Studies on Tobermorite-Like Calcium Silicate Hydrates

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Department of Transportation and Purdue University, West Lafayette, Indiana, 1963. ... members and Sloan Foundation; Indiana Department of Transportation.
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1963

Studies on Tobermorite-Like Calcium Silicate Hydrates : Technical Paper Sidney Diamond [email protected]

William Lee Dolch Joe L. White

Recommended Citation Diamond, S., W. L. Dolch, and J. L. White. Studies on Tobermorite-Like Calcium Silicate Hydrates : Technical Paper. Publication FHWA/IN/JHRP-63/33. Joint Highway Research Project, Indiana Department of Transportation and Purdue University, West Lafayette, Indiana, 1963. doi: 10.5703/ 1288284313642. This document has been made available through Purdue e-Pubs, a service of the Purdue University Libraries. Please contact [email protected] for additional information.

STUDIES ON TOBERMORITE-LIKE CALCIUM SILICATE HYDRATES

»

Technical Paper STUDIES ON TOBERMORITE-LIKE CALCIUM SILICATE HYDRATES

TO:

K. B. Woods, Director Joint Highway Research Project

Octoher 31, 19&3

Joint Highway Research Project

File: M>-9 Project: C-36-47I

The technical paper attached entitled "Studies on Tobermorite-Like Calcium Silicate Hydrates" by Sidney Diamond, W. L„ Dolch, and Joe L. White is submitted for approval of presentation and publication.. The presentation is proposed to the Annual Meeting of the Highway Research Board in Washington D»C, in January 196^. Publication would be by that organization e.

The paper is a part of the investigation known as "Calcium Silicate Hydrates" which was conducted by the Joint Highway Research Project utilizing HPS funds o The material is taken from the Final Report on this project which has been submitted for review and acceptance. In the event that approval for presentation has not been received by the date of presentation, the presentation will include a statement that review of the paper has not been made by the ISHC or the BPR„ This is the second paper which has been prepared from this research and which has been submitted for review* A third paper is contemplated and will be submitted upon completion of ito The paper is presented to the Board for approval of presentation and publication

Respectfully submitted,

?/.'/.

??u^£j

Ho Lo Michael, Secretary HIM: be

Attachment Copy: F. L. Ashbaucher J. R. Cooper

w

Lo Dolch

Wo F, F. Go

H. Goetz Fo Havey S. Hill A. Leonards

J. Ro R. M. J. T,n

F, D. E. Bo V. Jo

McLaughlin Miles Mills Scott Smythe Eoder

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2011 with funding from

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http://www.archive.org/details/studiesontobermoOOdiam

Technical Paper

STUDIES ON TOB£RUOEITE-LIKE CALCIUM SILICATE HYDRATES

By

Sidney Diamond, Graduate Assistant Wo L B Dolch, Research Associate Joe L. White, Professor of Agronomy Joint Highway Research Project Project: File:

C-36-47I 4-6-9

Prepared as Part of an Investigation Conducted by

Joint Highway Research Project Engineering Experiment Station Purdue University

in cooperation with Indiana State Highway Commission and the

Bureau of Public Roads

U S Department oi'Qommve Not Reviewed By

Not Released for Publication

Indiana State Highway Commission or the Bureau of Public Roada

Subject to Change

Purdue University Lafayette, Indiana October 31, 1963

STUDIES ON TOBERMORITE-LIKE CALCIUM SILICATE HYDRATES

ABSTRACT

Parallel studies were carried out on certain characteristics of CSH(l) synthesized at room temperature and on CSH(gel) produced by paste or bottle hydration of

p

-C^S, C_S and alite.

Instrumental

methods employed included x-ray diffraction, DTA, infrared spectroscopy, and electron microscopy.

Surface areas of the CSll(l) samples were

measured by water vapor adsorption and heats of adsorption were calculated,

Both CSH(l) and CSH(gel) were shown to have a negative

surface charge in the absence of Ca(QH) . p

A method was devised to

measure the cation exchange capacities of these materials, and the exchange capacities measured were the order of 5 "20 meq/lOOg.

The evidence suggests that CSH(gel) is a single, well-defined phase regardless of starting material or mode of hydration, and that 1

CSH(l) has well-defined properties regardless of variations in

composition o

The two phases are difficult to distinguish by x-ray

methods, but can be differentiated by the intensity of the high-

temperature exotherm on DTA, by particle shape as revealed by electron-

microscopic observation, and by the appearance of the main Si-0 vibration band region in infrared spectroscopy.

INTRODUCTION The poorly- crystallized calcium silicate hydrates that resemble the well-^crystallized mineral tobermorite comprise a group of materials

of importance to cement chemists, and are also of theoretical interest.

The present work is an attempt to characterize in detail some of the

properties of two of these phases, CSH(l) and CSH(gel). M tobermorite{G)." is also known as

The latter

The approach employed features

the study of a number of relevant properties of a suite of what is

hoped are representative materials of each kind, prepared in several different ways.

Methods of study include x-ray diffraction, DTA,

electron microscopy, infrared spectroscopy, water vapor— adsorption and several others.

Somewhat parallel studies were carried out with

certain synthetic well-crystallized tobermorites primarily to determine the effects of lattice substitution; these will be reported elsewhere.

Reference to much of the published work in this field is made difficult by the conflicting terminology used in designating the individual phases, and by failure of some workers consistently to

distinguish between tobermorite itself and the several poorly-crystallized phases now recognized.

A brief summary of some of the known properties of these materials will be presented before proceeding to the details of the present study.

Reviews by Taylor (l) and by Brunauer and Greenberg (2) contain

considerable information. CSH(l) is a poorly-crystallized synthetic calcium silicate hydrate

distinct from, but related to, tobermorite.

It can be prepared by

reaction at room temperature, or as a transient phase under hydrothermal

conditions (3)«

The structure is presumably a layer structure related

to that of tobermorite, but details are not known with certainty.

X-ray diffraction patterns display peaks at the positions of the strong (hkO) lines of tobermorite; a diffuse basal spacing is sometimes observed in the range from about 10A to about l4A, depending on the state of

hydration and on the Ca:Si ratio of the particular material (l). CSH(l) specimens showing similar x-ray patterns have been prepared in

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which the Ca:Si ratio may vary from 0.8 to about 1.5.

The DXA pattern

of CSH(l) is characterised by a strong, sharp high- temperature exothermic

peak at about 85O-90O C (h).

Electron microscopy reveals a particle

morphology generally described as consisting of crinkled or crumpled foils; the foils are usually only a few unit layers in thickness (5, 6).

CSH(gel) is produced by paste or bottle hydration of C-S, or by

paste or ball-mill hydration of $»CJ5, under room-temperature conditions (2).

X-ray diffraction shows only three peaks, corresponding to the

positions of the strongest (hkO) lines of tobermorite; basal spacings are not usually observed.

The detailed structure is unknown, but it

is thought to be related to that of tobermorite.

This is a comparatively

high-lime phase with Ca:Si ratio as high as 1.5, and possibly as high as 1.7»

CSH(gel) is usually considered to be mostly straight,

comparatively long fibers, the fibers themselves being composed of rolled up sheets.

An adequate DXA pattern for a pure CSH{gel) phase

has not previously been published, although partial information is

available (2).

Bottle hydration of 0»Q S is said to give rise to a distinct phase called CSH(lX) (7). which may also be formed on extended reaction of C-S in supersaturated lime solution (8), as an initial product in

hydrothermal reaction (3) and, reportedly, by reaction of calcium glycerate solution with silica gel (9)*

CSH(ll) is a lime-rich phase

with Cat Si ratio of 1.5-2*0; thus its composition overlaps that of CSH(gel).

In contrast to the latter, an x-ray basal spacing of about

10A is generally recorded (l).

It has been suggested that this phase

can be identified among calcium silicate hydrates by an x-ray peak at I.56A (10).

Again, the detailed structure is unknown.

The morphology

.

is fibrous; sometimes cigar-shaped bundles of fibers of distinctive

appearance are observed (5, 7).

The DTA pattern is marked by an

exothermic bulge at intermediate temperatures and by a relatively small high- temperature peak in the 85O C region (h)

PREPARATION OF SAMPLES CSH(I)

Seven samples of CSH(l) were prepared by several methods, all of which involved reactions at room temperature.

Five of these were

made by double decomposition reactions, and two were made by direct synthesis from lime and silica.

Four samples were prepared in the same general manner, in which

solutions of sodium silicate and a calcium salt were poured simultaneously into a third container and vigorously stirred, the calcium silicate

hydrate precipitating as large white floes

.

The sodium silicate used

was 0.5 M in each instance; the calcium salt solution used was 0.5 CaCl 9 in one sample, 0.5

M Ca(NO

)

in the others.

M

The molar ratios

of Ca to Si were 1.0 for the sample prepared with CaCl

and one of the

samples made with Ca(N0_)_, and 1.5 and 2.0 respectively for the other two samples made with Ca(N0-)_.

After precipitation the products were

diluted with distilled water, filtered over suction, washed several times, first with water, then with acetone, and finally with ether,

and then dried at 110 C.

A fifth sample was prepared by a more elaborate procedure, devised in an effort to promote microscopic homogeneity.

Two 10-ml Luer-lock

syringes were mounted obliquely to each other with their tips almost touching, so that when the two syringes were simultaneously depressed the two fine streams produced were intimately mixed and the combined

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droplets produced would fall into a flask mounted below the syringes.

The contents of the flask were stirred continuously.

Separate

reservoirs were attached to the two syringes so that they could be

repeatedly refilled without disturbing the arrangement.

Two hundred

ml each of solutions of sodium silicate and calcium nitrate were loaded into the respective reservoirs and mixed by simultaneously depressing the syringes , reloading, and repeating the process.

The concentrations

of the solutions were adjusted to yield a Ca:Si molar ratio of 3*5 to 1, in order to get a high-lime product.

After all the solutions

had been combined, the precipitated material was filtered and washed exhaustively, this time starting with saturated calcium hydroxide solution.

The washing was continued using a water-acetone mixture,

acetone, and finally ether, and then the washed sample was dried at

110 C under vacuum.

Two samples were prepared by direct reaction of a concentrated silica sol (Nalco-Ag 10-22, National Aluminate Company) with reagent-

grade Ga(0R)_.

The first preparation was made by direct addition

of the reagents in 1:1 molar proportion.

The resulting suspension was

diluted with distilled water and transferred to a polyethylene bottle. This was rotated on a roller mill for two days, then allowed to stand

undisturbed for three weeks.

The aged precipitate was then filtered,

the initially cloudy filtrate being recycled until the effluent solution

was clear.

The pH of the filtrate was 10.6, suggesting that all the

free Ca(0H)_ had reacted; consequently the sample was washed once with

water and dried.

A second preparation was made in the same way except

that a Ca:Si ratio of 2:1 was used; here the pH of the recycled and

clarified filtrate was 12-5, indicating that unreacted Ca(OH)

was

.

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The product was washed with water until the pH dropped

present:.

below 12.3 and x-ray examination disclosed the absence of crystalline

After one additional wash the sample was dried and stored.

Ca(OH) p .

For discussion purposes these samples are designated CSH(l)-l through CSH(l)-7, respectively.

Chemical analyses were carried out

on each of them by standard methods and the conventional compositional formulae determined.

These are given in Table

on preparatory methods.

1,

along with information

Considering that the mole ratio of starting

mixtures varied from 1:1 to 3«5:1> the fact that the observed Ca:Si ratios of the five samples made by double decomposition were all so close to

1

is somewhat unexpected.

In contrast, the CSH(l)-7 sample,

prepared by direct synthesis and aged prior to washing and drying,

had a Ca:Si ratio of almost 1.6:1.

Despite the fact that this ratio

is slightly higher than the upper limit normally ascribed to CSH(l),

this sample appears to be CSH(l) rather than CSH(ll), as will be made

clear later

CSHfeel)

CSE(gelJ samples were prepared by hydration of p-C S, C_S and alite.

Well-characterized samples of these cement compounds were

kindly contributed by D. L. Kantro and L. E. Copeland of the Portland Cement Association, and a second sample of alite of somewhat different

composition was donated by A. Klein of the University of California, Berkeley.

Paste hydration of the #-C S and C~S samples was carried

out at 23 C using a water: solids ratio of 0.7* and the hydration was

allowed to proceed for a period of seven months.

Bottle hydration at

the same temperature was carried out in polyethylene bottles rotated

on a wheel at about 30 rpm; in this case the water: solids ratio was

.

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Bottle hydration of thep-C_S and C„S samples was allowed to

9-0.

proceed for six months, and of the alltes for four months.

In all

experiments freshly-boiled distilled water that had been cooled to

below room temperature was used, and the containers were sealed against carbon dioxide penetration.

The designations for the specific samples to be discussed in this paper are given in Table 2.

In addition to the samples listed,

bottle hydration products for an additional sample of C_S and of alite were prepared and examined, but the results were essentially identical to those discussed.

The bottle hydration of C.S and of

alite specimens yielded a hydration product apparently similar in all significant respects to the other hydration products of the cement

minerals, and these products are considered to be CSH(gel) in this

report

CSH(II) Several attempts were made to prepare CSK(ll) by the synthesis

described by Toropov et. al.

(