that a more complete development of the hypothesis may change this conclusion. 2. From the considerations of the previous section we can conclude that in a tobermorite (G) hydrate of composition CaJ3izOY 3HZ0, one molecule of water is between the layers. As the vapor pressure of water is reduced, the interlayer water is lost continuously. On P-drying, about half of this water is lost, on D;drying, all of it. The calculated interlayer distance after D-drying is 9.3 A. It was found in this laboratory 1211 that the hydrate dried to this stage, even after soaking in water for a day, did not swell. Megaw and Kelsey 1131 proposed that in a strongly dried tobermorite, showing a c spacing of 9,6 & the silicate chains in one layer fitted into the grooves between those in the next adj scent layer. This would explain the strong attraction between adj scent layers, leading to the exclusion of water. Tobermorite (G), subjected to P-drying, showed some swelling upon immersion in water, but the swelling was slow and slight, After D-drying, the molecule contains only the hydroxylic water attached to the SiOl tetrahedral in the layers, and this water is much more firmly held than the interlayer water. When the above D-dried sample, having the formula Ca8SiZOl~ 2HZ0, was further dried over PZObfor four weeks to constant weight, only 5% of the water was lost. Thus, at a vapor pressure of the order of }~o00 of that used in D-drying, very little of the layer water was lost. It will be seen in the next section that tobermorite (G) is very finely divided in the c direction. This dimension of the crystallite is colloidal it even verges on the molecular. On the other hand, the dimension of the particles in the b direction, i.e., along the silicate chains, is quite large, it is of the order of a micron or several microns. Thus, speaking with some license, tobermorite (G) is a colloid in the c direction but not a colloid in the b direction. It is interesting that interlayer water is lost continuously, as water is usually lost by colloids, but the water content of the silicate chains remains almost constant over a wide range of vapor pressures. 3. The electron micrographs of tobermorite (G) hydrates show, predominantly, long straight fibers, rather like the ones shown in Figure 2c.

TOBERMORITEGEMHE

HEART OF CONCRETE

223

Figure 2h, obtained from tricalcium silicate hydrated for eight years, shows such fibers, as well as broken fragments of calcium hydroxide crystallite. It also shows some undispersed matter. Figure 2i, obtained from the same paste, indicates that the fibers are actually rolled up sheets, and this is seen more clearly in Figures 2j and 2k, obtained from dicalcium silicate pastes. At placea where the sheets are unrolled, one can see that their thickness is of the order of magnitude of a unit cell. The fibers are long, most of them longer than lLJ. Figure 21 shows an aggregation of fibers, obtained from a tricaIcium silicate paste. The ultrasonic vibrations, in this case, have only separated the fibers slightly but did not disperse them. The aggregation looks like a pile of matches, with the alternate rows crossing each other. 4. The adhesion of the tobermorite (G) particles to each other and to other bodies is responsible for the strengths of hardened pastes of tricalcium and dicalcium silicates; it is also the most important factor in the strengths of hardened portland cement pastes and concrete. The compressive strengths of hardened portland cement pastes exceed their tensile strengths by an order of magnitude, The compressive strengths of hardened calcium silicate pastes are about the same as those of hardened portland cement pastes. Although no data have been published on the tensile strengths of calcium silicate pastes, it seems likely that they are lower than those of portland cement pastes because calcium silicate pastes are dispersed easily by ultrasonic vibrations, whereas portland cement pastes are not. The great discrepancy between compressive and tensile strengths can be understood on the basis of the structure indicated by Figure 21. To produce failure in compression, one must work against the forces within the tobermorite crystallite, i.e., against valence forcesthough, of course, one is aided by the imperfections within the crystallite. On the other hand, to produce failure in tension, one merely has to overcome the adhesion between the tobermorite particles, so one works against van der Waals forces. 5. The hardened pastes of calcium silicates and portland cements are porous bodies, and changes in relative humidity cause movement of water into or out of the pore system. Entry of water results in swelling and removal of water in shrinkage of the paste. When concrete loses water, it shrinks, and this may produce cracking. Among all improvements in concrete that research may bring about, the one most desired by the construction industry is the elimination-or, at least, a great diminutionof shrinkage. Tobermorite gel is the most important factor in the shrinkage of concrete, just as it is the most important factor in the strength of concrete. Figure 3 represents three different mechanisms by which tobermorite (G) may swell upon entry of water (or shrink upon removal of water).

224

AMERICAN SCIENTIST

On the left side, the tobermorite is considered as a sheet, prior to rolling up into a fiber. It will be shown later that all stable tobermorite sheets are either two or three molecular layers thick, Water can enter between these layers, as was discussed before, with the result that the distance between the layers increases. Thus, entry of water produces a swelling of the sheet. %!n the middle Of Figure 3, tobermorite is considered as a fiber, and the cross section of a two-layer tobermorite is shown. Water can enter between the layers at X, which is the mechanism already discussed, but it can also enter at Y into the convolutions of the fiber. Water, in this case,

El
A B

(D

FIG. 3. Three mechanisms of expansion of tobermorite gel.

is adsorbed on the surface of the tobermorite in several layers, and this results in the swelling of the fiber. On the right side of Figure 3, tobermorite is considered as an aggregation of fibers, This is an idealized drawing of the aggregation of fibers shown in Figure 21. Water can enter between the fibers and separate the fibers from each other. This results in a swelling of the aggregation of fibers. Even the above three mechanisms do not exhaust all possibilities of swelling and shrinkage. Water can enter not only into the tiny pore spaces between the individual fibers but also into the much larger pore spaces that exist between aggregations of fibers. The pores between the gel particles are called gel pores, those between aggregations of gel particles are called capillary pores. Entry of water into the capillary pores also produces swelling of the hardened paste; in fact, at high relative humidities, this is probably the most important factor in dimensional changes.

TOBERMORITEGELAHE

HEART OF CONCRETE

225

The Surface

of Tobermorite

(G)

1. l?owers and Brownyard EMIwere the first to measure the specific surface areas of hardened portland cement pastes, using the B.E.T. method ma with water vapor as the adsorbate. They were able to demonstrate that surface area and porosity of the paste play decisive roles in determining the most important engineering properties of paste: strength, dimensional changes, permeability to water, and freezing of water in the pore system. Subsequent work in this laboratory has shown that about 75% of the colloidal fraction of hardened portland cement paste (the so-called (cement gel) is tobermorite gel, and about 80% of the specific surface of hardened portland cement paste is tobermorite gel surface. Work on the pore size distribution of hardened pastes of portland cements and calcium silicates is still in its early stages; it will not be reported, therefore, in the present paper. However, much work has been done on the surfaces of these pastes, It has been established that the specific surface areas and the compositions of the tobermorite gel in pastes of portland cements are the same as in pastes of the calcium silicates. 2. If the rolling of the tobermorite (G) sheets does not create spaces into which water cannot penetrate, the area measured by water adsorption for the fibers should be the same as that of the sheets prior to rolling. This area could be calculated from crystal structure data, if the thickness of the sheets were known. Because the thickness is very small, compared to the two other dimensions of the sheet, practically all of the surface area resides in the two sides of the sheet. The a and b dimensions of the orthorhombic pseudocell of tobermorite (G) are 5.59 and 3.64 A, respectively, If one places one molecule of composition CaJ3izOT 2Hz0 (D-dried tobermorite (G)) into the pseudocell and assumes that the sheet has the thickness of a single pseudocell, calculation gives a specific surface area of 755 m2/g. If the sheet has the thickness of two pscudocells (two molecular layers), the specific surface area is 377 m2/g, and if the thickness is three molecular layers, it is 252 m2/g. In these calculations, the areas along the edges of the sheets have been neglected, In a series of experiments EX1,in which we determined the surface energy of tobermorite (G), we made fourteen preparations, using clifferent starting materials (Ca3Si06 and Ca&liOJ, different waimr to solid ratios (0.7 and 9.0), and three different methods of preparation. The maximum surface area obtained was 376 m2/g, the minimum was 245 mz/g. From this we concluded that all tobermorite (G) particles were either two or three molecular layers thick. At the time of the writing of this paper, more than 100 tobermorite (G) preparations have been examined. In the early stages of hydration of the calcium silicates, we detected single-layer tobermor-

226

AMERICAN SCIENTIST

ites, as well as tobermorites that were more than three layers thick. In these early stages of hydration, the composition of the tobermorite went through changes, as I stated earlier. However, by the time the tobermorite reached its final and stable composition, the surface area also became stabilized, and in every instance it indicated two and three-layer tobermorites. The surface areas of the pastes obtained from the hydration of Ca&3iObindicated a predominance of two-layer tobermorites, those from Ca@i04, three-layer tobermorites, 3. Recent work IIU has established a relationship between the composition and the specific surface area of tobermoritc (G). The specific surface areas of stable tobermorites were plotted against the CaO/SiOz ratios, and a straight line was obtained. The equation of the least squares straight line, based on 44 pastes, was A = 865.0+ 42.9 (354.7+ 39.9)(Ca0/SiOJ (3)

where A is the specific surface area in m2/g, and (CaO/SiOJ is the molar CaO/SiOz ratio. This empirical equation indicates that the more lime there is in the tobermorite the lower the specific surface, which in turn indicates that increase in the lime content results in a larger fraction of three-layer and a smaller fraction of two-layer sheets. It has been suggested that lime has the ability to cement neighboring crystallite of tobermorite together [MI.13quation (3) indicates that lime can cement the layers of tobermorite, within the crystallite, to each other. The slope of the line shows that a unit increase in the molar CaO/SiOz ratio produces a decrease of 354.7 m2/g in the surface area. The decrease per molecule of tobermorite (G) is 19.4 ~z, if the calculation is made for the average composition, i.e., for a CaO/SiOz ratio of 1,55. ~he area contributed by a pseudocell is a b, which is 20.35 ~2. The 19.4 Az value calculated differs from this by less than 5 per cent, whereas the 19.4 ~z value itself has a standard error of 11 per cent, as equation (3) shows. Thus, it appears that a unit increase in the molar CaO/SiOz ratio is accompanied by the disappearance of a unit surface, the surface contributed by a pseudocell, The above calculations are based on a model in which the pseudocell always contains one molecule of tobermorite (G), regardless of composition, and the molecule always contains 2 atoms of silicon. This means that the weight of the pseudocell increases as the CaO/Si02 ratio increases; for example, an increase in the CaO/SiOz ratio from 1,50 to 1.60 means the addition of 0.10 molecule of CaO and 0.10 molecule of HZO to the pseudoccll. This, naturally, should be understood in the average sense, i.e., one molecule of lime and one molecule of water is added to one pseudocell out of ten. The model leads to the structures of two and three-layer tobcrmorite sheets shown in Figure 4. The CaO/SiOz ratios of the two and three-

TOBERMORITEGE&THE

HEART OF CONCRETE

227

layer sheets are 1.39 and 1.72, respectively, andthelowest and highest value obtained inthis laboratory were 1.39 and 1.75. The specific surface areas calculated on the basis of this model for the two and three-layer sheets are 387 and 240 m2/g, respectively, and the highest and lowest values obtained were 391 and 244 m2/g. Equation (3) leads to specific surface areas of 372 and 255 m~/g for CaO/SiO~ ratios of 1.39 and 1,72, respectively; these values differ by 3.9 and 6.2 per cent from the calculated values, which differences are well within the standard error of the curve. The modified Taylor-Howison model VNgives a good description of the CSH (I) subgroup of tobermorites, as was discussed earlier. That model leads to a constant pseudocell weight, in contrast with the model discussed above. If the Taylor-Howison model is valid also for the tobermorite (G) subgroup, the structures of the two and three-layer sheets are somewhat different from those shown in Figure 4. The differences are slight for the three-layer sheet: the surface contains 0.75 molecules
2- LAYER TOSERMORITE
0,77Co0 2 + I Si02 2Si02 2 coo 0,77 CoO+ 3-LAYER TOSERMORITE I===l::=sioz

coo
-(

_
..

_
2Si02-

h===l}Y::0+2si02
F

H
gclo_ ,

,,39

Si02

S102

= 1,72

FIG. 4. Two and three-layer tobermorites.

of CaO instead of 0.77, and the CaO content of the layers between the pseudocells is 1.50 molecules instead of 1.38, The differences are greater for the two-layer sheet: the surface contains 0.60 molecules of CaO and 1.14 molecules of SiOz instead of 0.77 and 1.00 as in Figure 4, and the layers between the pseudocells contain 1.21 molecules of CaO and 2.29 molecules of SiOz instead of no lime and 2,00 molecules of SiO~ as in Figure 4. Experiments are in progress to ascertain which of the two models is correct. 4. Earlier I stated that we used fourteen calcium silicate pastes for the determination of the surface energy of tobermorite (G). Surface energy is an abbreviation for surface total energy, and it is defined as the difference between the total energy of a molecule of a given substance in the surface layer and the total energy of the same molecule inside the body of that substance. If samples of a substance are obtained in different states of subdivision, and the heats of solution of these samples are plotted against their specific surface areas, the plot is a straight line, the

228

AMERICANSCIENTIST

slope of which is the surface energy. Such a plot is shown in Figure 5 for the tobermorite (G) preparations. The slope of the least squares straight line gives a surface energy of 386 + 20 ergs/cm2. Prior to this work, we determined the surface energies of calcium hydroxide 12s1 and hydrous amorphous silica ugI, and obtained the values of 1180 and 129 ergs/cm2, One would expect that the surface energy of tobermorite (G) is between these values for two reasons. Speaking with some license, the surface of the calcium silicate hydrate is a sort of (chemical mixture between the surfaces of calcium hydroxide and
490 r

m$
~ ~ 488 -r, 00

486 -

: : 484 . z 482 s # 48o . : 478 % : 3474 $ x 472 . 476 .

466 -

r-: no

: A 260 280

r- :: + Clzba 300 320 340

IOg Oh 360

$$ I+& 380 400

220

240

Specific

Surfoce

Area

of Ca,Si207.

2 H20 ( mete rs2/grn)

FIG. 5. Variation of the heat of solution of Ca@iz07. 2HZ0 with specific surface area,

hydrous silica, In addition, the calcium hydroxide used in the surface energy determination contained almost perfect crystals, the hydrous silica was amorphous, and the calcium silicate hydrate was intermediate between the two, it was poorly crystallized. The surface energy of tobermorite (G) is almost exactly the geometric mean between the surface energies of calcium hydroxide and hydrous amorphous silica. The point in Figure 5 which falls farthest away from the straight line is the one obtained for the preparation designated as D-49, and it is 2,6 cal/g too high. In all probability, this is a random error, but let us assume that it is not. Let us assume first that all of this difference is caused by some variation in the body structure, such as, for example, differences in crystal defects. The 2.6 cal/g amounts only to 0.58~o of the heat of solution. Let us assume next that none of this difference is caused by variation in the body structure, but all of it is caused by variation in the surface structure. This amounts only to 7.670 of the surface energy of

TOBERMORITEGEMHE tobermorite

HEART OF CONCRETE

229

(G). These figures refer to the preparation If the calculations

showing the max-

imum deviation.

were made for the average deviation,

which is 1.1 cal/g, the results would be less than half of the values given. One can conclude, therefore, that both the body structure and the surface structure of tobermorite (G) are highly reproducible.

ACKNOWLEDGMENT The electron micrographs of Figure 2 were obtained by Dr. L. E. Copeland and Mrs. Edith G. Schulz, and I wish to express my gratitude for their enthusiastic cooperation.
REFERENCES Lecture Presented at Institute of Civil Engineers, London, March 1. T. C. POWERS, 1956. Portland Cement Association Research Department Bulletin 90. G. F. CLARINQBULL and M. H. HEY, Mineral. Mug., ,29,960 (1952). S. BRUNAUER, L. E. COPELAND, and R. H. BRAGG,J. Phys. Chem., 60, 116 (Iwwi) ,- .-.,. 4. B. FRANKE, Z. anorg. u. allgem. Chem,, .247,180(1941). and R. H. BRAGG, Anal. Chem., 30, 196 (1958). 5. L. E. COPELAND S. BRUNAUER, and D. L. KANTRO, Anal. Chem., .28,896 (1956). 6. E. E. PRESSLER, S. BRUNAUMR, D. L. KANTRO, and C. H. WEISE,Anal. Chem., 7. E. E. PRESSLER, 8. S. A. GREENBERG, The Hydration of Tricalcium Silicate and &Dicalcium Silicate at Room Temperature, Proceedings of the Fourth International Symposium on the Chemistry of Cement, Washington, D. C.j 1960 (in uressh J. D. BE~NALj Proceedings of the Third International Symposium on the Chemistry of Cement, London, 1952, p. 216. Msg. Concrete Res., No. 11, J. D. BERNAL, J. W. JEFFnRY, and H. F. W. TAYLOR, 49 (Oct. 1952). D. L. KANTRO, S. BRUNAUER, and C. H. WEISE,The Development of Surface in the Hydration of Calcium Silicatesl in Solid Surfaces and the Solid-Gas Interface, Advances in Chemistry Series (in press). L. HELLER and H. F. W. TAYLOR,Crystallographic Data for the Calcium Silicates. Her Majestys Stationery Office, London, 1956. H. D. MIWAWand C. H, KELSEY,Nature (London), 177, 390 (1956). H. F. W. TAYLOR and J. W. HOWISON, Clay Minerals Bull., 3, 98(1956). A. VANBEMST, Bull. SOC. chim. beiges,, 64, 333 (1955). H. FUNK,Z. anorg. u. allgem. Chem., 291, 276 (1957). H. F, W. TAYLOR, J. Chem. Sot. (London), 3682(1950). H. H. STEINOUR, Chem. Rev., 40, 391 (1947). Proceeding of the Third International Symposium on the G. L. KALOUSBK, Chemistry of Cement,,London, 1952, p. 296. A. GRUDEMO, Proceedings of the Swedish Cement and Concrete Institute, Bulletin No. 26 (1955). S. BRUNAUER, D. L. KANTRO, and L, E. COPELAND, J. Am. Chem. Sot., 80, 761 (1958). L. HELLER and H. F W. TAYLOR, J. Chem. i30c. (London),, 2397 (1951). D. L. KANTRO, S. BRUNAUER, and C. H. WEISE,J. Cokmd i%, 14, 363 (1959). and H. F. W. TAYLOR) Msg. Concrete Res., 11, 151 J. A. GARD,J. W. HOWISON, (Icl!wl) .---.. ,. T. C. POWERS and T. L. BROWNYARD, Proc. Am. Concrete Inst., 43, 101, 249,
.93, 877 (1961). S. BRUNAUER and

9.

10.
11. 12.

15. 16. 17. 18. 19.

20.

21.
22. 23. 24. 25.

26. S. BRUNAUER, P. H. EMMETT, and E. TELLER, J. Am. Chem.JSoc., 60, 309(1938). 27. S. BRUNAUER, D. L. KANTRO,and C. H. WEW.E,Canadian J. Chem., 37, 714

469,549,669,845,933 (1947).

(1Q5Q) \---.. ,. 28., S. BRUNAUER, D. L. KANTRO,and C. H. WEME, Canadian J. Chem.. (1956). 29. S. BRUNAUER, D. L. KANTRO,and C. H. WEISE,Canadian J. Chem.,

34.729 .,

(1956).

84, 1483

Bulletins Published by the Research Department Research and Development Laboratories of the Portland Cement Association
100. List of Published Bulletins and Papers of the Research Department , May, 1959 (Also lists earlier research papers of the Portland

Cement Association).
101. Determination of the Apparent Density of Hydraulic Cement in Water Using a Vacuum Pycnometer, by C. L. Ford.
Reprinted from
ASTM Bulletin, No. 281, 81-84

(July,1958).

102. Long-Time Study of Cement Performance in ConcreteChapter 11. Report on Condition of Three Test Pavements After 15 Years of Service, by FRANK H. JACKSON.
Reprinted from Journal
10171082 (1957-1958)

of the American Concrete Institute

(June,1958);

Proceedings, 54,

103. Effect of Mixing and Curing Temperature on Concrete Strength,

by PAUL KLIEGER.
Reprinted from Journal
10631081 (1967-1958) .

of the American

Concrete Institute (June, 1958);

Proceedtn.gs, 64,

104. The Successive Determination of Manganese, Sodium and Potassium Oxide in Cement by Flame Photometry, by C. L. FORD.
Reprinted from ASTM
Bulletin, No. 238, 57-63
(October, 1958).

105. The Surface Energy of Tobermorite,

KANTRO and C. H. WEISE. Reprinted from Canadian

by STEPHEN BRUNAUER, D. L.
(April, 1959).

Journal of Chemistry, 37, 714-724

106. The Flow of Water in Hardened Portland Cement Paste, by T. C.

POWERS, H. M. MANN and L. E. COPELAND. Reprinted fromHighway Research Board Special Report
40,308-323 (1958).

107. The Ball-Mill Hydration of Tricalcium Silicate at Room Temperature, by D. L. KANTRO, STEPHEN BRUNAUER and C. H. WEISE.
Reprinted fromJournalof
Colloid Science, 14, 363-376
(1959).

108. Quantitative Determination of the Four Major Phases of Portland Cement by Combined X-Ray and Chemical Analysis, by L. E.
COPELAND, STEPHEN BRUNAUER, D. L. KANTRO, EDITH G. SCHULZ and C. H. WEISE.
Reprinted from

Analytical Chemistry, S1, 15211530

(September,

1959).

109. Function of New PCA Fire Research Laboratory, by C. C. CARLSON.

Reprinted f?om the 213 (May, 1959) .

Journal of the PCA Research and Deueloprnent Laboratories,

1, No. 2,

110. Capillary Continuity or Discontinuityy in Cement Pastes, by T. C.

POWERS, L. E. COPELANDand H. M. MANN. Reprinted fromtbe Journal of the PCA Research
38-48 (MaY, 1959).

and Development Laboratories,

1, No. 2,

111. Petrography of Cement and Concrete, by L. S. Brown.

Reprinted from the Journal 2334 (September, 1959).

of the PcA

Research and Development Laboratories,

1, No. 3,

112.

The Gravimetric Determination Cement, by C. L. FORD.

Reprinted fromASTM

of Strontium

Oxide in Portland

Bulletin, No. 246, 71-75 (April, 1960).

113. Quantitative Determination of the Four Major Phases in Portland Cement by X-Ray Analysis, by STEPHEN BRUNAUER, L. E. COPELAND,
D. L. KANTRO, C. H. WEISE and EDITH G. SCHULZ.
Rej?ted from

Proceedings of the American Society for Testing Materials, 59, 10911100

114. Long-Time Study of Cement Performance in ConcreteChapter 12. Concrete Exposed to Sea Water and Fresh Water, by I. L.
TYLER.
Reprinted from Journal

of the American Concrete Institute (March,

1960);

Proceedings, 56,

825-836 (1960).

115. A Gravimetric Method for the Determination Portland Cement, by C. L. FORD.

Reprinted fromASTM
Bulletin, No. 247, 77-80 (July, 1960).

of Barium Oxide in

116. The Thermodynamic Functions for the Solution of Calcium Hydroxide in Water, Mby s. A. GREENBERG and L. E. COPEIJAND.
Reprinted from Journa2

of Physical Chemistry, 64, 1057-1059 (August,

1960).

117. Investigation of Colloidal Hydrated Silicates. I. Volubility Products, by S. A. GREENBERG, T. N. CHANG and ELAINE ANDERSON.
from Reprinted Journal

of Physical Chemistry, 64, 11511156 (September,

1960).

118. Some Aspects of Durability and Volume Change of Concrete for Prestressing, by PAUL KLIEGER.
Reprinted from the (September, 1960).

Journal of the PC!A Research and Development Laboratories, 2, No. 3, 213

119. Concrete

Mix WaterHow
Journal 1960).

Impure

Can It Be? by HAROLD H.

STEINOUR. Reprinted from the

32-50 (September,

of the PCA Research and Development Laboratories, 2, No. 3,

120. Corrosion of Prestressed G. J. VERBECK.

Reprinted

Wire in Concrete,

by G. E. MONFOREand
1960);

from Journal of the American Concrete Institute (November, 57, 491-515 (September, 1960).

Proceedings,

121. Freezing and Thawing Tests of Lightweight Aggregate Concrete,

by PAUL KLIEGER and J. A. HANSON.

779-796 (1961).

Reprinted fromJournal

of the American Concrete Institute (January,

1961);

Proceedings, 57,

122. A Cement-Aggregate Reaction That Occurs With Certain SandGravel Aggregates, by WILLIAM LERCH.
Reprinted fromthe Journal
4250 (September, 1959).

of the PCA Research and Development Laboratories, 1, No. 3,

123. Volume

Changes
13-19 (September,

of Concrete
1960).

Affected

by Aggregate

Type,

by

HAROLD ROPER. Reprinted fromthe Journal

of the PCA Research and Development Laboratories, 2, No. 3,

124. A Short Method for the Flame Photometric Determination of Magnesium, Manganic, Sodium, and Potassium Oxides in Portland Cement, by C. L. FORD.
Reprinted fromASTM
Bulletin, No. 250, 25-29 (December,
1960).

125. Some

Physical Aspects of the Hydration of Portland Cement ,

Reprinted fromthe Journal
4756 (January, 1961).

by T. C. POWERS.
of the PCA Research and Development Laboratories, 9, No.

1,

126. Influence of Physical Characteristics of Aggregates on Frost Resistance of Concrete, by GEORGE VERBECK AND ROBERT LANDGREN.
R&&ted from Proceedings
of the American Society for Testing Materials, 60, 10631079

127. Determination of the Free Calcium Hydroxide Contents of Hydrated Portland Cements and Calcium Silicates, by E. E. PRESSLER,
STEPHEN BRUNAUER, D. L. KANTRO, and C. H. WEISE. Reprinted fromAnalytical Chemistry, W, No. 7, 877-882 (June, 1961).

128. An X-ray Diffraction Investigation of Hydrated Portland Cement Pastes, by D. L. Kantro, L. E. COPELAND, and ELAINER. ANDERSON.
Reprinted from Proceedings of the American Society for Testing Materials, 60, 10201035
(1960).

129. Dimensional Changes of Hardened Portland Cement Pastes Caused by Changes of Temperature, by R. A. HELMUTH.
Reprinted from Highway Research Board Proceedings 40, 316336 (1961).

130. Progress in the Chemistry

(May, 1961).

of Portland Cement,

18871960, by

HAROLD H. STEINOUR. Reprinted from the Journal of the PCA Research and Development Laboratories, 3, No. 2,2-11

131. Research on Fire Resistance of Prestressed Concrete, by HUBERT

WOODS,

including discussion by V. PASCHKIS, and authors closure.

Reprinted

ST 2, 59-60 (February, 1961); Closure, S7, ST

from Journal of the Structural Division, Pmceeding8 of the American Society of CiUi2Engineers, Pmt. Paper 2640, 86, ST 11, 5364 (November, 1960); Discussion, S7, 5,81 (June, 1961).

132. Centralized Control of Test Furnaces in the PCA Fire Research Laboratory, by PHIL J. TATMAN.
2226 (May, 1961)

Reprinted from the

Journal

of the PCA Research and Development Laboratories, 3, No. 2,

133. A Proposed Simple Test Method for Determining the Permeability of concrete,) $by 1. L. TYLER and BERNARD ERLIN.
Reprinted from the (September, 1961).

Journal of the PCA Research and Development Laboratories, 3, No. 3, 2-7

134. The Behavior at High Temperature of Steel Strand for Prestressed Concrete, by M. S. ABRAMS and C. R. CRUZ.
Reprinted from the (September, 1961).

Journal of the PCA Research and Development Laboratories, 3, No. 3, 819

135. Electron Optical Investigation of the Hydration of Products of Calcium Silicates and Portland Cement , by L. E. COPELAND and

EDITH G. SCHULZ.
Reprinted from the Journal 2-12 (January, 1962).

of the PCA Research and Development Laboratories, 4, No. 1,

136. Soil-Cement
1321

TechnologyA Resume, by MILES D. CATTON. Reprinted from the Journal of the PCA Research and Development Laboratories, 4, No.
(January, 1962).

1,

137. Surface Temperature Measurements With Felted Asbestos Pads,

by M. S.
138.

ABRAMS. Reprinted from the Journal of the PCA Research and Development Laboratories, 4, No. 1, 223o (January, 1962).

Tobermorite
Reprinted

GelThe
from the

Heart of Concrete,

by Stephen Brunauer.
(March, 1962).

American Scientist, 50, No. 1,210-229