Clay minerals in concrete aggregates of Kingston dolomitic limestone

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Clay minerals in concrete aggregates of Kingston dolomitic limestone

NATIONAL RESEARCH COUNCIL CANADA

DIVISION OF BUILDIBG RESEARCR

CLAY MINERALS

IN

CONCRETE AGGmGATES OF ICINGSTON DOLOMITIC LIMESTONE

by

J. E. G i l l o t t and R. Masson

Report; No. 191 of the

Division o f Building Research

OTTAWA February

1960

PREFACE

Extensive studies are being carried out by the Division in an attempt to identify the constituents of

a

dolomitic limestone from Kingston, Ontario, which cause it to expand when exposed to alkali. -serious expansion of concrete made with this limestone as coarse aggregate

has

occurred through reaction with cements having

a

substantial alkali content. The possibility of expansion cannot be assessed by any of the quick tests developed for other undesirable reactions. Limestones from other sources than that at present known to be reactive cannot be checked quickly for this characteristic but

must

be subjected to an expansion test extending over several months, and some quick check

test would be of great value.

Conversion of the clay mineral present in the

limestone has been suggested as a possible cause of expansion. The procedures followed in the isolation of clay fractions from the limestone and the results of analysis by X-ray diffraction techniques are now reported. The work was

carried out by the senior author, a research officer in the Building Materials Section, assisted by the junior author who held an appointment with the Division as a summer student in

1958.

It is the first work using X-ray diffraction

techniques to be carried out by the staff of the Division.

The Division has only recently acquired its own X-ray equipment, and is indebted to the Soil Chemistry Unit, Science Service, Department of Agriculture, Government of Canada, for the use of their equipment in the interim.

Ottawa

TABLE OF CONTh'NTS

INTRODUCTION

...

1

...

2.

HYPOTHESIS OF EXPANSIVE CLAY MINERAL 1

3. EXPERIMENTAL INVESTIGATION

...

2 3.1 Separation Techniques Employed

3 1 1 Electrical Method 3.1.2 Dispersion Technique 3.1.3 Hydrochloric Acid 3.1.4 Acetic Acid

3.1.5 Ammonium Acetate 3.1.6 Ion Exchange Resins 3.2 Analytical Procedure

4. DISCUSSION OF RESULTS

...*..

8

...

5.

CONCLUSION

9

REFERENCES

...~.~..~.~....~...~~~...

10

CLAY MINERALS

IW

COlVCRETE AGGIiEGATES OF KINGSTON DOLOlIIITIC LIMESTONE

J. E. Gi-3-lott and R. Masson

The p r e s e n t work forms p a r t of a program of

i n v e s t i g a t i o n s by t h e Division of Building Research of t h e National Research Council i n t o t h e causes underlying t h e

cracking and expansion of concrete i n t h e a r e a of Ringston, Ontario ( 6 ) . I n

1955

it was e s t z b l i s h e d t h a t abnormal

expansion i s t h e r e s u l t of a cement-aggregate r e a c t i o n i n v o l - v i n g t h e coarse a g g r e g a t e , a dolomitic limestone q u a r r i e d i n t h e neighbowhood of Kingston.

The rock i n t h e quarry was broadly c l a s s i f i e d on t h e b a s i s of depth from t h e s u r f a c e i n t o 0 t o 24 f e e t

( a g g r e s s i v e l y expansive i n c o n c r e t e ) and 24 t o 30 f e e t (known l o c a l l y a s t h e Green Band and n o t h o w n t o cause expansion). Samples t a k e n from t h e s e two zones were used

i n

t h e s t u d i e s now r e p o r t e d . I n a d d i t i o n , Ottawa Valley limestone, which i s n o t h o w n t o cause expansion i n c o n c r e t e , was used a s a

c o n t r o l . ASTid t e s t s t o d e t e m i a e t h e p o t e n t i a l r e a c t i v i t y of t h e c o a r s e aggregate gave n e g a t i v e r e s u l t s (11).

I t was found t h a t expansion could be prevented i f

lovr, i n s t e a d of h i g h , a l k a l i cement was used (11, p. 1 3 ) , b u t th.e underlying causes f o r t h e a g g r e s s i v e expansion remained obscure.

2. HYPOTHESIS OF EXPANSIVE C U Y TdINERAL

Work done elsewhere on behalf of t h e D i v i s i o n showed t h a t t h e c h i e f c l a y mineral i n t h e Kingston rocks i s i l l i t e , a mineral n o t normally expansible. However, it was p o s t u l a t e d t h a t i f an expansive mineral such a s montmorillonite developed from t h e i l l i t e because of a l k a l i a t t a c k , t h e expansion of t h e c o n c r e t e might be explained.

I l l i t e i s a t t p h y l l o s i l i c a t e of t h e t r i p h o r m i c type"

(8, p.

1 6 5 ) .

Tlze s t r o n g l y bonded b a s i c s t r u c t u r a l u n i t c o n s i s t s of a n aluminium-oxygen o c t a h e d r a l l a y e r sandwiched between two s h e e t s of silicon-oxygen t e t r a h e d r a with a p i c e s inwardly

d i r e c t e d . The s t r u c t ~ l r i s described a s t r i o c t a h e d r a l i f diva- l e n t c a t i o n s such a s Fe5+ o r ~ g 2 + occur, and d i o c t a h e d r a l i f t h e s e a r e replaced b$ t r i v a l e n t ~ 1 3 + i o n

( 5 ,

p.

65-9).

About one-sixth of t h e 514 a r e replaced by A l ? + , g i v i n g a n e t n e g a t i v e

charge t o t h e s h e e t s which i s bala2ced b i n t e r l a y e r K + c a t i o n s , possibly themselves replaced by CaLf, Me?(+ and Hf. The b a s i c s t r u c t w a l u n i t i n montmorl.ll.onite i s s i m i l a r , but t h e r e i s

more v a r i a t i o n and t h e n e t charge p e r u n i t c e l l l a y e r i s reduced from about 1

5

t o 0.6

_2;

There 5 s s u b s t i t u t i o n w i t h i n t h e

s h e e t s of ~lf7+ f o r S i and of magnesium, i r o n , z i n c , e t c . , f o r aluminium. A s with t h e i l l i t e - t y p e minerals, t h e montmorillonites a r e subdivided i n t o d i o c t a h e d r a l and t r i o c t a h e d r a l s e r i e s .

Charge unbalance i n t h e tetral~edxaal s h e e t s may be p a r t i a l l y , though never e n t i r e l y , compensated f o r by s u b s t i t u t i o n s i n t h e octahedral sheet where t h e n e t charge deficiency i s l a r g e l y located. I n i l l i t e , however, t h e charge i s n e a r e r t h e s u r f a c e i n t h e t e t r a h e d r a l l a y e r s . This screening e f f e c t i n t h e mont- m o r i l l o n i t e s may i n p a r t explain t h e i r h i g h exchange capacity and expansion w i t h p o l a r molecules which d i f f e r e n t i a t e them from t h e i l l i t e s .

It has been demonstrated i n t h e l a b o r a t o r y t h a t

i l l i t e can be made t o show expansion i f t h e i n t e r l a y e r potassium i o n s a r e e i t h e r p r e c i p i t a t e d out o r replaced by exchange by

magnesium ( 4 , 1 3 ) . Sodium c o b a l t i n i t r i t e brought about- p r e c i - p i t a t i o n e i t h e r i n cold o r on heating, and h e a t i n g on t h e water- b a t h w i t h magnesilxn c h l o r i d e promoted t h e exchange r e a c t i o n .

I n t h e l a t t e r c a s e , t h e potassium was replaced by magnesium which h a s a h i g h e r hydration energy.

The rocks f r o m both U n g s t o n and t h e Ottawa Valley c o n t a i n i l l i t e i n t h e c l a y f r a c t i o n , but those from Xingston a r e more dolomitic and hence have a h i g h e r content of magnesium.

The s o l u b i l i t y product of magnesium hydroxide i s much lower t h a n t h a t of magnesi~un carbonate, and i n a n a l k a l i n e environment

magnesium hydroxide may be f o m e d i n considerable q u a n t i t y .

During t h i s react-ion magnesium ions derived from t h e dolomite may be i n a r e a c t i v e s t a t e and it seems p o s s i b l e t h a t a replacement of potassium from between t h e s i l i c a t e l a y e r s of t h e i l l i t e may take place. Such a transformation v-rould produce a c l a y mineral capable of expansion.

I n o r d e r t o i n v e s t i g a t e t h i s hypothesis it was

necessary t o s e p a r a t e t h e c l a y minerals p r e s e n t i n t h e aggregate from t h e carbonates.

Dolomite i s only slowly s o l u b l e i n weak a c i d s , but c e r t a i n t y p e s of montrnorillonite a r e known t o be a c i d s o l u b l e ; hence a method had t o be developed which could remove t h e dolomite b u t leave t h e c l a y f r a c t i o n unaltered.

The aggregate wso pulverized, e i t h e r by a motor-driven mortar and p e s t l e , a hammer m i l l , o r by hand t o a grade s i z e

which passed 200 mesh on the

U.S.

Bureau of Standards copper sieves. No material was rejected and care was taken to ensure that it was truly representative of the aggregate used in the

concrete.

Separation Techniques Employed 3.1.1 Electrical Method

Initially, an attempt was made to exploit the elec- trically charged colloidal nature of clay minerals to separate them from the carbonates. Colloids are known to migrate under an electrical potential and hence the negatively charged clay minerals should become concentrated at the positive electrode. That this did not occur in practice was possibly the result of interference with the charges on the clay minerals by the

carbonates.

3.1.2 Dispersion Technique

Clay minerals may be kept in suspension by the addi- tion of dispersing agents such as sodium hexa-meta phosphate. Hence a suspension of clay minerals and carbonates set aside

for sedimentation should show an increasing concentration of clay in the higher parts of the sedimentation column.

A

partial concentration of clay.minerals was achieved by this techniqu.e. Unfortunately calcium phosphate hydrate apparently forms when the sample is heated, as is sometimes necessary for c1a.y mineral identification, and hence a reaction between the dispersing agent and sample takes place which may exert an adverse effect on identification.

Subsequently, attempts were made to dissolve out the carbonates from the less soluble clay minerals. Reagents

employed to conceiitrate the clay fraction included: hydroch- loric acid, acetic acid, ammonium acetate3, and two types of ion exchange resin

(7,

10).

Hydrochloric Acid

Hydrochloric acid in an excess of four times the

theoretical volume was used at concentrations of 0.05N, 0,1N, lN

and 5N. A concentration of 0.1N took 16 hours, stirred in the cold, to remove the carbonates, and at this dilution it was hoped that the clay concentrate would be mineralogically

unaffected. To test this, hectorite, an acid soluble mineral of the montmorillonite group, was added,

Procedure: Five hundred mill-ilitres of 0.1N HC1 (pH1) were added to

0.6

gm of pulverized limestone. After approximately 16 hours' mechanical stirring at room temperature all dolomite

and calcite had been removed (Figs.4,5).

In

a subsequent experiment, 0.1 per cent hectorite was added to the limestone and a similar procedure followed. X-ray analysis of the

residue failed to detect hectorit-e, altho~~gh chlorite and illite were successful1.y identified, The failure to detect hectorite indicated that hydrochloric acid was unsatisfactory for the purpose (10).

3.1.4

Acetic Acid

Previous work has shown (10, p. 683) that by the use of

4.4

molar acetic acid hectorite may be concentrated from

a

mixture containing calcite, though less success was reported

in the case of dolomite (10, p.

685).

However, it was believed worth while to investigate its potentialities.

Procedure: Two hundred millilitres of

4.4

molar acetic acid were added to

5

gm of powdered limestone and stirred at room temperature for a minimum period of

16

hours. An excess of acid was added to ensure a sufficiently high acid concentration towards the end of the reaction. The slurry was filtered

through Whatman

42

filter paper in a crucible, washed with distilled water, and transferred with a few millilitres of distilled water to a specimen bottle. X-ray analysis on the diffractometer indicated a fairly complete removal of both calcite and dolomite. The clay minerals, illite and chlorite, were both detected.

A

similar procedure was followed with two samples of powdered dolomitic limestone to which hectorite in a concentra- tion of 0.1 and 1.0 per cent were added.

In

neither case was the hectorite detected by X-ray analysis (Pig. 8). Further use of acetic acid was suspended.

3.1.5

Ammonium Acetate

On

the suggestion of G. Brown

(3)

trials were con- ducted with

4.4

molar ammonium acetate, but it was found that after

72

hours' stirring at room temperature the dolomTte and calcite were only partly removed. It was concluded that the complete removal of dolomite and calcite by this reagent was likely to be an unduly lengthy procedure.

3.1.6

Ion Ekchange Resins

Ion exchange resins have been employed by previous workers to separate clay minerals from carbonate rocks. Lloyd

(7)

describes a technique using a resin-filled column.

Column Technique-Procedure: A 3-foot column of 2-inch diameter glass tubing was fitted at'the bottom with a 100-mesh screen and an adapter connected to a suction flask (see Fig. 1).

The t u b e was f i l l e d w i t h a commercial c a t i o n exchange r e s i n

( 1 R 1 2 0 ) , which was charged with exchangeable hydrogen i o n s by alloiving an ~ / 1 0 s o l u t i o n of hydrochloric a c i d t o p e r c o l a t e slowly down t h e column. The r e s i n was t h e n washed w i t h d i s -

t i l l e d water u n t i l t h e a d d i t i o n of a few m i l l i l i t r e s of s i l v e r n i t r a t e t o t h e washings showed no opalescence. A t h i n

s l u r ~ j

of 1 0 gm of pulverized limestone was introduced a t t h e t o p of t h e co111mn and t h e r e s i d u e c o l l e c t e d i n t h e s u c t i o n f l a s k a t t h e bottom.

The y i e l d obtained was small a s t h e r e w a s d i f f i c u l t y i n washing t h e limestone p a r t i c l e s through t h e column because t h e y adhered t o -bile r e s i n . Recover27 was t o o low t o permit r e - c y c l i n g and t h e r e s i d u e which was obtained s t i l l showed a l a r g e content of both c a l c i t e and dolomite on X-ray examina- t i o n .

Batch Techaique: An a l t e r n a % i v e technique, using Rohm and Haas commercial r e s i n IRC-50, has a l s o been described ( 1 0 ) .

It uses a r t f f i c i a l mixtures, one of which c o n t a i n s

95

p e r cent dolomite, Zs p e r c e n t q ~ ~ a r t z , and 2.k p e r c e n t h e c t o r i t e . I n t h i s case a temperature of 80 t o 8 5 ' ~ i s necessary t o remove t h e dolomite.

A s it appeared possible' t h a t montmorillonite might be

p r e s e n t i n a c o n c e n t r a t i o n lower t h a n 24 p e r cent i n t h e

Kingston r e a c t i v e aggregate

it

was believed t h a t a s t i l l more gradual treatment was d e s i r a b l e . Accordingly, experiments were performed t o determine whether t h e teclmique described i n

Reference 10 could be modified. It was found t h a t a l l t h e dolo- mite could be removed and. h e c t o r i t e , i n a concentration a s l o w a s 1 p e r c e n t , detected by t h e following modified technique: Batch Techlique-Procedure:

2.5

2

_{0.2 gm of limes-tone, ground} t o pass 200 mesh, were weighed out and t r a n s f e r r e d t o a 400-ml beaker. Approximately 150 m l o f d i s t i l l e d water were added toget'ner w i t h 70 r n l of i o n exchange r e s i n IRC-50, measured out

i n a graduated c y l i n d e r , and t h e whole s t i r r e d t o f0rm.a homo- genous s l u r r y . It was found t h a t t h i s volwne of water was

g e n e r a l l y s u f f i c i e n t t o allow f o r evaporation i n t h e water bath. The beaker was then placed i n a 14-gal water 'oath maintained a t 70°C f o r a 3-how cycle. The s l u r r y was s t i r r e d g e n t l y and continuously w i t h a l a b o r a t o r y s t i r r e r r o t a t i n g a t low speed so t h a t t h e r e s i n p a r t i c l e s were n o t broken down. The s t i r r i n g ensured adequate c o n t a c t between t h e r e s i n and limestone

p a r t i c l e s . A t t h e end of t h e 3-how cycle t h e s l u r r y w a s sieved through b o l t i n g c l o t h of 100 mesh ( P i g s . 2 ,

3 ) .

Resin r e t a i n e d

on t h e c l o t h s i e v e was thoroughly washed w i t h a f i n e j e t of d i s t i l l e d water u n t i l a l l t h e r e s i d u e from t h e limestone had passed through. This was b e s t accomplished by d i r e c t i n g t h e j e t o f d i s t i l l e d water on t h e surface of t h e s i e v e a t an angle of

about

45

degrees.

The

dark, clay mineral residue from the 1im.estone co61d 'be rea.dily seen against the white background of resin and bol'ting cloth, and washing was continued until only resin remained on the sieve,

The suspension of residue was returned to the beaker,

70

ml of fresh resin added, and the beaker re2laced in the

water bath for a furkher 3-hour cycle. The slurry was again

filtered, and after the sieve had been washed to ensure that all the clay had passed through, the suspension was transferred to a 1000-ml graduated cylinder. The volume was made up to 500 ml and left to sediment for

16

hours. The ion exchange resin apparently acts as

a

dispersing agent as the clay remains

in suspension. This result contrasts with that of attempting to combine sedimentation with hydrochloric acid treatment, when the residue completely sedirnented overnight.

A

dispersing

agent would have been required in this case.

After sedimentation, the top

50

ml were withdrawn from the 1000-ml cylinder, care being taken not to disturb the suspension unduly, and centrifuged for

5

hours or until the supernatant liquid was clear. This was decanted and the solid residue transferred to a specimen bottle with the aid

of

a few millilitres of water to await X-ray analysis.

3 . 2 _{Analytical Procedure}

Initially, the residue was tested chemically for calcium and magnesium carbonates, but it was not possible by chemical means to determine the effect of the reagents on the clay fraction. Subsequently, X-ray methods were employed to overcome this limitation.

Many clay minerals have

a

well developed cleavage and platy form owing to the weak bond between one alumina-silica sandwich and the next. Ynis allows displacements in the "abl' crystallographic plane leading to irregularity in stacking and destructive interference between scattered X-rays. The most important reflections which occur are from the basal pSanes

( O O ~ ) , and to enhance these reflections the clay minerals are often oriented on a slide by sedimentation. Long spacings are common and the experimental technique must be adequate to record the low Bragg angles. The same lattice spacings are found in different clay minerals, and consequently coincident X-ray reflections are recorded.

To

identify the component minerals the sample may have to be heated or treated with organic liquids or acids. Variable lattice spacings lead to broad, poorly

defined reflections. Random intergrowbhs give a peak which represents the apparent spacing

(14)

and a non-integral

The l a t t i c e spacing between t h e b a s a l p l a n e s of montmorillonite v a r i e s with humidity, b u t a c h a r a c t e r i s t i c and d e f i n i t e expansion occurs w i t h e t h y l e n e g l y c o l o r

g l y c e r o l , and t r e a t m e n t with t h i s compound o f t e n enables a p o s i t i v e i d e n t i f i c a t i o n t o be made. C h l o r i t e may be confused w i t h k a o l i n i t e , b u t t h e y d i f f e r i n response t o h e a t t r e a t g e n t . A t 550°C t h e f i r s - t o r d e r c h l o r i t e r e f l e c t i o n a t about

1 4

A

becomes i n t e n s i f i e d

( 5 ,

p. 8 7 ) and h i g h e r o r d e r s a r e l o s t , whereas t h e k a o l i n i t e l a t t i c e becomes d i s o r d e r e d and a l l

r s P l e c t i o n s tend t o vanish.

A standard procedure was followed throughout t h e

p r e s e n t work. A homogenous suspension of t h e pomdered m a t e r i a l i n a few m i l l i l i t r e s of water was prepared. Generally, simple shaking of t h e specimen b o t t l e was s u f f i c i e n t t o achieve t h i s , s i n c e a s mentioned previously t h e i o n exchange r e s i n IRC-50 a c t e d a s i t s own d i s p e r s i n g agent. I n some i n s t a n c e s however a more even d i s p e r s i o n was achieved by t r e a t m e n t f o r a few

minutes i n a mechanical 'rhornogenizer". The suspension was then t r a n s f e r r e d with a n eye dropper t o a g l a s s microscope s l i d e and allowed t o evaporate slowly on a w a r m e l e c t r i c p l a t e .

X-ray examination was c a r r i e d out on t h e d i f f r a c t o ~ n e t e r s e t t o record over an a n g u l a r range such t h a t t h e s t r o n g dolomite and c a l c i t e peaks would be recorded i f e i t h e r mineral was p r e s e n t .

The s l i d e was t h e n saturateci l i g h t l y w i t h e t h y l e n e g l y c o l by means of an atomizer. A f t e r a few minutes t h e s i g n i - f i c a n t low a n g l e region was re-examined on t h e d i f f r a c t o p e t e r , t h e scan, which i n v a r i a b l y included t h e main i l l i t e ( 1 0 A )

r e f l e c t i o n , being made from both high and low a n g l e s f o r compari- son and t o allow f o r p o s s i b l e backlash i n t h e g e a r s . The s l i d e was t h e n heated f o r 1 hour a t 550°C i n a t h e r m o s t a t i c a l l y

c o n t r o l l e d muffle and re-examined with t h e d i f f r a c t o m e t e r . I n some i n s t a n c e s t h e sample was heated stepwise a t 350, 450, 550 and 700°C with X-ray examination a f t e r each h e a t t r e a t m e n t .

A more a c c u r a t e r e s u l t can be obtained w i t h t h e d i f f r a c t o m e t e r i f t h e Geiger counter i s moved manually i n a stepwise f a s h i o n a f t e r a f i x e d count has been recorded . a t each a n g u l a r s e t t i n g . By t h i s procedure one may c a l c u l a t e from t h e number of counts t h e probable s t a t i s t i c a l e r r o r i n each recording.

I n t h e p r e s e n t work 3200 counts were r e g i s t e r e d a t each a n g u l a r s e t t i n g . This g i v e s a p r o b a b i l i t y of 50 p e r c e n t t h a t t h e

value d e v i a t e s by l e s s t h a n 1.18 p e r c e n t from t h e t r u e v a l u e ; a p r o b a b i l i t y of 90 p e r c e n t t h a t t h e value d e v i a t e s by l e s s t h a n 2.89 p e r c e n t f r o m t h e t r u e v a l u e ; and a p r o b a b i l i t y of

99 p e r cent t h a t t h e value d e v i a t e s by l e s s than 4.56 p e r c e n t from t h e t r u e value ( 9 ) .

Samples examined by t h i s technique included t h e

r i m

m a t e r i a l from t h e aggregate, m a t e r i a l from i n n e r p a r t s of t h e rimmed aggregate fragments, and non-rimmed aggregate. I n a d d i t i o n a composite sample o f beds t a k e n f r o m t h e 6 - t o 7 - f t , 10.5-to 1 2 - f t , and 20-to 21-ft l e v e l s i n t h e 0 - t o 2 4 - f t s e r i e s was examined f o r comparison. This composite sample was prepared

i n a manner i d e n t i c a l t o t h a t used. i n s e p a r a t i n g t h e rock from t h e concrete, and a d e n t i s t ' s d r i l l was employed t o concentrate t h e rock p r i o r t o s e p a r a t i o n of t h e c l a y mineral f r a c t i o n .

In

some c a s e s , Debye-Scherrer photographs were employed t o remove doubt a s t o t h e presence o r absence of f a i n t r e f l e c t i o n s ,

It i s a l s o p o s s i b l e by measurement of t h e "dm-value of t h e (060) r e f l e c t i o n and estimation of t h e i n t e n s i t y of t h e second o r d e r b a s a l r e f l e c t i o n t o e s t a b l i s h whether t h e c l a y micas belong t o t h e d i o c t a h e d r a l o r t r i o c t a h e d r a l s e r i e s

( 2 , p . 1 5 9 ) .

Complete d e t a i l s of experimental r e s u l t s a r e included i n t a b u l a r form a t t h e end of t h e r e p o r t and s e l e c t e d d i f f r a c t o - grams a r e reproduced i n Figs. 4 t o 23. Figures 4 t o 9 i l l u s - t r a t e t h e e f f e c t on c l a y minerals of t h e method of s e p a r a t i o n from carbonates. Figure 8 shows t h a t h e c t o r i t e , added i n a

concentration of 1 p e r c e n t , was n o t resolved on t h e d i f f r a c t i o n p a t t e r n when cold 4.4 molar a c e t i c ' a c i d was used a s s e p a r a t i n g agent. This c o n t r a s t s with t h e g l y c o l a t e d sample, separated from carbonate by means of i o n exchange r e s i n a m b e r l i t e IRC-50, and shown i n Fig. 9. Figures 10 t o 23 show t h a t t h e same c l a y minerals a r e p r e s e n t i n u n t r e a t e d rocks, i n a l k a l i t r e a t e d rocks known t o have expanded ( A l k i n f i g u r e s ) , and i n rocks used f o r aggrecate i n concrete beans which a r e a l s o known t o have expan- ded. The aggregate was t r e a t e d i n t h r e e f r a c t i o n s on t h e b a s i s of i t s p h y s i c a l appearance, and t h e c l a y minerals separated as previously described. A d e n t i s t ' s d r i l l was employed t o con- c e n t r a t e narrow dark r i m s s ~ w r o u n d i n g some of t h e aggregate, t h e c e n t r a l p o r t i o n s o f t h e rimmed aggregate, and t h e non-rimmed ag,pegate.

4.

DISCUSSION OF RESULTS

The dominant c l a y mineral i n t h e KXngston and Ottawa Valley samples examined i s i l l i t e . T h a t from t h e Ottawa Valley

i s probably more degraded t h a n t h a t from ELngston a s d i f f r a c t i o n peaks a r e broader and weaker. The D e b y e - S c h e r r e r p a t t e r n s

i n d i c a t e t h a t t h e i l l i t e belongs t o t h e d i o c t a h e d r a l s e r i e s i n each case. The only o t h e r c l a y mineral i d e n t i f i e d i s ckllorite, which

i n

a l l c a s e s gave weaker r e f l e c t i o n s t h a n # i d t h e i l l i t e . The c h l o r i t e f i r s t o r d e r r e f l e c t i o n a t about 1 4

A

d i d n o t always appear on t h e diffractograrn of t h e heated sample, owing

s u p p o s i t i o n it was decided t o examine t h e p a r t i c u l a r a n g u l a r r e g i o n by means of t h e f i x e d count technique. The a n g u l a r range covered was extended t o i n c l u d e t h e r e g i o n i n which a peak would occur on t h e a d d i t i o n of g l y c o l t o expansive c l a y minerals.

0

The

1 4

A r e f l e c t i o n was p r e s e n t i n a l l samples

examined, though o f much l e s s i n t e n s i t y t h a n t h e second o r d e r c h l o r i t e r e f l e c t i o n (approximately 7

1).

A f t e r h e a t i n g a t 550°C t h e

7

x , r e f l e c t i o n disappeared, but no corresponding i n c r e a s e of t h e

1 4

A r e f l e c t i o n wa.s found when a f i x e d count was recorded, and i n some c a s e s t h e r e f l e c t i o n apparent13 broadened.

I r o n - c h l o r i t e s examined by Weiss and Rowland ( 1 2 ) show a l e s s e r i n c r e a s e i n (001) i n t e n s i t y and a l e s s e r decrease i n

( 0 0 2 ) i n t e n s i t y than m a p e s i a n c h l o r i t e s . However, i n t h e Kingston samples t h e (002) r e f l e c t i o n i n v a r i a b l y disappeared completely while t h e (001) r e f l e c t i o n a p p a r e n t l y v a r i e d i n i t s respoxse t o h e a t t r e a t m e n t . It i s t e n t a t i v e l y concluded t h a t t h e r e i s a mixture of c h l o r i t e and v e r m i c u l i t e p r e s e n t . I n t h e a i r - d r s t a t e t h e v e r m i c u l i t e and c h l o r i t e both c o n t r i b u t e t o t h e 1 4 r e f l e g t i o n , b u t t h e l a r g e r p a r t i s contributed by v e r m i c u l i t e . The

7

A r e f l e c t i o n i s l a r g e l y due t o t h e c h i o r i t e . On h e a t i n g , t h e v e r m i c u l i t e c o n t r i b u t i o n t o t h e 1 4 A r e f l e c t i o n d i s a p p e a r s , b u t t h e c h l o r i t e c o n t r i b u t i o n i s enhanced. The i n t e n s i t y of t h e 1 4 A r e f l e c t i o n a f t e r h e a t i n g depends on t h e p r o p o r t i o n s of c h l o r i t e and v e r m i c u l i t e i n t h e o r i g i n a l mixture. oThose c a s e s i n which c h l o r i t e i s dominant show an enhanced 14 A peak, but when t h e r e i s more v e r m i c u l i t e t h e c h l o r i t e c o n t r i b u t i o n , though i n c r e a s e d , r e s u l t s i n a peak of only approximately t h e same h e i g h t a s t h a t r e s u l t i n g from t h e j o i n t v e r m i c u l i t e p l u s c h l o r i t e peak p r i o r t o h e a t i n g . .Because of t h e l a r g e i l l i t e f i r s t o r d e r r e f l e c t i o n a t about 10 A , it i s n o t possibl-e t o show unequivocally t h a t t h e v e r m i c u l i t e spacing h a s c o l l a p s e d t o t h i s approximate value.

The c l a y minerals s e p a r a t e d from t h e rocks s u b j e c t e d t o a t t a c k by a l k a l i n e s o l u t i o n s which simulate t h e c o n d i t i o n s i n c o n c r e t e do n o t a p p a r e n t l y d i f f e r from t h o s e i n t h e u n t r e a t e d rocks. The same i s t r u e f o r t h e c l a y mineral f r a c t i o n of t h e rimS surrounding a f f e c t e d aggregate i n c o n c r e t e , f o r t h e c e n t r e s of t h e rimmed aggregate, and a l s o f o r t h e non-rimmed aggregate. I n no case was evidence found f o r expansive c l a y minerals.

The l a c k of evidence f o r expansive c l a y minerals

i n d i c a t e s t h a t it i s u n l i k e l y t h a t t h e expansion of t h e Kingston aggregate can be a t t r i b u t e d t o t h i s cause.

2. Brindley, G.W. (ed.).

X-ray identification and crystal

structures of clay minerals. Min. Soc., London,

1951,

p*159*

3.

Brown,

G.

Rothamsted Experimental Station, Personal

Communication.

4.

Caillhe, S., S. H h i n , and R. Guennelon. Experimental

transformation of mica into various types of clay

minerals by separation of the layers. Comptes Rendues

des s6ancesdeltacadamie des sciences,

-

228,

1741, 1949.

5. Grim, R.E, Clay Mineralogy. McGraw Hill, New York, 1953.

6.

Legget, R.

F., and E.

G, Swenson.

A concrete problem at

Kingston,

Ontario:'

N.

R.C., DBR Internal Report No.

115, May, 1957.

7,

Lloyd,

R,M, A technique for separating clay minerals from

limestones. Jour. Sed, .Pet,

-

24, No. 3, 218.

8.

Mackenzie, R.C.

The differential thermal investigation of

clays. Min. Soc., London,

1957.

9.

Parrish,

W. X-ray intensity measurements with counter tubes.

Philips Tech. Rev.,

-

17, No.

7-8,

Jan-Feb 1956. p. 206-221,

10.

Ray, S.,

H.R. Gault, and C.G. Dodd. The separation of clay

minerals from carbonate rocks, Am. Min. 42, No.

-

9

and

10,

1957. p.681-5.

11. Swenson,

E.G.

A Canadian reactive aggregate undetected by

A.S,T.M. tests. A.S.T.M.

Bull,, No. 226, Dec. 1957.

'

12. Yeiss, E.J. and R.A. Rowland. Oscillating heating X-ray

diffractometer studies of clay mineral dehydroxylation.

Am.

Mi-n. 4 l , 1956. p.117-126.

13. 'IVhite, J.L.

Transformation of illite into montmorillonite.

Soil Science Soc. America, Proc.,

15,

1950. p.129-133.

14. Yoder,

H.S. and

HOP,

Eugster. Synthetic and Natural

Muscovites, Geochimica et Cosmochimica Acta,

-

8,

No.

V A C U U G L A S S C O L U M N S U P P O R T S H S I E V E M E T A L B A S E BSM 182

F I G U R E I

I O N E X C H A N G E C O L U M N

PYREX RIM ALUMINUM R I M HOLDING T H E C L O T H I N P L A C E ROUND WOODEN SUPPORT PYREX EVAPORATING D I S H

F I G U R E

2

F I G U R E

3

C L O T H S I E V E

Figure 4

0

The m i n e r a l s i d e n t i f i e d a r e : i l l i t e (lO.29A,

0 0

5.01A, 3.36A); c h l o r i t e and ( ? ) k a o l i n i t e

0 0 0 0 0

(7.19A, 4.7A, 3.5A); q u a r t z (3.364, 4.3A);

0 0

f e l s p r (3.2A) ; t h e 4.5A peak i s a t t r i b u t e d t o t h e (020) r e f l e c t i o n of mica-type c l a y m i n e r a l s .

Figure 5

A f t e r h e a t i n g of t h e above sample f o r 1 hour a t 550°C t h e h i g h o r d e r c h l o r i t e o r k a o l i n i t e

0 r e f l e c t i o n s a r e a b s e n t . The peak a t 14.434

0 confirms t h a t c h l o r i t e i s p r e s e n t . The lO.29A i l l i t e r e f l e c t i o n i s s h a r p e r which probably i n d i c a t e s t h a t t h e s t r u c t u r e of t h e unheated m i n e r a l i s somewhat degraded.

SETTING OF GENERAL ELECTRIC CO. DIFFRACTOMETER

EXIT S L I T : 3' TIME CONSTANT: 2

SOCLER SLITS: MEDIUM RESOLUTION X-RADIATION: Cr

RECEIVING SLIT: 0.2O FILTER : V

RESPONSE: LINEAR KV: 5 0

FULL SCALE DEFLECTION: 2 0 0 c . p . s . m A : 16

Figure 6

0 0

Minerals i d e n t i f i e d a r e : i l l i t e (10.19A, 5.08A,

0 0 0

3.36A) ; c h l o r i t e and ( ? ) k a o l i n i t e (14.75A, 7,16A,

0 0 0 0

4*76A, 3.54A) q u a r t z (3.36A9 4.28A) and f e l s p a r 0

(3.26;). The peak a t 4.498 i s a t t r i b u t e d t o t h e (020) r e f l e c t i o n of mica-type c l a y m i n e r a l s . There i s no a p p a r e n t s i g n i f i c a n t s h i f t i n peak- p o s i t i o n s a f t e r t r e a t m e n t w i t h e t h y l e n e g l y o o l which would i n d i c a t e t h e presence of expansive c l a y m i n e r a l s . The added 0.1% h e c t o r i t e

i s

t h u s n o t d e t e c t a b l e . F i g u r e 7 A f t e r h e a t i n g o f t h e above sample f o r 1 h o u r a t 550°C t h e low o r d e r c h l o r i t e a n d , o r k a o l i n i t e peaks a r e a b s e n t . The f i r s t o r d e r r e f l e c t i o n h a s become somewhat enhanced and t h e s p a c i n g

0 h a s shown a s l i g h t c o l l a p s e t o 14.27A.

SETTING OF GENERAL ELECTRIC CO. DIFFRACTOMETER

EXIT S L I T : 3' TIME CONSTANT: 2 SOLLER SLITS: MEDIUM RESOLUTION X

-

RADIATION : Cr

RECEIVING SLIT: 0.2' FILTER : V

RESPONSE: LINEAR K V : 5 0 FULL SCALE DEFLECTION: 2 0 0 c . p . s . m A : 16

Figure

8

0 0

Minerals i d e n t i f i e d a r e

:

i l l i t e (10.27A, 5.03A,

0 0 0

3,36A); c h l o r i t e and

( ? )

k a o l i n i t e (14.75A, 7,19A,

0 0 0 0

4.76A, 3.55A); quartz (3.36A, 4.3A), f e l s p a r

0

(3.268, 3.21;).

There

i s

no s i g n i f i c a n t s h i f t

i n I n t e r p l a n a r Spacing on treatment with ethylene

glycol so t h a t the added

1%

h e c t o r i t e i s not

deteotable.

Ihe marked s h i f t i n 'Interplanar Spacing from

0 0 0

15.09A t o 18.7A

-

19.3A on treatment with

ethylene glycol i n d i c a t e s t h a t t h e added

1%

h e c t o r i t e

i s

present i n detectable ooncentration.

This i n d i c a t e s t h a t t h e separation prooedure

employed i s a s a t i s f a o t o r y method f o r concentra-

t i n g

aoid-soluble c l a y minerals from dolomite.

C a l c i t e and dolomite a r e removed by t h e procedure

.'

SETTING OF GENERAL ELECTRIC CO. DIFFRACTOMETER

X R D - 5

E X I T S L I T : 3 "

SOLLER SLITS: MEDIUM RESOLUTION RECEIVING SLIT: 0 . 2 "

RESPONSE: LINEAR

FULL SCALE DEFLECTION: 2 0 0 c.p.s.

TIME CONSTANT: 2 X - R A D I A T I O N : Cr

FILTER : V

K V : 5 0

rnA: 16

Figure 1 0

0 0

Minerals i d e n t i f i e d a r e : i l l i t e (lO.27A, 5.01A,

0 0 0

3.34A); c h l o r i t e and ( ? ) k a o l i n i t e (14.59A, 7.16A,

0

3.5A).

The sample shows no s i g n i f i c a n t change on treatment w i t h ethylene glycol. Treatment of t h e rock i n a l k a l i n e s o l u t i o n f o r s e v e r a l months h a s produced a d e t e c t a b l e change i n c l a y mineral content and t h e r e i s no evidence f o r a n expansive c l a y mineral.

Figure 11

On h e a t i n g t o 550°C f o r 1 hour t h e i l l i t e

r e f l e c t i o n s a r e enhanced and sharpened suggesting t h e c o l l a p s e of mixed l a y e r s t r u c t u r e s . m e

first o r d e r c h l o r i t e r e f l e c t i o n p e r s i s t s and h i g h e r o r d e r s have vanished.

SETTING OF GENERAL ELECTRIC CO. DIFFRACTOMETER

EXIT S L I T : 3 " TIME CONSTANT: 2

SOLLER SLITS: MEDIUM RESOLUTION X-RADIATION: Cr

RECEIVING SLIT: 0.2" FILTER: V

RESPONSE: LINEAR KV: 5 0

FULL SCALE DEFLECTION: 2 0 0 c . p . s . m A : 16

Figure 1 2

-

0 0

Minerals i d e n t i f i e d a r e : i l l i t e (10.19A, 5.01A,

0 0 0

3.3A); c h l o r i t e and ( ? ) k a o l i n i t e (14.75A9 7.1A),

There i s no s i g n i f i c a n t change on t r e a t m e n t w i t h e t h y l e n e g l y c o l , The _{c l a y m i n e r a l s i d e n t i f i e d} a r e a p p a r e n t l y t h e same a s i n t h e 0 '

-

24' sample, Figure 1 3 A f t e r h e a t i n g f o r 1 hour a t 550°C t h e first 0 o r d e r c h l o r i t e r e f l e c t i o n (14,43A) i s enhanced and h i g h e r o r d e r s have vanished, The i l l i t e peaks a r e a l s o i n c r e a s e d i n h e i g h t and a r e f l e c -

0

t i o n a t 4.5A h a s appeared, This i s a t t r i b u t e d

t o t h e (020) r e f l e c t i o n from mica-type c l a y m i n e r a l s . The main i l l i t e peak i s enhanced and

sharpened and h a s moved t o correspond t o a

s l i g h t l y lower I n t e r p l a n a r Spacing, This pro- bably i m p l i e s some degradation i n t h e s t r u c t u r e of t h e mineral.

SETTING OF GENERAL ELECTRIC CO. DIFFRACTOMETER

EXIT S L I T : 3 " TIME CONSTANT: 2

SOLLER SLITS: MEDIUM RESOLUTION X-RADIATION: Cr

RECEIVING SLIT: 0 . 2 ' FILTER: V

RESPONSE : LINEAR K V : 5 0

FULL SCALE DEFLECTION: 200 c.p.s. m A : 16

Figure 1 4

0 0

Minerals i d e n t i f i e d a r e : i l l i t e (10.27A, 5.03A,

0 0

3.

7j51)

; c h l o r i t e and k a o l i n i t e ( ? ) (14.43A, 7

.

24A,

0 0

4.75A, 3.57A). After treatment with ethylene g l y c o l 0

t h e r e i s an apparent doubling o f t h e 1 O A i l l i t e peak 0

and a small "peak" a t 11.94A has appeared. These f e a t u r e s a r e not duplicated on t h e re-run over t h e same region and a r e not regarded a s s i g n i f i - cant. The clay minerals separated from t h e rock subjected t o a l k a l i n e a t t a c k do n o t appear t o d i f f e r from those present i n the untreated rock.

Figure 15

After heating f o r 1 hour a t 550°C the f i r s t order i s t h e only c h l o r i t e r e f l e c t i o n which remains. lIhe i l l i t e peak i s sharper and higher and h a s moved t o correspond t o a s l i g h t l y lower value of t h e I n t e r p l a n a r Spacing. This

i s

taken t o i n d i c a t e some degradation and disorder i n t h e unheated material.

SETTING OF GENERAL ELECTRIC CO. DIFFRACTOMETER

EXIT S L I T : 3'

SOLLER SLITS: MEDIUM RESOLUTION RECEIVING SLIT: 0 . 2 '

RESPONSE: LINEAR

FULL SCALE DEFLECTION: 2 0 0 c.p.s.

TIME CONSTANT: 2 X-RADIATION: Cr FILTER : V

K V : 5 0 m A : 16

Figure 1 6

Minerals i d e n t i f i e d a r e i l l i t e (double peak a t

0 0 0 0

11.53A and 10.27A, t h e peaks a t 3.69A and 3.59A

could r e p r e s e n t e i t h e r t h e t h i r d o r d e r of t h e i l l i t e 0

peak o r t h e second o r d e r of t h e 7.248 peak a t t r i b u t e d

0

t o c h l o r i t e ) ; c h l o r i t e o r k a o l i n i t e ( ? ) (7.24A) q u a r t z

0 0

( ? ) (3.36A) ; f e l s p a r (3.21A). A f t e r treatment with ethylene g l y c o l t h e double peak i n t h e r e g i o n of t h e f i r s t o r d e r i l l i t e peak h a s become a f e a t u r e - l e s s hump on which n e i t h e r peak is c l e a r l y resolved.

0

A f t e r heatine; f o r 1 hour a t 550°C t h e 7.248 r e f l e o - t i o n vanished, The first o r d e r c h l o r i t e though weak was recognized on a Debye-Schemer photograph.

Figure 17

Minerals i d e n t i f i e d a r e i l l i t e ( t h e r e

i s

a similar doubling of t h e first o r d e r r e f l e c t i o n noted i n

0 0

Fig. 1 6 ) ; c h l o r i t e and ( ? ) k a o l i n i t e (14.75A, 7.16A,

0 0 0 0 0

3.57A); q u a r t z (3.36A, 4.29A); f e l s p a r (3.208, 3.26A). m e r e i s no evidence f o r expansive m a t e r i a l a f t e r treatment w i t h g l y c o l , The c l a y m i n e r a l s a p p a r e n t l y do n o t d i f f e r from those p r e s e n t i n t h e rock which h a s n o t been s u b j e c t e d t o a l k a l i n e a t t a c k (Fig. 1 6 ) .

The form of t h e i l l i t e peaks on both Fig, 16

and Fig. 17 i n d i c a t e s d i s o r d e r and a more degraded s t x u c t u r e i s suggested than i n t h e Kingston

Figure

18

0 0

The

mineral i d e n t i f i e d

is:

i l l i t e (10.586, 4.956,

0

3.376).

A f t e r treatment

w i t h

ethylene g l y c o l

0

t h e r e

i s s l i g h t evidence f o r

a

peak a t 16,8A,

Figure 19

After h e a t i n g of t h e above sample f o r

1

hour

a t

550°C t h e r e

i s a slight

i n c r e a s e of t h e peak

0

a t 14.5

-

15,778 which confirms t h e presence of

SCALE FACTOR: I MULTIPLIER: 0 . 6 TIME CONSTANT: 16 DIVERGENCE: I " SCATTER SLIT: I " RECEIVING SLIT: , 0 0 3 '

SCANNING RATE: l o / MIN. X-RADIATION : Co FILTER: Fe

K V : 4 0 m A : 15

Mgure 20

0 The minerals i d e n t i f i e d a r e i l l i t e (10.47A,

0 0

5.07A, 3.34A) and quartz (3.341, 4.31;). There i s no s i g n i f i c a n t change on treatment with

0

ethylene glycol, IChe peak a t 7,14A corresponds t o t h e second order r e f l e c t i o n of e i t h e r c h l o r i t e o r venuiculite.

Figure 21

After heating of t h e above sample f o r 1 hour a t

0

550°C t h e r e i s a weak r e f l e c t i o n a t 14.44

-

15.31A which suggests t h a t c h l o r i t e i s present.

Figure

22

The minerals i d e n t i f i e d a r e

:

i l l i t e (10,26i),

0 0 0

c h l o r i t e

( ? )

(14.65A),

quartz

(3.36A, 4.278).

0

The r e f l e c t i o n a t 4.55A i s a t t r i b u t e d t o t h e (020)

of t h e mica-type c l a y minerals,

!lhe sample shows

no s i g n i f i c a n t change on treatment with ethylene

glycol.

A f t e r heating t h e above sample f o r

1

hour a t

0

550°C t h e r e

i s

a n enhanced r e f l e c t i o n a t 15.08A

SETTING OF NORTH AMERICAN PHILIPS (NORELCO) DIFFRACTOMETER SCALE FACTOR: I MULTIPLIER: 0 . 6 TIME CONSTANT: 16 DIVERGENCE: l o SCATTER SLIT: l o RECEIVING SLIT: , 0 0 3 '

SCANNING RATE: lo / MIN.

X-RADIATION: Co FILTER: Fe K V 4 0 m A : 15

APPENDIX A ANALYTICAL RESULTS

HYDROCHLORIC ACID Sample 1. 3 gm KO t o 24 f t

I

2. 0.5 gm nE1t 1 3.,0.5 gm KGn + 0.1 per cent hectorite

1

Glycolated No change : Hectorite n o t

detected Analytical Treatment of Sample Oriented s l i d e Glycolated Heated 1 hour a t 550°C Oriented s l i d e Glycolated Heated 550°C 1 hour Oriented s l i d e Result of X-ray Analysis Ro dolomite, no c a l c i t e . I l l i t e , c h l o r i t e ? Eo change 0

1 4 A peak strong. Higher order r s f l e c t i o n s vanish : c h l o r i t e confirmed No dolomite, no c a l c i t e . Felspar, quartz, i l l i t e , c h l o r i t e ? Bo change 0

14 A peak stronger. Higher orders vanish : c h l o r i t e confirmed No dolomite, no c a l c i t e . I l l i t e , c h l o r i t e Separation Frocedure ;6 hours s t i r r i n g a t room temperature Volume, N o m l i t y e t c . of Reagent 2000 m l 0.1N

I

23 hours s t i r r i n g a t room temperature 18 hours s t i r r i n g a t room temperature

-

500 m l 0 . U 500 m l 0.1N

PCFX'IC ACID Sample 4. 5 gm KO to 24 ft 5. 1.8 gm "KG

Volume, Normality etc. of Reagent

-

-

-

~

200 ml 4.4M

-

100 ml 4.4M Separation Procedure 16 hours stirring at room temperature Stirred 23 hours at room temperature Analytical Treatment of Sample

-

Oriented slide Glycolated Heated 1 hour at 550°C Oriented slide 6. 6 gm KO to 24 ft + 0.1 per cent hectorite 7. 2.5 gm KO to 24 ft + 1 per cent hectorite

.-

Result of X-ray Analysis No dolomite, no calcite. Illite and chlorite?

No change

0

14 A peak enhanced. Higher

orders vanish, chlorite

confirmed

.

Illite, chlorite peaks weak.

Oriented slide

Glycolated

Oriented slide

Glycolated

Illite, chlorite

I

Bo change. hectorite not detected.

Illite, chlorite, probably

q u a r t z .

1Po change. hectorite not detected. Stirred 16 hours at room temperature Stirred 22 hours at room temperature 200 ml 4.4M

--

200 ml 4.4M

AMMONIUM ACETATE

Sample Separation Procedure

Oriented s l i d e

Volume, Normality e t c .

I

A n a l y t i c a l Treatment

I

Result of

of Reagent of Sample X-ray Analysis

I

S t i r r e d 16 hours a t

room temperature Strong dolomite moderate c a l c i t e , q u a r t z , f e l s p a r . No clay-mineral r e f l e c t i o n s . 200 m l 4.4M - S t i r r e d 72 hours a t 1000 m l 4.0M room temperature - - Oriented s l i d e

I

- Strong dolomite, c a l c i t e weaker. AMBERLITE I R 120

?

W Sample 10. 10 gm KO t o 24 f t c

Separation Procedure Volume, Normality e t c . A n a l y t i c a l Treatment Result of

of Reagent of Sample X-ray Analysis

-

R e s i n f i l l e d c o l u m n 1 8 0 0 m l o f r e s i n Oriented s l i d e I n t e n s e dolomite r e f l e c t i o n , s t r o n g c a l c i t e , f e l s p a r , quartz, weak i l l i t e and c h l o r i t e

Sample 11. 5.5 gm KO t o 24 f t 12. 5.5 gm KO t o 24 f t + 0.1 p e r c e n t h e c t o r i t e 13. 5.5 gm KO t o 24 f t + 0.1 per cent h e c t o r i t e

14. 2.5

-

Four 3-hour c y c l e s 70 m l of f r e s h Oriented s l i d e No dolomite, no c a l c i t e .

W K G ~ a t 70°C r e s i n added a t I l l i t e , c h l o r i t e . each cycle Separation Procedure: Batch Technique One 4-hour c y c l e a t 70°C

One 2-hour cycle a t 70°C Two 2-hour c y c l e s a t 70°C PTVO 3-hour c y c l e s a t 70°C I Volume of Resin 140 m l 140 m l f r e s h r e s i n 140 m l r e s i n regenerated f o r second cycle 140 m l r e s i n . Fresh r e s i n f o r second cycle A n a l y t i c a l Treatment of Sample Oriented s l i d e Oriented s l i d e Glycolated Oriented s l i d e Glycolated Result of X-ray Analysis No dolomite. I l l i t e , c h l o r i t e . Strong dolomite r e f l e c t i o n . Eo change : h e c t o r i t e not detected.

Reduced dolomite peak. I l l i t e , c h l o r i t e .

Weak r e f l e c t i o n a t 17.5 ( ? )

Sample 15. 2.5 gm KO t o 24 f t + 0.1 per c e n t h e c t o r i t e 16. 2.5 gm KO t o 24 f t + 1 p e r cent h e c t o r i t e 117. 2.5 pm KO t o 24 f t + 1 per c e n t h e c t o r i t e Separation Procedure: Batch Technique Four 3-hour c y c l e s a t 70°C Four 3-hour c y c l e s a t 70°C ICwo 3-hour c y c l e s a t 70°C 16 hours sedirnen- t a t i o n , and 50 m l p i p e t t e d from t o p Result of X-ray Analysis KO dolomite, no c a l c i t e . Quartz, f e l s p a r , i l l i t e , c h l o r i t e . No change: h e c t o r i t e n o t d e t e c t e d . Volume of Resin 70 m l of f r e s h r e s i n a t each cycle A n a l y t i c a l Treatment of Sample Oriented s l i d e Glycolated

-

70 m l of f r e s h r e s i n a t each c y c l e 70 m l of f r e s h r e s i n a t each cycle Heated 1 hour a t 550°C

-

Oriented s l i d e Glycolated Oriented s l i d e Glycolated l o

14 A peak enhanced. Higher o r d e r s vanish o r weak. C h l o r i t e conf inned. No dolomite, no c a l c i t e . Quartz, f e l s p a r , i l l i t e

,

c h l o r i t e . No change : h e c t o r i t e n o t detected. I l l i t e , c h l o r i t e 0 Reflection a t 17.8 A : h e c t o r - i t e d e t e c t e d .

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-

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.

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"

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-

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s o o m , S k S W

;"

o r l o a m a U P a l 0 0 E : a 0 al.A cn r - e a t 5 r - a a al +..-I- al e t ' w.4 k I ~ O (\I+' ? $ s 00 rl

E

m g f i d C S A P 3 2 . 2 I n r l m a l a k + d P . ~ r l m a a m 3 c ; P ~ r l ~ i P a , r i .O a..-IcH k fi 0 0 - P r l a P r l V) m r(

R e s u l t of X-ray A n a l y s i s

0

1 0 A i l l i t e peak w i t h double

maxima. Weak peak ( ? ) a t

15.08 A c h l o r i t e .

Broad d i f f u s e peak around

0 1 0 A i l l i t e b r e a k i n g down. 0 Veak 1 4 A r e f l e c t i o n ( ? ) c h l o r i t e . F i r s t o r d e r i l l i t e . I l l i t e peak d i f f u s e . I l l i t e peak sharpened. F i r s t and t h i r d o r d e r i l l i t e .

First and second o r d e r peaks

o f i l l i t e , no c h l o r i t e . I l l i t e : f i r s t , second, and t h i r d o r d e r i l l i t e peaks. A n a l y t i c a l Treatment of Sample Heated 550°C 1 hour Heated 700°C 1 h o u r Film. Randomly o r i e n - t e d powder i n c a p i l - l a r y . Heated 550°C 1 hour. - O r i e n t e d s l i d e Glycolated Heated 350°C 1 h o u r Heated 450°C 1 h o u r D i f f r a c t o m e t e r r e - a l i g n e d and sample h e a t e d a t 450°C re- run.

-

Heated 550°C 1 h o u r Volume of Resin

-

-1) -Sample 19. ( c o n t i n u e d ) 2.5 gm C . V . l ( Xta-:?a '2ille;r l i r s t o n e a f t e r t r e a t m e n t i n 21!c31Lxe s o l u t i o 2 ) . S e p a r a t i o n Frocedure : Batch Technique - S e d i m e n t a t i o n c o l m shaken up and a f t e r 16 h o u r s sedimenta- t i o n , 50 m l p i p e t t e d from t o p .

Sanple 20. 2.76 gn ( FAxgst on Green Band. a f t e r s e - v e r a l months S e p a r a t i o n Procedure : Batch Technique 50 m l p i p e t t e d from s e d i m e n t a t i o n column a f t e r 1 0 days s e d i - mentation. Volume of Resin Pro 3-hour c y c l e s a t 70°C. 16 hours s e d i - n e n t a t i o n and 50 m l p i p e t t e d from t o p . A n a l y t i c a l Treatment of Sanple 70 m l of f r e s h r e s i n a t each c y c l e .

-

--

O r i e n t e d s l i d e .

--

G l y c o l a t e d Heated 550°C 1 hour

-

Oriented s l i d e

-

Glycolated Heated 550°C 1 h o u r Heated 700°C 1$ h o u r s R e s u l t of X-ray A n a l y s i s I l l i t e , c h l o r i t e . - - - 0 Yeak peak ( ? ) a t 11.94 A . 0 1 4 -4 peak p e r s i s t s b u t n o t en- hanced-abnom:al behaviour. 0 7 A peak vanished : c h l o r i t e . 1- - --- -- I l l i t e

-

s t r o n g f i r s t , second and t h i r d o r d e r r e f l e c z i o n . C h l o r i t e ( ? ) s t r o n g 7 A r e f l e c t i o n . 0 P i r s t i l l i t e peak depressed 7 A c h l o r i t e ( ? ) peak depressed. No evidence f o r expansive m a t e r i a l . P r o b a b l e f i r s t o r d e r c h l o r i t e , h i g h e r o r d e r s v a n i s h

-

r e s u l t i n c o n c l u s i v e . I l l i t e peaks sharpened. I l l i t e peaks s t r o n g . C h i o r i t e - r e s u l t i n c o n c l u s i v e , 1 4

A

r e f l e c t i o n weak.

AMBERLITE IRC-50 Sample 20. (continued) 2.76 gm ( :angston Green Band a f t e r s e - veral months in a'ka1ine s o l u t i o n ) 21. 2 . 4 8 8 ~ KC t o 24 f t IVS ( Kingston 0 t o 24 f t rock a f t e r s e v e r a l months in a l k a l i n e s o l u t i c m ) S e p a r a t i o n Procedure: Batch Technique Sedimentation column shaken up and a f t e r 16 hours sedimenta- t i o n 50 m l p i p e t t e d from t o p .

Volume of Resin A n a l f i i c a l Treatment of Sample F i l m . Randomly o r i e n - t e d powder in c a p i l - l a r y . Sample heated 550°C 1 hour. Oriented s l i d e Glycolated

I

Result of X-ray Analysis 0 14 A r e f l e c t i o n p r e s e n t , b u t weak. Conclude c h l o r i t e p r e s e n t . C h l o r i t e ( ? ) f i r s t , second, and f o u r t h o r d e r r e f l e c t i o n s . I l l i t e - f i r s t , second and t h i r d o r d e r r e f l e c t i o n s p r e s e n t . F i r s t i l l i t e depressed. ?To evidence f o r expansive Heated 350°C 1 hour Heated 450°C 1 hour Heated 550°C 1 hour Oriented s l i d e Glycolated I !Two 3-hour c y c l e s a t 70°C. 16 hours s e d i - mentation and 50 m l p i p e t t e d from t o p . m a t e r i a l . C h l o r i t e and i l l i t e peaks p e r s i s t . C h l o r i t e and l l l i t e peaks p e r s i s t . I l l i t e peaks p e r s i s t

-

f i r s t o r d e r c h l o r i t e weak. I l l i t e

-

f i r s t , second, and t h i r d o r d e r peaks. C h l o r i t e

-

f i r s t , second, and f o u r t h o r d e r peaks. I l l i t a and c h l o r i t e peaks depressed. No evidence f o r ex- pansive m a t e r i a l .

70 m l of f r e s h r e s i n a t each c y c l e

AMBERLITE IRC -50 C Result of X-ray Analysis I l l i t e

-

f i r s t , second, and t h i r d o r d e r peaks. C h l o r i t e

( ? ) a l l peaks vanished

-

abnor- n a l behaviour.

I l l i t e - first, second and t h i r d o r d e r peaks. C h i o r i t e

-

f i r s t o r d e r weak, second o r d e r s t r o n g , f o l l r t h o r d e r s t r o n g . I l l i t e

-

peaks depressed. C h l o r i t e

-

f i r s t o r d e r peak s l i g h t l y s t r o n g e r , second o r d e r peak depressed. I l l i t e

-

first and t h i r d o r d e r peaks only and of reduced in- t e n s i t y . C h l o r i t e

-

no peaks p r e s e n t .

I l l i t e

-

f i r s t , second, and t h i r d o r d e r peaks enhanced. C h l o r i t e

-

weak f i r s t o r d e r r e f l e c t i o n only. Weak peak ( ? )

a t 11.14 A.

I l l i t e

-

first, second, and

t h i r d o r d e r peaks. C h l o r i t e

-

no f i r s t o r d e r , weak second o r d e r . Eo evidence f o r expansive m a t e r i a l . Sample 21, (continued) 2.488 gm W t o 24 f t IVS ( Kingston 0 t o 24 f t rock a f t e r s e v e r a l months i n a l k a l i n e s o l u t i o n ) A n a l y t i c a l Treatment of Sample Heated 1 hour 550°C Hew o r i e n t e d s l i d e made t o r e - i n v e s t i - g a t e whether c h l o r - i t e i s p r e s e n t Glycolated Heated 1 hour 550°C. Clay m a t e r i a l c u r l e d up on s l i d e . Clay homogenized and r e - deposited. S l i d e re-heated f o r 1 hour a t 550°C Oriented s l i d e Glycolated Separation Procedure: Batch Technique Sedimentation column shaken up and a f t e r 16 hours sedimenta- t i o n 50 m l p i p e t t e d from top. Volume of Resin

L

Result of

X-ray Analysis

-

0

Chlorite

-

weak 14 A peak no

0

7 A r e f l e c t i o n .

Chlorite

-

no peaks present. I l l i t e

-

peaks s t i l l present. I l l i t e

-

peaks q u i t e strong. Chlorite

-

no convincing peaks. I l l i t e

-

f i r s t , second, and t h i r d order r e f l e c t i o n strong. Chlorite

-

f i r s t peak weak, second order strong, t h i r d and foGrth order present.

No evidence f o r expansive material.

I l l i t e

-

f i r s t , second, and t h i r d order peaks strong. Chlorite

-

double peak a t

0 0

14.6 A and 15.77 A , peak a t 7.96

i.

The above peaks a r e not repro- duceable on repeated runs on t h e diffractorneter.

I l l i t e

-

first, second, and t h i r d order peaks. Chlorite

-

no peaks which could be a t t r i - buted t o c h l o r i t e . Analytical Treatment of Sanple Heated 1 hour 350°C Heated 1 hour 450°C Heated 1 hour 550°C Oriented s l i d e Glycolated Heated 550°C 1 hour Heated 700°C 1i hours Volume of Resin Sample 21. (continued) 2.488 gm KO t o 24 f t IVS ( Xingston 0 t o 24 f t rock a f t e r several months i n a l k a l i n e solution) Separation Procedure: Batch Technique Top 50 m l pipetted fron sedimentation column a f t e r 3 days sedimentation