Calhoun: The NPS Institutional Archive

Theses and Dissertations Thesis Collection

1951

The identification and investigation of the expansion

characteristics of clays by X-ray diffraction

Dearth, Keith H.

Troy, New York : Rensselaer Polytechnic Institute ;

ybrary

U. S. Naval Postgraduate School

Monterey, Caliloniia

THE IjjENTIFIChTION AUD Ii:]VESTlGi--TIOw

OF TJIE

EXPANSION CKaRaCTERISTj.CS OF CLrY^I

3Y. X-.RAY DIFFRACTION

Submitted to the Faculty of

Rensselaer Polytechnic Institute

in

Partial Fulfillment of the

requirements for the degree of

Master of Civil Engineering

by

KEITH K. DEARTH

and

RICHARD C. WILLIAMS

May 1951

ACKNOV/LEDGEMEN T S

The authors gratefully acknowledge the guidance and

encouragGment given them by Professor E. J. Kilcawley of

the Division of Soil Mechanics, Department of Civil Engin-

eering, Rensselaer Polytechnic Institute,

To Doctor Arthur A. Burr of the Department of Metal-

lurgy they wish to express their sincere appreciation for

his Valuable advice and assistance v;ithout v/hich this

the sis v/oul d hav o been impo s s ib 1 e

,

Acknowledgement is also made to Mr. Ralph E. Winslow,

Head of the Dopartmont of Architc; cture , for his skill in

the production of a sample extruding device.

An expression of gratitude is made to the following

for their services and advice:

Dr. Sydney Poss, ii.ssociate Professor of Colloid Science,

R. P. I.

Dr. W. E, Bradley - State G-eological Survey Division,

University of Illinois,

Dr. F. G. Nachod - Sterling-Winthrop Research Institute.

E. B. ''feed - Acting Head, Research and Geology Division,

U. S. Department of tlie Interior, Bureau of Reclamation.

S. V. Ballou, Colloid assistant, Cneiiistry Department,

R. P. I.

R. G. Starr, Chemistry Department, R. P. I.

\$(=.^0

TABLii: OF CONTENTS

Part Page

I Introduction 1

II Theor^r 4

III Apparatus 10

IV Procedure 13

V Results and Conclusions 29

VI RecornnGndations 33

VII Appendix 41

Dix fraction Data 42

Illustrations of Apparatus 81

Sai.iple Cor:iputa.tions 84

References , , . , 85

PART I

INTRODUCTION

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INTRODUCTION

During the thirty-nine years since Laue discovered

that x-rays interact with crystalline materials to give

diffraction effects, x-ray diffraction has become an

exceedingly valuable tool to industry and research. The

chemist and physicist as well as the minerologist have

found, in x-ray diffraction, a powerful adjunct and often

a substitute for more costly and time consuming analyses.

The metallurgist recognizes x-ray crystal structure analy-

sis as the outstanding contribution of the science of

physics to the study of alloys. X-ray diffraction has

permitted the soil scientist to make some of his greatest

strides toward a more complete knowledge of soil make-up

and behavior.

In 1950, using x-ray diffraction, Hendricks and Fry

discovered that the clay materials of soil were crystal-

line. This was definitely confirmed in 1031 by Kelley,

Dore and Brown and these discoveries led directly to the

identification of specific substances establishing them to

be composed principally of given clay minerals^ ', Since

that time, investigators have used x-ray diffraction to

study the crystalline structure of the clay minerals, to

establish a system of their precise identification, to

study the hydration characteristics and behavior due to

the wetting of expanding lattice clays, and to study the

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base exchange mechanism of clays,

Quantitative analysis by x-ray diffraction has been

put to extensive use in the field of chemistry and it is

believed that the same can be achieved in the soils field.

The principal objective of this thesis was the devel-

opment of a good TECHNIQUE for the x-ray diffraction of

clays such that the penetration and reflection of x-rays

were a maximum with a minimum ar-iount of exposure giving a

clear and complete diffraction pattern. This entailed:

(1) Arriving at an optimum clay particle size; (2) estab-

lishing a procedure whereby the clay sample, both dry and

then fully hydrated, was easily prepared for mounting in

the x-ray camera so as to have the proper shape, size and

consistency; (3) choosing the most advantageous x-ray

target material and the optimiim radiation line and series

of that material; (4) determining the proper x-ray photo-

graphic film and exposure time; and finally, (5) proper

interpretation of the resulting diffraction pattern so as

to determine the identification of the clay and study its

expansion characteristics due to the effects of homo-ionic

saturation and hydration.

Such research is not new as it has been done many

tines before, and numerous results have been published.

However, very little information has been published cover-

ing the actual procedures followed and what methods of

sample preparation were used. Practically no data is

offered in those published results which enable us to

-5-

detemiino such essontial information as particle size,

specimen size, ion content of clay, moisture content and

origin of clay. Without such information available, the

results are of no practical value.

With the above criticisms in mind, it was decided to

make it a subsequent objective of this thesis to establish

a definite procedure for the x-ray diffraction of clays

which can be readily followed and applied toward future

investigations of soils incorporating such possibilities

as identifying and measuring the components making up the

soil, determining the state of chemical combination of the

constituent elements, determining the nature of the ad-

sorbed ions, aiid obtaining an indication of the processes

involved in t}ie deposition, consolidation, and induration

of the soils.

PART II

TI-IEORY

-4-

11 crv.Tciillj 118 :..i^.ttoi" r^ Gi.'.p0 3-.^1 cf rxto.n/.' nr- "'.olC;Cul3S

-l.n,i'.}. "9 i^ffK 11 "I r:' .c:-i i. TTiar/.ior thc-.t tliey foiTi dr^f-.ni to f .-.:-:;..j :! os of

:ri.-:n(i .:-^i.na.i-T x- Tc:^-. ^ >' bo -'erLerted b\ t'ls.is pla^-^e:; Ir th

.

'?r-c £ of tne (;rys"oal, tho Bra^;g'3''"- \vGre ablo to rr-iduce ':..£<:,: ^

original -.TiatherLatically complex analysis of this I ntc:''action

between x-rays and crystalline matter to terms of .^r'^at sim-

plicity. In fi^ijre 1, two such planes A3 and CD rei-resent

one of the many families of planes found in a cryr^tal. Two

rays orrif and gnoph of tho defined x-ray boaiii arc showi to

bo partly roflectod from those pianos v/hon striking thorn

with an incident and reflected ani"^!© of Q, According to tho

laws of optics^^)^ these reflected rays must be in phase to

be observed as a reflection. Consequently, ray gnoph must bo

longer than ray omf by an integral value of the wave length

Pl • Inspection reveals that this path difference is tho

distance nop and that no = d sin ©, and op - d sin 9; thus

nop s 2d sin <^ s n -'^

, which is tho statom.ont of Bragg' s

law(3): "A given wave length will be reflected in a given

spectral order only when tho glancing angle takes a unique

value e".

.^

tvS

Figure 1, Reflection of x-ray"*-boam from planes in face of cr^^taL

-5-

Tho formation of i refloctcd bef-n l:. oo- i-i.it lojiocI by tho

GxistencG of equally spaced layers of particles, but not upon

the regular spacing of these particles within the layers.

Those sets of net planes which are densely populated

comrnonly occur as crystal faces and emit high intensities of

reflection whereas those net planes of sparse population do

not occur as face planes and emit low intensities of reflec-

tion,

A crystal is essentially a pattern. The atoms are

arran.^ed according to a plan, such that the same configura-

tion is repeated at regular intervals in all throe dimensions.

V/hen a pattern is three dimensional, as in a crystal, tho

array of points at which the pattern repeats is a "space-

lattice". 3y joining the points space can be divided into

a series of parallel- sided unit cells efich of which contains

a complete unit of pattern. The ivhole structure is formed by

stackin,^ unit cells side by side. The volume of each unit

Cell is the so.r:ie,

Tho axes of the unit coll are designated as a, b =and c

as shown in fi>zure 2^ '

ZH0' '

Ll

Figure 2. Unit Cell

The edges of the unit cell are termed "unit translations"

in the pattern,.

Tho various planes of a crystal are designated by their

intercepts (h, k, 1) on the reference axes a, b, c respective-

—o~

ly. 1 plf.nn .•^bich is •porponciicular t<^ :•''...': o->.'.-x:U: ;/r d p-^-rallol

to the a and b axos is aesir-natod as a (0 ^) p?i.ane.

Those points of the spaco-latticG at which the patterns

of a crystal repeat are occupied by atoms and are termed

"lattice particles or points". Any plane of a crystal which

is occupied by lattice points is known as a "crystal plane"

or "net plane", A crystal face is always parallel to a net

plane.

External crystal faces are parallel to the more densely

crowded net planes of the space lattice.

Spherical waves are created when x-rays, which are

electromagnetic waves, cause forced oscillations of the

planetary electrons of the atoms v;hich they traverse, the

electrons absorbing energy from the x-rays when moving away

from the nucleus and radiating energy in all directions when

moving tov/ard the nucleus. The dimensions of the space-lat-

tice are of the same order of magnitude as the wave lengths

of x-rays and this three-dimensional point system will pro-

duce very narrow pencils of rays only in those directions in

which these spherical waves are in phase. These reinforced

waves are the rays that produce the individual spots in x-ray

patterns (Laue, rotation, Weissen.berg, etc.) obtained from

single crystals. If the single crystal is replaced by a large

number of smaller crystals, that is, a powder, their statis-

tical orientation, unless preferred orientation effects result

owing to peculiar crystal shapes, then must produce a whole

series of such discrete pencils, so that as a result a contin-

uous diffraction cone is obtained. If this cone is now re-

corded on ?^ photo,'_;raphic fir-n placed o-...^;.--.:..dicula.r to the cone

axis, tho diffraction effect is obtained as a lino miich is in

the form of a ring, A pattern on which the diffraction rings

from all families of planes have been recorded is usually

rofcrrod to as a powder pattern and consists of a series of

concentric rings on a flat film, or axes of rings on a cylin-

drical strip of film,

A fixed space arrangement of atoms '.vith definite fixed

distances between them must always produce precisely the same

x-ray pattern, F'urthermore, if the same space arrangement

is retained but the distances between atom centers are

changed, the x-ray pattern will retain its same general appear-

ance but v/ill either expand or contract. On the other hand,

if the space arrangement is altered, the pattern is changed.

Consequently, x-ray diffraction patterns arc a sort of finger-

print of crystalline materials. 2ach individual substance

present in a mixture will produce its tinique diffraction

effects, so that the pattern derived from the mixture is a

composite of the patterns of all tho materials or compounds

in the mixture. Furthermore, the intensities of the lines

of tho individual patterns are a function of tho relative

amount of the material present in the mixture, so that the

method also has quantitative aspects.

The clay minerals offer a fascinating field of study

for x-ray analysis, the exploration of which has only been

coiTimonced, The typical minerals are micaceous in structure,

consisting of thin hexagonal flakes with perfect cleavage.

There can be little doubt that all are based upon the sheet

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of linked totrahodral groups v/hich is characteristic of the

mica minerals.

The principal constituents of the lattices of the

various clay minerals are the unit cells of the silicon-

oxygen tetrahedron and the aluminum-hydroxyl octahedron

which arc bonded together by electrostatic forces and form

the tetrahedral silica sheet or chain and the Gibbsite sheet

rcspoctivoly.

X-ray diagrams of clays show two separate series of

linos (or bands), one due to the "two dimensional crystallites"

(indices h, k, 1), the other a single series of orders,

indexed (0 1), due to the intersheet separation. Only the

latter series changes in adsorption reactions, and from it

the (0 1) spacing, and thus the separation of the structural

sheets are readily deduced. In adsorptive reactions with

these minerals (particularly montmorillonite)

, molecules of

water and ions can penetrate between the structural sheets,

thus expanding the whole crystallite structure, a change

detectable by x-ray diffraction and thus enabling the study

of the expansion characteristics of the clay minerals.

The remarkable activity of montmorillonite in adsorption

is 210 doubt connected with a common peculiarity of its crys-

talline structure, which is such that regular (two-dimension-

ally crystalline) sheets are superposed without any regular-

ity (except for constant separation) and are held together

by relatively weak forces.

As for the application of x-ray diffraction for the

identification of clay minerals, the interpretation of the

-9-

data roquiroG th(; convorslon of the lines in th;j x-ray powdor

pattern to their corresponding interplanar distance so that

Hanawalt ' s ''^) method employing the card file of x-ray diffrac-

tion data can be used; or an extended series of standard

patterns which are used for direct comparison,.

PART III

APPARATUS

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APPARATUS

SLSCTRODIkLYZBR . The electrodialyzer used was a

standard three- cell 3RADPIELD type operating with 110 volts

D.C. Each of the three cells is separated fror.i the other

by cellophane diaphrams which are impermeable to water but

highly permeable to ions. The diaphrams are mounted between

U-shaped rubber gaskets which in turn are backed by metal

plates. This entire arrangement is clamped together forming

a sandwich v^hich encloses tlie three separate cells. This

three- cell arrangement is conveniently mounted on a stand.

The two outer compartments are the cathode and anode while

the central cell contains the material which is to be

electrodialyzed. The cathode is a nickel screen and the

anode is a platinLun screen both of which are placed inside

the cells designated as the cathode and anode colls re-

spectively. A glass tube arrangement is inserted into the

cathode and anodo cells and tap water is run through it

continuously such that adequate cooling of the poles is

affected.

The sample, mixed with distilled water to form a sol,

is placed into the central cell. The outer cells are

filled with distilled wator which is continuously replaced

in the cathode cell from a source located above the equip-

ment, the water being fed by gravity flow and maintained

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at a constant level within the cell by a simple overflow

arrangement. The anode is periodically replenished with

distilled water by manual draining and rofillinr*, only

periodic replacement of the distilled water being neces-

sary since the anion content of clays is slight compared

to the cation content.

This DRaDPIELD eloctrodialyzcr was maniofacturcd by

the Central Scientific Co. (Conco) and the wiring diagram

is as shown in Figure 3,

1^"mode

eloctrodialyzcr-*^—-j

'He atho do

110 V D.C,

300 ohm re si stance

\ L

Figure 3, Wiring diagram of the BRaDPIELD three- cellelectrodialyzer.

The theory of eloctrodialysis of clays will not be

attempted here as there are many fine references pertaining

to this, one of vhich is exceptionally good^^'.

Figure A (page 82, Appendix) is a photograph of the

assembly used for the eloctrodialysis of the Rock River,

Wyoming Bentonite,

APPARATUS FOR THE lOillC SATURATION OP HYDROG-EN BEN-

TONITE. This apparatus merely consisted of a 600 ml

beaker containing the hydrogen bentonite as received from

the electrodialyzer, o mechanical stirrer employing a glass

stirring rod, a 50 ml burette containing the appropriate

"12-

hydroxide compound, and a BECia.iAM pH motor Model vdth

calomel electrodes. The clay, still in sol form, was

beat ^vith the stirrer wliile the hydroxide compound was

slov/ly added. The calomel electrodes of the pH meter were

kept immersed in the sol thus enabling a constant recording

of the pH of the material,

SiiMPLE EXTRUDER. This extruding device is best illus-

trated by Figure 4. The dry powdered clay is mixed with

¥- cylindrical plunger

cylindrical chamber

stand

- o»0r-0"' hole

Figure, 4. Sample Extruder,

a suitable binder j IXico Household Cement, and is packed

into the cylindrical chamber. The turned down portion of

the cylindrical plunger, which fits into the chamoer with

cxtremol^^ close tolerance, is used to compress the clay

in the chamber thus forcing it to be extruded through the

0.020" hole producing a thread-like clay sample 0.020" in

diameter. The stand is used to support the complete

assembly. High grade steel n'as used in the production oT

each piece of this extruder. A photograph of this complete

assembly is shown in figure A (page 8l , Appendix),

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X-RaY equipment. The general set up for taking X-ray

diffraction patterns of clays is illustrated in Figure 5.

"1

T7<s"

T 4 ^i

Figure 5, Schematic diagrojn illustrating general set-upfor the X-ray diffraction of clays.

T is a current transformer, X is an x-ray tube, F is a

filter, S]_ and Sg are slits in thin sheets of lead, is

the rrio-Linted clay pov'der sample and C is a narrow strip of

photographic film bent over a semi- circular strip of brass

concentric with the clay sample. This diagram is highly

simplified to better illustrate the fundamental considera-

tions involved.

The filter is a shset of metal chosen of such material

that it specially absorbs all v/ave lengths shorter than the

desired one, leaving practically nothing but a single in-

tense line, VriQoL line of the K series of the anode material.

For a copper target, the proper filter is nickel. X-rays

first pass through the filter v^hicii absorbs all but a single

wave length,' then through the two slits which confine them

to a narrow beam (about 1 mra wide); then through tiie pow-

dered clay sample which scatters or "reflects" a very small

fraction of them; and thence to the center of the photo-

graphic film (which can be a flat film as well as a cylin-

drical strip of film). '-^/hen the film, is developed it shows.

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in addition to tho over-exposed portion in the center where

the direct bean strikes, a series of other 13?igs on each

side of the center. These linos constitute the diffraction

pattern of the clay sample (see previous section on THEORY),

An x-ray tube with a copper target and a nickel filter

were chosen for tho work in this thesis as the <?^ lino of

the K series of this material gives maximum sample pene-

tration with minimum exposure (three hours).

No x-ray tiieory nor wiring diagrams for the particular

x-ray used in this thesis will bo given a.s they are quite

involved and are discussed at length in any standard text

dealing with x-rays and radiography.

For the rjeneral Electric diffraction tube used in

in this work tho maximura kilovoltago is 50 K-v,P, and the

maximum tube current is 20 milliamps,

A photograph of the x-ray tube is shown in figure B

(page 82 , Appendix),

POWDER CAMERA. Tlie DEBYE SCHERRER powder camera is

widely accepted as an excellent x-ray camera for obtaining

x-ray diffraction patterns of powdered samples. A drawing

of this powder camera, used in this work, is given in

figure 7 (P^-ge 83 , Appendix) and a photograph of it in

position v/ith the x-ray tube is shown in figure

(page 82 , Appendix). It is essentially a brass cylinder,

closed at one end, with a brass collar which fits, with

close tolerance, concentrically inside. A strip of x-ray

film tv;o inches wide fits against tho inside of tho cylin-

-15-

dor and is pressed flat against it by a simple knob and

slide arrangement which engages the ends of the film and

by sliding along th(3 cylinder's perimeter, forces the film

to be flush against it. The collar, v;hich has a slit along

its perimeter to allow the passage of x-rays to the film,

fits inside tho cylinder against the film thus holding the

film secure in its position. The slit is covered with

opaque paper to protect the film from exposure to light

and yet does not hinder the passage cf x-rays. The two-

slit arrangement as described under the x-ray apparatus

section is made possible by a tapered spindle which is

inserted through tho cylinder, the film, and the collar and

projects inwardly training toward t.he exact center of the

cylinder. This spindle has a 0.030'' diameter hole drilled

through it and thus serves the purpose of narrowing or

collimating the x-rays to 0,030" in width. With proper

alignment of the camera, the narrowed x-rays are directed

toward tlie ssiraple by the collimation spindle. The camera

is mounted on a stand which makes possible the adjustment

of the camera about horizontal axes at right angles to each

other.

The sample, which must be in the form of a cylinder

about 0,2 inm in diameter and one inch long, is mounted

in a small sample,' holding tube which fits Inside a well

in the center of the camera. The x-rays, reduced to 0,030"

width, are directed to the s;\nple by tho collimation spin-

dle, pass thr'.-.ugh tho sample being reflected during this

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transit, and continue on through another spindle which

fits through the cylinder diametrically opposite the ccl-

lination spindle. This second spindle plays the role of

alloTving the x-rays to pass through the entire assembly

so that they can be detected on an x-ray-sensitive screen

mounted on a small stick which is held in the operator's

hand. Proper alignment of the powder camera is accom-

plished when a concentrated x-ray b(5am is seen scintilla-

ting from the s croon,

PI^iT Cassette. This is nothing more than a metal

rectangular frame for holding and mounting, into position

before the x-ray tube, 5" x 7" flrt, rectangular photo-

graphic film. A 5" X 7" piece of opaque paper, which pro-

tects the film from exposure to light but dees not hinder

the passage of x-rays, is placed into the frame and then

5" X 7" flat film is placed inside the frame against the

paper. A 5" x 7" piece of stiff cardboard is then placed

against the film and everything is finally sandwiched to-

gether by a metal backing v?hich is forced against the

cardboard by two springs v/hich boar against the frame.

This assembly is mounted before the x-ray tube and a

0,020" pinhole arrangement narrows tlie beams which are

directed at the cassette 6 cm. aviray. A small lead plug

suspended by a wire is placed against the cassette where

the x-rays strike so as to absorb the direct beam. The

sample, again in the foriii of a small tube or cylinder, is

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moimted across the ccntor of the pinhole such that the

narrowed x-rr\7 boains pass through it and aro rcflooted onto

the filr;i in the cassette giving tho desired diffraction

rings.

A photograph of the flat cassette in position with

the x-ray tube is s}iov;n in figures {P'-g« 82, Appendix),

MEaSIIPvIMCt device. This is used to measure the radii

of the diffraction rings of the diffraction patterns

appearing on tlio negatives. The fi].n, both strip ciixd rec-

tangular, is clamped in a horizontal position and a slide

viewer 'vith a reading hair and vernier is placed v/ith the

hair coinciding with the ring being read. The radius of

the ring is then coriputed from the reading on the vc;rnior.

The measuring device is placed ever a light-box so that

the light shining up through the film enhances the reading

of the film,

DEVELOPING AND PRINTING EQUIPMENT. Standard devel-

oping and printing equipment was used in developing and

printing the diffraction patterns.

PART IV

PROCEDURE

-13-

PROCEDURE

Rock River, Wyoming Bentonite; Dry 3ranch, deoi jj^xa.

KaoDinibe; and Joliet, Illinois Illite - Bearing Ghrle wore

chosen as representative of the three basic clay types.

The cations H'^ , Naf , kI and Ca"^'^ were selectad fo-

the ionic saturation of the clays as thoy ;-ire coamonly

found in clays in nature.

In order to study the expansion charac bericii;!'." of

the chosen clays due to their hydration, the prepared

clay samples were first oven dried at 110*^0. for 24 hours

and were then completely saturated with distilled v/ater.

Each clay v/as passed through a No. 200 mesh sieve in

an attempt to arrive at the optimum particle size for sharp

x-ray diffraction patterns,

HOMO- IONIC Saturation O? clays. The Bentonite was

placed in a mechanical mixer along with distilled water

and was thoroughly mixed producing a clay sol which was

placed into the central coll of the Bradfield electrodia-

lyzer. Ellectrodialysis of this clay sol was allowed to

continue until the pH was reduced to 3,2 as compared to

the original pH of 7.9. The pli determinations were made

with the use of a standard Beckman pPI meter, Electro-

dialyzing a clay sol to a pH of 3.0 to 3.5 produces a pure

HT clayC^). The H^ bentonite sol with a pH of 3.2 was

-19-

reraoved from the electrodialyzor and a portion of it was

placed into a 600 ml. boakor. Using the drraiif^enent as

described under APPARATUS, the sol was beat continuously

while a 0,1 normal solution of sodium hydroxide was slowly

added until a constant pH reading of 8.2 was obtaint-d.

This m.othod was in accordance with roforence ^7) I'o: the

preparation of a relatively pure sodium cj.ay^ l c c a tj c i jm.

and calcii.m bentonito v.'ere also prepared l:v t/c'.^ •r.'i'thod

using 0,1 norma] solutions of potass: un Yr- Irox? C-^ -.o.-d

calci'.:m li^.'^c'roiT.ide respectively in plL'Ce o" i;ho ^,v-'u:'.'\ni

hydroxide

.

The corresponding homo-ionic samples of kaolinite

and illite along with more bentonito were prepared by \V.

D. Ennis and J. C. Hufft^^^, by the potentiomotric ti-

tration method starting with hydrogen clays which were

obtained by displacement with hydrochloric acid.

The following sam.ples were made available for x-ray

diffraction studies: H^ , Naf, K^" and Carf bentonite using

olectrodialysis to obtain the H^ bentonite; H^ , Na"*", k^" and

Ca'J'f bentonito, illite, and kaolinite using HCl displace-

ment to got the RT clays; and the original or as received

samples of bentonito, illite, rind kaolinite. X-ray dif-

fraction patterns were taken of each of the above samples

in the oven-dry state (110°G. for 24 hours) and the com-

pletely hydratod state,

PREPaRaTIOLI of clay SALlPLilS i^'OR X-RAY DIFFRaCTIOII,

-20- •

After obtaining the prepared clay samples, a suitable

method for mounting the samples in the x-ray camera had

to be devised. Before the method of mounting the pow-

dered specimen, whether dry or fullj'" h^'-drated, could bo

selected, the optimum thickness of the sample to bo used

had to bo determined. An approximation as to the thick-

ness required was arrived at by the substitution of

estimated values in the equation^^/ t - £ where t is the

optimum thickness and^^^is the linear absorption coef-

ficient calculated from the mass absorption coefficient

according to the relationship: \^- d^p(^

= dfPA(^)A f ^B^pB f PC(^---J

d being the density of the material, p the elemental

fraction in the compound and "^ the mass absorption coef-

ficients of the elements for the wave length of the

radiation used. As previously mentioned, only an approx-

imation of the optimum thickness was obtained hj substi-

tution in this equation as d and p had to be estimated,

their actual values being unavailable. This approximate

thickness was 0.20 riim. Past researchers had packed their

samples into capillary tubes made of glass but this was

ruled out because measurements on Pyrex tubes with wall

thickness just sufficient to permit careful handling

showed forty to fifty percent absorption of the CuK«i?(_

radiation. Plastic materials (materials with amorphous

patterns and impermeable to moisture) were preferred to

-21-

glass and in this respect, polyethylene tubing was first

used to make the specimens. The tubing ^vas filled with

a clay sample, the ends were sealed by squeezing the

plastic with hot tweezers, and the whole was pressed flat

to about 0,2 mm. thickness. This proved unsatisfactory

as the sample was not the proper shape nor thickness tmd

the resulting pattern was highly diffuse and distorted.

The size of the tubing was reduced and tightly packed

v/ith some of the c^ry powdered clay so as to approximato

a cylinder about 0.2 mm. in diameter. This improved the

sharpness of the pattern but did not remove the distor-

tion duo to its not being truly cylindrical. An attempt

v/as then made at rolling the pov/der between two glass

slides using Dupont Duco cement as a binder. The cement

also acts as a diluent, and if kept to a minimum, generally

does not affect the background of the diffraction pattern,

/ Q \

According to Schieltz^ ', "Vtoen Dupont household Duco

cement is used as a binder for the powdered montmorillonite-

type clay samples, the difjneter and sharpness of the

innermost lino in the pattern gives some information con-

cerning the identity of the adsorbed cations. Preliminary

observations indicate that a broad diffuse line represents

a mixture of cations, whereas c. sharp narrow line repre-

sents a relatively pure single cation". This method of

the tvro glass slides proved inadequate, however, as it was

too difficult to obtain the right si^e and shape of speci-

-22-

mcn. It \vas finally decided to try extruding the clay

using Duco cement again as a binder and clay conditioner.

This, of course, could only be applied to the dry samples.

An extruding device (see APPARATUS) was thereupon designed

such that the clay could be extruded into a thread-like

specimen through a 0.013" diameter hole. This diameter

proved to be too small requiring a long exposure time

and the hole was increased in diameter to 0,020", This

proved to be highly satisfactory as the dry clay, mixed

with a minimum amount of cement, was quickly and easily

extruded; the resulting specimen had the proper cylin-

drical shape, the right thickness and the right consis-

tency such that the resulting patterns were sharp, com-

ploto and uniform. The specimen also proved to be durable,

withstanding a great deal of handling without breaking and

could be easily reclaimed and filed away for future ref-

erence and use, A minimiim amount of sample (loss than

0.01 gram) produced several specimens two inches in length.

All the final dry specimens v/ore prepared for the x-ray

by this extrusion method.

The preparation of saturated clay samples for x-ray

diffraction proved to be a more perplexing problem.

Naturally, extrusion was out of the question. Other in-

vestigators had packed clay pastes into glass tubing of

various diameters sealing them with a waterproof cement

such as DoKhotonsky cement or plastocene in order that no

-23-

noisturo bo lost diiring x-raying. As previously mentioned,

glass has high x-ray absorption and also has a halo-like

diffraction pattern with long exposures. The use of plastic

materials was the natural recourse and polyethylene having

failed, it was decided to attempt the making of smaller,

rigid plastic tubing by coating an annealed copper wire of

the desired size with a plastic solution and removing the

formed tubing after the solution had dried. Polyethylene,

Polystyrene, Lucite and Duco cement were each dissolved

and formed on a wire, but cacli proved too difficult to

remove from the '.vire wlicn dried. Success was finally

achieved using ethyl cellulose dissolved in methyl ethyl

ketone and xylol^ ', The annealed copper wire was

straightened by a minimura am.ount of stretching and was

cut into two inch lengths. The dissolved plastic was

applied to the wires and allowed to dry in an oven at

SC^C. for 48 hours. After removal from the oven, the

coated wires were gently stretched thus breaking the bond

bctwoon the plastic and ^vire permitting the removal of the

tubes. Drying the plastic-coated wires for periods in

excess of 48 hours resulted in the development of a

stronger bond between the plastic and wire, making the

removal of the plastic tube too difficult. It should

also be noted that if the wire is stretched too much

while being straiglitcned, ductility is sacrificed and the

v;iro breaks whiles being drawn to permit removal of the

-24-

tubing,

A photograph of tho tubes is shown in Figure B , p. 8l,

Appendix,

The tubus made in this manner were cylindrical, the

right size and rigid such that they could easily be han-

dled. They wore filled by inserting one end into the hy-

drated clay sample and running tho wire, on which the

tubes were formed, through the tubes into the sample. The

wire was then pulled through in the opposite direction and

thus created a vacuum such that tho clay paste was drav/n

into position in the tubes. Possible leakage of tubes

was checV;ed by drawing the clay paste inside and then

pushing it out again to see if any escape of the clay took

place through the tube walls. Having boon filled with the

hydrate d samples, the tubes were scaled by pinching the

ends with hot tweezers or by dipping the ends into the

dissolved plastic and allowing the plastic to dry. Unfor-

tunately, neither method vms thoroughly effective as the

samijles di'ied cut n.fter 6 or 8 hours thus necessitating

ir.Lmediate x-raying after tho filling of the tubes, A more

effective means of sealing the tubus is yet to be found,

Tho first tubes made in this manner were formed on

No, 36 B?c S gauge wire resulting in a tube diameter of

0.127 mm. These tubes proved to be too small requiring

excessive exposure times and No, 24 B<?^S gauge wire was

then usf.^d .giving a tube dlametur of 0.5 r.im. This proved

-25-

to bo ideal as the patterns of the hydrated sarxples con-

tained in these tubes wore complete, sharp and uniform

requiring only three hours exposure, the same amount of

tine as was required with the final extruded dry specimens.

It should be noted at this point that the hydrated

sariplos wore obtained by boating the homo-ionic saturated

clays and the as received clays in a mechanical beater

with excessive amounts of distilled water for fifteen to

twenty minutes after which they were allowed to stand

until placed into the tubes for x-raying.

The dry samples were prepared by drying the treated

clays and the as received clays, grinding them with mor-

tar pnd pestle, passing them through a No. 200 mesh sieve

and drying them in an oven at llO^C. for 24 hours. Those

particle sizes passing the No. 200 mesh sieve proved to be

ideal for sharp, clear diffraction patterns,

PROCEDURE FOR OSTAlIIINa TIII^ DIPFRaCTION PATTERNS.

The x-ray spocimons of the dry and hydrated samples were

secured in the sample holder of the Dcbye Sherrer Powder

Camera (see APPiiRnTUo), the camera was properly aligned

and a three hour exposure was allowed. Kodak type^^x-ray

film was used in the camera as it gives the best contrast

for such vvork at a higher relative speed. The «C line of

the K series of Copper was used as the radiation as it

gives maximum penetration with a minimijira exposure.

The Dcbyo Sherrer Camera proved inadequate for taking

-26-

diffraction patterns of the bentonite samples as the inner-

most rin[^ occurred in that region on the film where the

hole for the spindle, opposite the collimation spindle, was

punched. In attempting to correct for this, the oC line of

the K series for Chronium radiation was used as the wave

length is about twice that of the corresponding copper

radiation and thus would increase the diameter of the inner-

most ring; hov/over, this also proved inadequate, a flat

cassette involving flat film which did not have to be

punched with holes was then used v;ith satisfactory results.

The same was feared for the illite patterns so the cassette

was used for five of them until it was discovered that there

was no inner ring for this pattern, whereupon the powder

camera was used. The lattice spacing of 1:aolinite is such

that the powder camera was ideal for kaolinito patterns.

Refer to the discussion for the flat cassette in Part III

(APPARATUS).

Standard darkroom procedure was followed in developing

the resulting diffraction patterns. A developing tank v»ras

provided with the proper developing solution, wash water

and fixing solution. The film v/as left in the developing

solution for seven minutes, washed for one minute, fixed

for tv/enty minutes and finally washed for thirty minutes

after which it v/as allowed to dry,

REiiDING Tliii pjiTT^RN .a;D COLIPUTIKO Till:; d-SP.iCIHG, The

radii of all visible rings on the patterns were read from

-27-

tho nogatives using tho rnoasuring instrument described

under APPARATUS and the d-spacings of the rings were com-

puted. These rings represent tho various families of

planes in the respective clay crystals with the innermost

rings for bontonito and kaolinite clays representing the

basal, not or d^Qi plane (see THEORY). The illite clays

had no inner ring (see RiiSuLTS AND CONCLUSIONS), The

method of computation for tho d-syjacings for tho patterns

obtained using tho powder camera, is as follows:

camera andfilm diffraction ring

x-rays

2TrT .. X360 " 26

2e = 560 3:

2 7rv

e = 22^;vr

Bragg' s law: n ">'-:-• .^d sin 8

d R n V2sine

Substitute for 6:

2s in

(

90 X ) wherein n-1, r-5.7 cm., X is^'r m.casured in cm. with vernier,

V s 1.54a'^ for CuKaC radiation,and d is the computed spacing inA^.

-28-

For the flat cassette:

diffraction ring

sanplo.

pinhole

film

1 ^x-rays

tan 20 = X, where ^ and S areS

measured and © is computed,

d s ^. where n - 1,

2sine> s 1,54A'^ and d is the com-

puted spacing in A°,

METHOD FOR IDENTIPI CATION OF CLiiYS, The d-spaclngs

for all visible rings arc computed and recorded along

with the relative intensity of each ring as determined by

eye, the most intense having, a relative intensity of the

order 1, the second n:;st intense having an order of rela-

tive intensity of 2, etc. These computed and recorded

d-spacin;'T;s and orders of relative intensity are then com-

pared directly v^/ith that A.S.T.M. IHDSX GiiRD which matches

most closely (see page i|2 , APFKIIDIX) , This method of

identification using A.S.T.ivi. Index Cards is known as the

HjvNA':'/f.LT method^ ^),

The other niethoo of identification is simply direct

comparison of the pattern of the unknown with other pat-

terns cf similar materials, and by direct matching or

similarity of patterns, the unknown is identified. See

RESULTS AND CONCLUSIONS for further discussion of iden-

tification procedures,

POSITIVE PRINTS OF Pi^TTERNS. Positive prints of

all diffraction patterns v/ere made on glossy printing

paper follov;ing the standard procedure for printing.

FART V

RESULTS iiND CONCLUSIONS

29.

RESULTS AND CONCLUSIONS

The clay particle size passing a IIo. 200 nesh sieve

and retained on a No, 325 mesh sieve proved to be the op-

timum particle size for obtaining sharp and complete

x-ray diffraction patterns. Those particle sizes not

passing a No. 200 mesh sieve were toe large giving "Laue

spots''^ ', scattered spots, v/hich disfigured the patterns

(see the pattern for the dry , as received bontonite).

Particle sizes much smaller than those passing a No, 325

mesh sieve were too small requiring excessive times of

exposure and giving patterns wliich vvore diffuse.

Use of the extruding device, v;ith Duco cement as a

binder, producing thread-like samples 0.020" in diameter

was successful in tnat the specimens were the proper shape,

size and consistency giving the sharp, complete patterns

which appear in. the APPJiNDlX, (See APPENDIX for prints of

all patterns).

The inadequacy of the use ci: polyethylene tubing and

of rolling the SiLrvplu between glass slides is illustrated

by the i\jspective patterns.

Ethyl cellulose tubing formed on copper wire 0.5 mm.

in diameter was the solution for mountijig the hydrated

samples, Sliarp, clear and undictortcd patterns resulted

from this method. Difficulty was experienced in effectively

-30-

seali2'i5 "tlio tubes and slight loss of moisturo occurrod

rr:aking it impossiblti to rotain the samples in their orig-

inally hydratcd stato. Dehydration occurred at a rate

too slow to affect the diffraction patterns.

The inethods used for proparin;-?, both the dry and

hydratod saxiiples are siriplo and quick and produce specimens

which are ca.sy to handle.

The oC line of the K series of copper radiation gave

maximum sample penetration v;ith minimum exposure.

The Debyc Shcrrer powder camera, 5.7 cm. in diameter,

was satisfactory for kaolinite and illite diffraction

patterns. The large basal plane, spacing occurring in the

bentonite could not be recorded using the powder camera

making necessary the use of the flat cassette discussed

\mder APPARATUS.

Of the x-riiv film.s available, I'odak Industrial x-ray

film Type K is the best for x-ray diffraction of cla^'-s as

it gives the maximum contrast with tlie highest relaLive

speed.

The interpretation of tlie diffraction patterns was

limiited to the analysis of int.jrplanar spacings only (see

pages 36 and 37 for a complete tabulation of these

spacings). No attempt at crystal analysis was made as

it requires extensive knowledge and experience in crystal-

logra]3hy.

In agreom.ent ^"ith the theory/ of the activity of ben-

-31-

tonite in adsorption reactions v;ith various cations and

with water, the diffraction patterns of the Rock River,

Wyoming bcntonite showed a marked change in the basal plane

spacing. The change in spacing varied in accordance with

the nature of the adsorbed ion, or ions, and v/ith the

degree of hydration. A comparison of the basal piano

spacings of the bontonito prepared by electrodialysis and

titration is as follows;

Ovon-dry: ":i ? Ca •> Na > K

Full2' hydra tod: H > Ma > K - Ca

Hot change (swelling) : Ila > K > Ca > H

For the bontonito prepa.red by KCl iisplacement o.nd poton-

tiometric titration;

Ovon-dry: PI > H > Ca > Na

Fully hydrat.sd: H> Ca )K and Na were not obtain-)ablc l'oi" j.-'ijRFons n,i_Lch are

Net change: (sv/cjlling): H > Cc ;explair.ed bolow,

f-i o\Barshad*' ^^' obtain^;d the following results for bentonitos of

difforont origins:

Ovon-dry (time and turnperaturu unknown): Ca > il > K > Na

rlydratod (immorsed in wator): Na ^ IT > Ca > K

Hot change (.rvolling) : Na > H > Ca > K

The dirrerencos \.n the above results are beliovod due to:

(1) different mt 'I'aodE used ici preparation of aamplo-s with

subsequent differanct- in quality of sa'-.plos, and (2) unlike

degrees of h^z-dratioii and dehydration. In strict accordance

v;ith thr: crys-L.a3 radii and the h;^drpted rrdii of the cations

-32-

involvod, the ordor of basal plane spacing should be:

Dry: Ca»K»Na (?H)

Hydratod: Na^K^'Ca (?H)

Throe J'easons why this order of spacing was not obtained

are

:

(1) The methods used for the preparation of the samples

arc open to question as no positive means of sample analysis

was undertaken, i.e., it was not known if the clays were

tr\.ily homo-ionic.

(2) It is doubtful if the complete dehydration of a clay can

bo accomplished without destroying the lattice structure

and if dehydrated ions can exist within the clay.

(3) Drying homo-ionic clays under the same conditions docs

not mean that each has the sane moisture content.

The innermost ring of a montmorillonite typo clay is

an indication of the nature of the adsorbed ion and the

extent to which the clay has completed its reaction with

water. A sharp ring denotes that the clay is principally

saturated with only one ion whereas a broad, diffuse ring

indicates sorturation with a mixture of ions. (See benton-

ite patterns, pages 57 and 59 ). With a complete set of

standards including such information as the origin of the

clay, method of preparation, and condition of moisture, it

Tvould be possible to more nearly establish the identity of

the adsorbed ion of a homo-ionic clay by comparison of

basal plane spacings. This could not be applied to clays

-OcJ-

saturatcd v/ith ions v/hich have tho sar.io valence and hy-

dratod .;..nd dehydrated radii such as Ca'^'' and r.ig'''^o

Sinco such standards are not presently available, x-ray

diffraction cannot be used to establish definitely tho iden-

tity of the adsorbed ion or ions.

If the reaction botv/eon bentonite and "/ater lias not

reached completion, i.e., the clf;.y is in the process of ad-

sorbing Vv'ater into its lattice structure, the innerraost ring

appciars broad and diffuse.

Due to the similarity in the d^^^^-^. cpecings of the ben-

tonite scnpl'.s x-rayod, it is believed that they were all

predominantly lrydro^,en bontonites ^vith varying decrees of

the hydrogen ion rupl3.ced by the other respective ions,.

ixic i'la'-^ K .--p^.-^ Ca-J-I bontonites h'-.d basal plane spacings

'^,'hich corresponded more nearly to the spacing for the hy-

drogen bentonite than to the spacings as establislied by

other investigators(^) (^^)^^^^(12) ^^^ bentonite saturated

with the oth'-r ions,

Thii interplanar spacings of kaolinite remained constant

showing that the lattice structure of kaolinite is such that

ions and rsioleculos of water r^.re adsorbed on the surface of

this clay rather than v>^ithin the structure itself,

T/ie illite v-'Mple used had no inner ring indicating

thr.t insufficient illite was present in trie naterials. By

direct corriparison of the diffraction pattern of this ria-

terial, it was found to be similar to the pattern for an

-34-

( n \

lllltQ~[^lfuic:'.i\tn. nhrilf, iiP! i'o-and in rot oronco ^ ''

' .

Tha Hanav.'alt '.nothod Tor the idontifi(iation of clays

fron thDir diffraction patterns involves the use of ArS»

T.i'I. card indices wherein the intorplanar .spacings and

relative orders of intensity" of the unknov.Ti are conparod

vv'ith those appearing en the index cards. This riochod is

illustrated in fi glares B and B , pages l\.2 and 60 ,

but is of limited value as the nui7iber of index cards for

clay .ninerals is insufficient and the cards lack such

necessary inf orn;ation as the origJ.n cf tlio clay, condition

of moisture, and ion content.

The method of direct comparison of pcatterns of un-

knov.rns 'vith pattor^is cf known mat'.;ri;.ls is a quick and easy

method of determining tno typo of clay mineral. Excellent

patterns of kno:vn clav minerals which could bo used for

dir'^. ct Goriiparison are shown in figure 6 , page 80 •

The possible sources of error in the x-ray analysis

of clays in this thesis are:

(1) Uncontrolled moisture, both dry and hydrated,

(2) nicroscopic irrcgulnrities in shape of specimen which

may create slii^ht djist^rtlons,

(3) Possible) film shrinkage - considered negligible due to

careful developing.

(4) Sample, when mounted in the pov/der camera., Liay deviate

from a vertical straight line thus offering possible source

of distortion.

-35-

(5) Errors involved in neasuring distance froiri center of

sariplo to surface of filn in flat cassette.

(6) Hurian errors involved with use of measuring device for

radii of diffraction rings.

X-ray diffraction is of inestimable value for the

study of clay minerals for the following reasons^^^:

(a) The technique required to make x-ray patterns is

relatively simple,

(b) Since tliis method is indostructivc , tiie sample can

bo used for further studios by other methods,

(c) Only a very small amount (loss than 0,01 of a

gram) of the material is needed to make up a sample.

(d) Only a limited accuracy in m.easurom.cnts is neces-

sary when making a qualitative analysis,

(e) A file of diffraction patterns constitutes a per-

manent re cord

,

It must be noted, however, that x-ray diffraction is

not a p£inacoa for all problems and its utility is usually

considerably enhanced if it is used in connection with

other methods, especially differential thermal, chemical,

and spectrographic analyses. This is particularly true

for the invc^stir^ation of complex mixtures because at the

present time, an appreciable amount of a constituent, from

one to thirty percent'-'-''"'), must be present in a mixture

before its presence can be detected. Use of improved

techniques shoul'i do much to correct this situation(8)

,

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Part VI

RlilCOKMlCKDATIOriS

-30-

RKCOKMJNI^ATIOIJS

In ordor to fully utilize th<; method of x-rqy diffraction

for tho analysis of clay minerals, it is important that a

complete file of standard diffraction patterns be established

for all the natural minerals under tlie montraorillonite,

illito, and l:aolinite gi'oups of basic clay minerals. Each of

tho minerals constituting! the file of standard patterns

should be x-rayed in its natural state. Also the bentonites

and illitos should be carefully tx;ated such that each is

purely saturated with single types of cations in tho Hoff-

meistor series. They can then be x-rayed producing complete,

clear and uniform diffraction patterns forming a necessary

part of the file of standard patterns. Further v\,'orl: should

also be done in carefully treating these clays such that

varying percentages of different ions are adsorbed within

their lattices. It is fully realized that such work would

be extremely difficult, but at the same time, it is con-

sidered necessary for a complete file. Included with each

of the above patterns should bo the following important

information: origin of clay, method used for ionic satura-

tion, quantitative and qualitative analysis of clay, con-

dition of moisture giving percent hydration, and tabulated

intorplanar spacings and orders of relative intensities.

Such information could be obtained and checked by the

advantageous uso of other motliods of clav analysis including

-39-

,c,p,-o.tr'ococniG tstudlos, dificz'ontial thonnal analysis, op-

tical analysis, deriydration curves, and quantitative and

vqualitativo chemical analysis. Several of the foregoing

methods of analysis should always be used in conjunction

with x-ray analysis of clays, '"/ith a complete set of

standard patterns as outlined above, x-ray analysis would

bo a quick, accurate and easy method for determining the

type of clay, structural classification, nature of adsorbed

ion and positive identification, ^Vithout the prescribed

information which should be included with eacli pattern, the

file of patterns would be rel-itively worthless.

An interesting and valuable, study would be that of

determining the swollinx characteristics in detail of ex-

pandin.^ lattice-type clays by care^fully controlled methods

for successive def^reos of hydration, using x-ray diffrac-

tions to detect and record the pro^^ress of swelling of the

clay from its "dry" state to its completely hydratod state.

This could serve as an informative insight as to the nature

of the swelling of clays due to hydration.

Associations of montmorillonito i-'ith organic materials

have been studied from time to time and it is recommended

that further research be conducted in this field as it has

already resulted in important discoveries relating to moro

accurate and detailed analyses of clays by x-ray diffraction^ ^^ )

The tecimique of x-raj diffractions a;; developed in

tills th(;Eis is conGJdered higlily satisfactory and easv to

-40-

dnp?:.icn.te ; howcvor, it is rocoinrnandod that fu1;urG investi-

gators in this work devise a ••loro offoctlve rnothod for

sualin'.^ tlif; •wio.ll plastic tubes so that no escape of raois-

ture vvil3. occur from the hydratod clay samples , Such future

invcsti ;atcrs sliould also become inore farailiar with the

science of crystallography thereby putting theinselves in a

more advantageous position to extract information, in

addition to what was brought out in this thesis, from the

diffraction' patterns.

Calibrabion of the powder camera using a known stan-

dard such as NaCl 'ind the use of equivalc;nt radii for the

calculations of d-spacings rocorded on flat cassettes are

recommended for tlio elimination of any possible sources of

error duo to a non-vertical sample mounted in the powder

camera and duo to iiiaccuracies involved in measuring the

distance from the conte->^ of the- sample to the surface of

the film in r . flat c a s s e 1 1 e

,

P.JiT VII

APPENDIX

f 1

Figure A. Bontonlto pattern obta5.nod by use of polyethylonotubin-^ mounted in powder camera. Note irregularity anddiffuscness of pattora. No inner ring appoars en right sidein area of hole«

Fi.r^urc B. Bentonito pattern using extruded dry sariple mountedin powder cariera. Note inprovorr'tont over figure A in sharpnessand uniformity of diffraction rin^s. No inner ring appoarsin area nf hole.

Figure C. Bontonit..; pattern using j;5lass 3lidr;S to roll pow-d'jrod SMriplvi nixed with Duco C(ir.ient, Note irregularity anddiffuseness -^f pattern.

Figure D. Bentonito patturn usinnj th(j oC lino of the K s-^riesof Chromium radiation. No inner ring o.ppears in area of hole*

i

RingNo.

TYPICAL DIFFRACTION PATTERN OF BENTONITE

A.Tiock River, Vifyoming Bcntonite: As receivedand oven dried at llO^C for 24 hours.

I

Radiusin cm.

0.6951.9152.1452.6452.9853.1054.927.165

Order ofIntensity

1426

3578

mterplanarDistance (a°)

13.385.004.503.743.363.252.281.82

d il2. 214.4^3.1 -

Viii.oo|o.5qo.n(

-"i1

40 20 ' 81

' Bentonite

;

'

z =

.Ao3 ^0* '^O"

A= Cai Da

' n= Ws Gs

dm ao

V= .708

12.204.483.142.561.68

I/I 1

1.000.500.200.150.05

1.498 0.15

1.2881.250

0.030.03

d3nA°7.=.7Ce

i/r

^. A.S.T.M. Index Card for Bentonite

Remarks: Origin, adsorbed ions and moisturecontent of a.S.T.M. Bentonite unknown,

i

43

Rinn; (Radius|Ordor of

i t

No, jin cm .j

Intcnf^ity

1 _ i

2 - i

5 2.155 i 14 2.1^95 ^ 25 ^^ )

6 -

7i

8 ^ *

9 Ij..l9 31011 i

!

12i

IntcrplanarD:

:::i=

r^'i stance (A*^) i

1^.503.93

2.56

Clay Typo: BENTONITE

Adsorbed Ion: As-received

Romar]:s: Fully Hydrated

44

t:I Rinn; l Radius

No. m cm.Order ofIntensity

IntcrplanarDistance (a'^)

1

2o4

56

7

89

101112

0.60i

1.93 !

2.15512.39 i

2.6I1.5j

2.995I

3.65I

i|-.19j

7.2I

1526

k3

8

..x..^-.

15.39I^..96

I1-.50

3.7I4-

3.36

2.862.56

2.121.81

Clay Typo: BEIITONITE

nAdsorbed Ion: _^__

Romar 1 : s : Slectrodialyzed, Ph Oven-dpy

45

RingIRadius

{•JO, (in cr.i.

Order ofIntensity

j

Intcrplanari Disti'-nce (a*^)

1

25'-X

55

7

89

101112

2.11].

2.59

i|.l8

i

L

1

2

k

20.3

3.36

2.57

X:

Clay Typo

:

BENTONITE

Adsorbed Ion: H^

Romarics: Electrodlalyzed, Fully Kydrated

4G

Rinr^ iRadius Order ofiJO,

1

234

56

7

89

101112

I in cm.j Intensity

i

0.67I

! -I

i

2.11^.I

; _ I

i 3.0i+I

i

:I

!

I4-.17 I

I

i

1

2

k

3

i

IntcrplanarI

i Distance (A^) \

13.69

3.32

2.58

Clay Typo: BBITTCNITE

Adsorbed Ion: Ca

Remarks: Electrodlalyzed, Oven-dry

4r

Rinr^ (Radius I Order of]jo . 1 1 n cia, i Intons i ty

1

234

5

6

7

89

101112

0.1|.8

2.165

3.03

i k.22

1

2

3

InterplanarDistance (A^)

19.2?

3.33

2.56

Clay Type: BENTCITITE

Cai-idsorbod Ion: .____

Homar I : s : Electrodialyzed, Fully Hydrated

48

\Rins Radius Order of Intcrplanar |

: Ho

,

in cm. Intensity ^istance (A°) i

1 0.701 1 13.25

2.171

12 k'k^

5

5 3.00 3 3.357

8 3^66I|..22

i i2.8i|.

10 - 1

J

' 11 - 1

12

„.J

Clay Type: B2NT0ETTE

Adsorbed Ion: Ua

Remarks: Electrodialyzed, Oven-dry

i

49

Rinr^ iRadiUv<5 i Order ofI I

No, lin cm. j Intensity

1

2o4

5

6

7

89

101112

jIntcrplanar

i Distance (A^)

I

0.k72i!

-'

i

I

2.17I

I 3.02 I

I4.19

i

l-Ll,

1

2

3

k

I

1945

3.3I1-

2.56

Clay Typo: BENTONITE

NaAdsorbed Ion:

Romarks: Electrodialyzed, Fully Hydrated

50

Rin^ iRadius i Order oflio , j in en.

| Intonsityi

InterplanarDistance (A^) i

1

^— r-

—

' 0.7021

1 13.111-

L

' 2 j

o4

2.1781

2 It-.i+S

5 1—1

6

7 3-ii i k 3.251

8 __

9

1011.203 1 3 2.56

11 i

12

Clay Tyi30 : BENTONITE

Ad sorb eci Ion: K

Romarks : Electrodialyzed, Oven-dry

I

bl

Ring jRadiusj

Order ofNo. tin cm.

jIntensity

i

Intcrplanari Distance (A^)

1

254

5

6

7

89

101112

Io.[^8 !

i

-j

I

2--^i

i

i k'2.

.^.L

1

2

Clay T:,'Pg: BSIITCNITI

KAdsorbed Ion:

Remarks: Electrodialyzed, Fully Hydrated

bZ

TRins i Radius {Order ofNo. lin cm.

j Intensityj

Interplanar1 Distance (A^ )

1

23

0.672

2.16

T

5 ~i

6 3.01 1

VI

8_ 1

9 1+.21i

10 1

11 i

1

12 7.2j

1 13.79

2 k.k^

3 3.3k.

k 2.56

5 1.82

Clay Typo: BENTOrTITE

Adsorbed Ion: H

Romarlcs: HCl Displaced, Oven-dry

53

Rm^ iRadiUv"?

I-jO. jin cm.Order ofIntens ity

InterplanarDistance (A°)

1

2o

6

7

89

101112

i0.1^55

I

i-

I

I2.11^

I

I I i

1 2.96 !

i"

!

1

1

2

3

k

...1

20.3

il-.52

3.37

2.59

Clay Typo: B2NT0HITE

Adsorbed Ion: E

Rom p r>ir s : KGl Displacement, Fully Hydrated

54

Rin3 Ratiius Order of Intorplanar j

No. in cm. Intensity Distcince (a^) 1

' 1i

0.682 1 13.622o4r:

1

\2.17

: 2.295mm

3k

i^-.^6

O

6

7\ 3.025!

-

2 3.32 1

1

8

1 9: 10

i

1

i -I J4-.22

I]-.^85

I|.98 f

17.2)4.

.L ..^.J

5786

2.562.I1J4-

2.261.81

Clay Typo: BENTONITE

iidsorbed Ion: ;a

R o/m « r> I r s : HCl Displacement, Oven-dry

5^)

I Rinn; jFiadius j Order ofNo.

I

in CM.jIntensity

IntcrplanarDistanc e (A*^) i

1

234

5

6

7

89

101112

2.165I

3.013

[{..21

12

3

Clay Typo: BENT NIT]

Adsorbed Ion: Ca

Rom p rlf s : HCl Displacement, Fully Hydrated

56

RingIlo

.

iRadius j Order ofijn en.

IIntensity

jInterplanar j

i Distance (A°) i

: 1 0.70i

12 1.9a

!

2.16 1

5o 24

i

5 2.675i k

6 3.01 i 37

8 _ i

i9 I1.22 1 6

i 10 » 1

111

i

! 12i

1

I.

7.2i|i 7

13.1+9

3.693.33

2.56

1.81

. 1

Clay T^-pe: BEITTONITB

Adsorbed Ion: Na

Hcinwri's: HCl Displacement, Oven-dry

b(

Rins i Radius i Order ofj

Intcrplanar5 ,,

jin en.1 Inttmsity j Distance (A° )

' 1

4

5

1 1.91|

1 2.175

12.78

-1

1

1

j

1

12

3

i

i k'%

i k.OO! 3.581o

7

89

10' 11

3.18

1+.75

1

i

i

i

7

968

1

3.19

1 2.61).

! 2.3fi-2.111.

121

1

1 I

Clay Typo : BENTOFITE

Adsorb 6d Ion:

s: HCl ]

Na

Romar]: Displacement, Fully Hydrat ed

58

\Hins Radius i Order of

i

Inttjrplanar'. ho. in cm. t Intensitv- i Dislbance (A°)

' 1 0.67 T 1i 13.89

1 2 1.91^. 1i^

t

l]-.95

. 3 2.17{ 2 k-M

4 2.67 i 6 3.715

1^ s

t6 3.01 1 3 3.357 ~

i

1

8 3.7 ! 7 2.829 l|..22

j 5J

2.5510 _ j

1

11^ i

1 12 7.li^-! 8

i

1

1

1.81^.

Clay Tyiic : BENTONITE

Adsorboci Ion: He K

Romarlrs ! KCl Displacement, Oven-dPY

59

Ring i RadiusjOrdor of

No . {1n cr.i . j Int o n s 1 1^,^

IntcrplanarDistan c e (a^ )

1

23

o

7

8

1.99

2.77

91

3.8910

1 5.17 ;

111

-

12I

-

1

2

h3

Clay Type

:

BENTONITE

Adsorbed Ion: K

Rom

»

r^v s ; HCl Displacement, Fully Hydrated

TYPICAL DIFFRACTION PATTERN OF I^OLINITE

A. Georgia Kaolinite: Saturated with Ca'*"*' ionand oven dried at llO^C for 24 hours.

bU

! Ring : Radius Order of Interplanar|

iNo.

1in cm. Intensity

1

Distance {A°) 1

1 'l.221 ^

- .„..

7.21\ 9 ,'l.99 4 4.43

i3 '2.115 6 4.18

J

^ 2.475 2 3.585 2.64 8 5.355S 3.475 7 2.568'7 5.575 7 2.508 3.825 5 2.349 3.895 9 2.297

10 4.425 11 2.03511 5.475 10 1.66812 6.195

1

5 1.49

d fe.59

^1I

1.00

12.5 10

'7."2J4.45|d ini >=.708

O.SO 0.80

10

Al2Si205(0H)4Kaolinite

Z =

Ao= bo= CosA r C 3

D =

n w - e s

7.204.45

'

4.304.204 . 04

I/I

0.800.800.640.480.32

din ^> = .7CE

TTso1.671,54

3.59 I 1.002.56 t 0.482.502.341.99

1 1.901.85

0.480.800.320.080.08

i/i:

0.080.400.16

1.490! 0.561.310 0.08l.S9j0.161,24010.16

A.S.T.M. Index Card for Kaolinite

Remarks: Origin, adsorbed ions and moisture

content of A.S.T.M. Kaolinite unknown.

Gl

i

Ring;Radius Order of

No, j in cm. 1 Intensity

'' Int[ Dis

erplanartance (ii°)

V.18i1 1,225

;2

2 ;

1

1

1

•

1

3 ! 2.115i

1 1 4,18

4 2.455I

5 5.61 1

-.--.. -^ -1 S.461

2.58i !

Q |_3.56

I

1

1 2.51

7 ;

3.81 1 5

"1

2.35 j

i

• 8 ; 4

'

j

.__,9_„ 1 ^50 »— 1

1

2.00 J

10 1

-- j

1

1

.__ii 1_..-zzj:---

!

1

12 6.2n 1.49

Clay Typo: KAOLINITE

Adsorbed Ion: AS-RECEIVED

Remark s : ven -dr

y

%

G2

! Rmn;IRadius j

Order of! in cm. I Intonsity

2,00 i

\ Interplanar !

IDistance (a°)

|

J7,^12

I

4,41 i

i- ^ i 2.48 j

4.17_

5.57

3.49

! 5.55

': 5.85

k-'.oo

8_

,11.

12

3.91?L__..i..._ ...J.

4.54

5 . 50

6,221

^54_

2_,30_

1.98

.l.?JS_

1.49

I

i

H

Clay Type: K^OLOITE

Adsorbed Ion: AS-^iiCEIVED

Remarks: Fully hydrated

63

j

Ringi

No,

1

IRadius 1 Order of

Im cm.

"F-i Intonsitv

1.22 ! 2

\ Interplanar !

\Distance (k^) !

f 7.21 !

2.455i

Jt-l

!

-5_i

;.-_._.6...

!,. 7_,

i 8

I

:io_

i

i 11

I 5.46t

3

6

4.18

5.59

.56 I

(

1 T-5.85 i

: ._M1_.I.

4

5

2 . 58

2.51

-L...

•-

1

6.13

2.55

2._32 _ j

1.49

Clay Type: KAOLINITE

Adsorbed Ion: H

Remarks: Oven-dry

64

I

Ring: No

,

2

A

; RadiusiOrder ofIntonsitym cm.—

^^^^-F- =d=^i

\1.255

' 1.995 i

1

5

' Interplanar5Distance (A°)

;7.13

t

' 4.42i_

*__2._ie5

! 2.475

6

—;-3,475

I"—

,_-6

8.

jLO^

12

;3.57

'

3.815

j_5.89

j4.525

5.475

-.4—

.

6.185

2

7

7

4

8_

9

9

5

.4.19.

3.58

2.57

2.50

M-2.55

_? •_3P..

1.99_

1.67

1,49

--

!

i

i—

n

Clay Type: KAOLIMTE

Adsorbed Ion:'^

Remarks: Fully hydrsted

G5

RingNo.

IRadius j Order of

Intensity:i=.

^ Interplanar !

\Distance (h^) \

\ 7.15 i

2.00 4,41

3 ;2.11

i6 f 4,19

4 12,485 j 2 5,56

5 ! 5.43 : 7 2.57{

6 i_ 5.57

7' 5,82

7 1 2,50

4 !

1

2,34

8 : 5.395J_

8 2^50.. ..J

9^ . i. 4.63 1 9\ 1.99

i

ip__ [5.08J

9

1

1.79 j

11' 5.48

.-L.^"-. -._ 1

-- i

1

_ . ..4_

1,671

.12 : 6,20 5I

1,49!

Clay Type: KAOLIMITE

Adsorbed Ion: CA

Remark s : ^'v 1 ly h;y dra t ed

66

!Ring

INo.

; Rad5-usI

Order of• in cm. ! Intonsit^r

.:__ ii^ss J __ _ 1

i2.02 i 3

\ mterplanarIDistance (A°)

7.13:„-..-^

4 . 37

\ 3 ;2.135

; 6,

4-13j

i ^i

2,50I

2 3.54Ii

! 5 !

S,515: 5 2.54

1 6 3.b05j

5 2.48

i 7 3.865j

4i

2 * 32

'<

B 3.93 12,2@ j

! 9 L ^•^'^!

1,9S

|_ 10 1 5.125j

3 1.77i

1 i

I 11 5.525; 9 I 1.65 1

i 12 i 6,235 j 7 1.48 !

Clay Typo: KAOLINITE

Adsorbed Ion: NA

R eiTiark s : v en-dry

67

RingNo,

IRadius

j Ordor of\ Interplanar

I

in cm. ! Intonsity;Distance (ii°) I

Clay TyiDe: KAOLINITP.

Adsorbed Ion: K^

Remarks: Fijilly hydrvqtfd

68

jNo •

;Radius

j Order ofIin cm. I Intonsitv

'

j __ , ..."..

: Intorplanar !

(Distance (A°) i

t-

4

._^

.,-6..

JLO_

12

l.fS

2.085

7.15

...4-

_5^

\

2̂.51

4.22 i

.4^5— J

3^55 1

k

.-.. ._4-.

5,85i

i

[.

2.33

6.20 1.49

Clay T3'pe: KAOLIlvTTE

Adsorbed Ion: K

Remarks: Oven-dry

G9

RingNo,

.1.

3_

.A

5

I

Radiusin cm.

4Order ofIntonsity

1.^3 5I

2.01i

1

2.1

2.49

3.5C

_6

7

3j. 59___ !

3.84 1 4

8_

9

3.91!

-L-4.56

!

101

j

~

11i 1 -

--..12_ \6.23

I

5

! Interplanari

Distance (A°)

-4

7.13

4.3:

4.17

3.55

2 . 49

2.33

2.28

1.98

-^

1.48

Clay Type: KiVOLINITS

Adsorbed Ion: i^

Remarks: Fully liydrated

70

TYPICAL DIFFRACTION PATTERN OF ILLIT2 BEaRIWG SHALE

Illinois Illite Bearing Shale: As receivedand oven dried at llO^C. for 24 hours

Ring Radius Order of InterplanarNo. in cm. Intensity Distance (A°)

1 1.99 2 4.432 2.095 3 4.223 2.415 9 3.664 2.680 1 3.30

5.505 4 2.556 5.035 5 1.8047 6.03 6 1.5288 6.20 8 1.499 6.85 7 1.362

10 - ..

11 .— — ..12

i

1

~ "• ^

71

No.i Radius i Ordor of

ir.'uiIntens ity

1

234

5

1.9052.1452.272.552.99

o

7

89

10

4.395.425.057.10

11 _ __ _

12 _ _ —

..'Li"

2

41

6

i Intcrplanarstance

T lAll

5.034.514.283.723.36

2.482.142. CO1.82

Clay Typo: ILLITE

Adsorbed Ion: .i3-iu:ci:iV3:D

Romarif s

;

?ully hyirated

RingNo,

.1.

2

IRadius

+m cm.

Order ofIntensity

1.395 I

f

! Interplanar!Distance (A^)

•^.42

3.

4_

_5_

2.05

£.36

4.31

! 2,525j

8_

10

4. r-

7:. . 38

b.OO

15

5.92

6.08

-f-o

8

1,81

1..55_

1.52

6.72 1,38

Clay Type: ILLITE

Adsorbed Ion: H

Remarks: Oven-dry

73

Ring ! Rad5.us' in cm.

Order of\ Interplanar !

Intensity | Distance (a°)j

2.

7.!

r

4 , on

.26

8_

_10_

13

' 2.64 J 1

__!3.455 I 2_

- .__ - 5 .62j ^_

__l _ijdi^__4_ -__^

2.58

2.47

_4.555_^

4.99

5.97

_6._15

3.77

.4--4

7

5

3

2_^5_

_1_.>99_

1.82-A

1.54 j

1.5!

1.58

Clay Type: ILLITF

Adsorbed Ion:

R oinark s : F"" 1 11y 'ay dr.-) ted

74

\Kins

^ Ko,

12o4

5

5

7u

910111213

Radin

ius I Order ofcm.

iIntensi ty

2.

2.

2.

4.

4.

1526

i 5

99 I

145 i

41i

45 !

125 I

7.15i

4

1

3

j

Intcrplanari Distance (A^ )

4.504.29

3.362.592.472.141.991.84

._.,x., _^_

Clay Type:

Adsorbed Ion:

Romarlrs

:

ILLITECA

Oven- dry

75

I Rins!

"~1

Radiusj

Order of Intcrplanar ;

\ Wo. in cm,j

Intonsity Distance (A^) i

! 1 1.895 6 5.062 2.13 2 4.545 2.25 4.324 2.635 3 3.755 2.96 1 3.396 4.12 4 2.607 4.385| 10 2.488 5.48 i 9 2.149 5.11

111 1.99

1 10 7.11 ! 8 1.821

^^ —

12 — — .•..

13 i _i J[ ^_^ i_ m V •— .w. ....,«• ... .1 « « . .

Clay THrpe:

Adsorbed Ion:

Remarks

:

H.-^ITE

j\ii ly Iiy ar-a ted

76

Rinc

h-No,

i

.1

i 21

1

1

1

3

A

IRadius

Jin cm.

1.9

I

Order ofi IntGnsity

Interplanar !

Distance (A°)|

4.43

2.08L

4.24•T

5 ; ~ —J . „.

6... . L 5.49 !4

!

i T1

8_

_10_

13

5. 045.,._L...

5.02

6. IS

5.82 7 1.37

1.801

1

1.53j

1.49i

Clay Type:

Adsorbed Ion:

Remarks:

luLITE

KA

OYea-'lry

77

Rin3No,

jRadius Order oftin cm.

iIntensi ty

j

Interplanar !

i Distance (A^) I

1

234

56789

101112

2.145!2.265

2.995i4.159

7.13 i

3

1

4

4; 524.31

3.362.59

1.33

Clay Typo

:

Adsorbed Ion:

Remarks

:

"ully hydra ted

78

RinjWo,

RadiUvSin cm.

Order ofjIntcrplanar

! Distance (a'^)

1

234

5o

7

89

101112

i

1.90! 2.125

j

2.235• 2.63

I

2.965I

^.105

I

4.39 j

j

5.44 !

i 5.115I

* 7.115 I

o

2

5314

109

127

5.034.554.343.753.352; 602.482.141.991.82

Clay Type:

Adsorbed Ion:

Romarl's

:

ILLITE

Oven-dry

79

InterplanarDistance (a°)

j

15 6,77b 1.58

Clay Type: ILLITE

Adsorbed Ion: ^

Remarks: FuIIa/ hydrsted

80

81

Figure A. Extruding device shov/lng extruded sample

mm

Figure B. Plastic capillary tubing showing:Tube with forming wire partially v/ithdrawn.Plastic tubingPlastic tube, filled and sealed by heat.

Tubes are of 0.5 21m inner diameter.

82

V-»

.?

r

Figure A. Bradfield three cell electrodialyzer

Figure B. X-ray tube and pov/der camerasleft - Flat cassette and baseright - Debye-Sherrer powder camera

83

\

V

I

'r

L^'

^

r

•J

^k Vi

^:?

'^ Kkl f > (.-,

?i

-)

•^<

>^ ,^

q'f^ k

"0 M.^^ <>

-^

^ ^04-.

^s^NV)

O

SAMPLE COMPUTATIONS

Ijcbyo-Shorror powder canora:

84

2sin(9££)Vr

where n - order - 1

> s wave length r 1.54 A'^

Z z radius of diffr;iction ririfj; in question

r z canera radius - 5.7 cm,

d 3 Intorplanar spacin^j in A^,

for as-received Kaolinite - oven dri^j: -,^1,226 cm,

- 7.18 A°.1 1 X 1.54 A^^ool =

2 sin( 90xl.;:^'P5 cm . ^

^x 5.7 cm.

Flat Cassette Camera;

d T - ^ >-

2 sin (tan-1^)S

whore s - distance from sample to film :; 6,0 cm.

For as-rocoived Bentonito-oven dry VqoI ~ 0,695 cm,

c] ^ _ 1 X 1.54 cm,^ool =

-8

2 sin (tan-1 0«695 cm. x

6.0 cm.

= 15,38 aO

I

85

REFERENCES

1. Moycr, C.F., "The Dirfraction of Lit^ht, X-rays, andIlatorial Farticlos", First Edition, University ofChicago Press, Chicago, Illinois, 1934.

2. Jonkins and ''/h.ite, "Fundamentals of Physical Optics",First Edition, Now York, McC-raw-i-Till , 1937.

3. Bragg, 'V.L., "Atomic Structure of Minerals", CornellUniversity Press, 1937,

4. Hanawalt, J.D., Rinne, H.\7. , and Frevel, L.I'I. , Ind.and 'un;2» Chor.istry, Anal. Ed., vol. 10, pp.457ff., 1938.

5. Loddcsol, Aasuluv, "Factors Affecting the Amount ofElectrodialyzable Ions Lib orated Fror.i Some Soils":Soil Sci. Soc. An. Proc, vol. 33, op 187-211.

6. rilcav/l^y, E.J., Unpublished notes on Clay Minerals.

7. Buswell, A.'^I., and Dudenbostcl, i<.F., "SpectroscopicStudios of Base-exchange Materials": An. Chen. Soc. Jour

.

,

vol. 65, Tip, 2554-2558.

8. Schieltz, LJ. Cyril, "X-Ray Analysis", S^Tiposiun on Sub-surface Creological Methods, Second -]dltion, ColoradoSchool of Minos, pp. 211-240.

9. Ennis, '"'.D. and Hufft, J.C., "An Investigation of theEffect of Ionic Substitution on the Attcrborg Plas-ticity Constants of Certain Clay Minerals", RensselaerPolytecimic Institute, Troy, t;ew York, 1951,

10. 3eu, Iv?'rl E., "Iniproven(;nts in a Method for PreparingPlastic Fowdor-Sanple Capillary Tubes", The Review ofScientific Instruments Monthly, vol. 22, Ho. 1, p. 62,January 1951,

11. Mull, A. ''/., "a New Method of Cnv^mical Analysis", Amer-ican Chemical Society Journal, vol. 41, pp". 1168ff., 1919

12. Barshad, J., "The Effect of the Interlayer Cations onthe "iJxpansion of the Mica Typo of Crystal Lattice",American Minerologist , vol. 35, pp. 225ff, 1950.

13. Brocky, S, , "F,T I. News'', Pittsburgh Testing Labora-^. c^ ri .-.: s , P 1 ^ t s I. u:" gh'. , F ( ;nn sy 1 vani a

,

86

14. Aldrich,'T

I

Aldrich, D.C, Hcllrian, ?1.:t., .-.nd Jackson, I,;.L.,

'Kydratlon Control of Nontnorillonite as RoquirGd forIts Identification and Estimation by X-ray DiffractionI'lethods", Soil Science Soc. i-un, Proc, vol. 57,pp. 215ff., 1944.

15. Bradley, ^7, P., "Diagnostic Criteria for Clay Minerals",T'le Ancrican Minerologist , vol, 30, pp, 704ff, 1945,

16. Hendricks, S,3., Nelson, R.H., and Alexander, L.T,,"Hydration Mechanism of the Clay I-ineral ?^ontraorillonitoSaturated with Various Cations", aiti. Chem. Soc, Jour,,vol. 6?., pp. 1457ff., 1940.

17. r.ac'Jwan, D,II,C., "Goriplexes of Clays with OrganicCompounds", Tran. Farad. Soc, vol, 44, pp. 349ff,, 1948,

18. MacE^van, D.M.C, "T'lo Id(.3ntification and •']stination of theMontriorillonite vroup of Minerals '-vith Special Heforencoto Soil Clavs", Jour. Soc. Caen. Indus,, vol. 65,pp. 208ff., 194S,

10. Marshall, C'l. , "Colloid Clienistry of tVie SilicateIv;ino ral s ^'

, Xc adeni c Press In c . , lie v; York , 1949,

20. Jackson, ?J.L. and Hellnan, II. N., "X-ray Diffraction Pro-cedure for Positive Differentiation of MontmorillonitoFrom Hydrous I.Iica", Soil Sci. Soc. kh. Proc, , vol. 6,pp. loSff., 1941.

21. Ross, C.S., und Ecndricks, Sterling 3., "Ilinerals o£ the'./lontnorillonite Group", i:ioological Survey Professional ^

Paper 205 3, U. S. Preological Survey, 1945.

I

The!DlSl

Tl

of

15620Thesis DearthD188

The identification and in-

vestigation of the expansioncharacteristics of clays "by x-raydiffraction.

r. 'J.

U. S. Naval Postgraduate School

Monterey, California