Scholars' Mine Scholars' Mine

Masters Theses Student Theses and Dissertations

1951

Mineral composition in relation to particle size for a Missouri Mineral composition in relation to particle size for a Missouri

plastic fire clay plastic fire clay

John Edward May

Follow this and additional works at: https://scholarsmine.mst.edu/masters_theses

Part of the Geology Commons

Department: Department:

Recommended Citation Recommended Citation May, John Edward, "Mineral composition in relation to particle size for a Missouri plastic fire clay" (1951). Masters Theses. 2992. https://scholarsmine.mst.edu/masters_theses/2992

This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact scholarsmine@mst.edu.

MINERAL COMPOSITION IN RELATION TO

PARTICLE SIZE FOR A :MISSOURI PLASTIC FIRE

BY

JOFm EDWARD MAY

A

THESIS

submitted to the faculty o:r the

SCHOOL OF MINES Al\Jl) METALLURGY OF ·THE UNIVERSITY OF MISSOURI

in partial filf1llment of the work ·required for the

Degree o:r

MASTER OF SCIENCE, GEOLOGY MAJOR

Rolla., Missouri

Approved by-

1951

~~-----­Professor of Geology

C.ONTENTS

Acknowledgments. • • • • • • • • •.• • • • • • • • • • • • • • • • • • • • • •.• • • 11

List of Illustrations ••••••••••..•••••••• ·••••••••• i11

List of Tables ••••••••.••• . • ••.•••.••.• ~ • • .. •. • • • • • • • . i v

Introduction ••••.•.•••••••••••••••••..••..•••••••.•. , .• •. 1

Sample Location. • • • • • • •.• . •. • • . • . • • • • • • • • • • • • • • • • • • • 4

Review of Literature •••••••••••••.•••••••• •....... 5.

Segrega.tion of Clay Mineral. • • • • • • • • • • • • • • • • • 5

Dirt erent 1a.l FJ.o ccula t 1Qn .. .,..... • • • • • • • • • • • • • • • 6

Diff~rent1e.l Electrophoresis................... 8

B ize Segrega.tion ••••.•••••.•• _. •.• • • • • • • •.• • • • •.• • 9

Mineralogy of Missouri Fire Clays •••••••• •...... •• 12

Preliminary . Experiments. • . • • • • • • • • • • • • • • •.• • • • •.• • • • 15

Pr~l1minary Disaggregation.................... 18

Detail of Deflocculation Method.............. 18

Mechanica.1 D1sa.ggreg8 tion. • • • • • • • • •.• • • • • • • • • • 19

EJ.e.ctrod:talysis •••••••••••••.•.••.•••••••••.•.•• ·• 19

Hydrochloric Acid Let}ching..... •• • • • • • • • • • ••• • 21

Sodium Pyrophosphate Treatment •• . • ••••• •·····•·•·•f• 21

Stabilisation of Clay •••••••••• .-.............. 24

Total · Preliminary Conclusi~ns •••••• ~ - · •.• ~ •• · ·· ;· 26

Met boer Adopted ••••• .•••• ~; ••.••• · •••• , ~_ •.•• • ••• ~ •••••• ·-.. 27

Procedure •••••••••••••••••••••••••.•••••. ~.. •.• 27

Quantitative Pa~ticle Size Ana.1ysis............... 30

Procedure .•••••.•••••.•••.••• .•• '! •• •• ·• • .• • .• • • .• • • .• • • 31

Ta.billla.t1on of Results........................ 31 .

Base Excha.nge Capacity ••••••••• -~. . • • • . • • • • • • • • • • • • 34

Met hod. ••••••••••.• • ·• · -·· • • • •· • • • • • · • • • • • • • • • • •·· · ·· 35

Distillation ••••••.•••..•••.••••••..••••••••• 36

Results •••••••••••••••••••.••••.••••••••• • •.•.• 37

Discussion ................................. .. ... . 37

c 1 i ' . . . · one us on ••••••••.••• •.• •••.••••••.••••••••• ~ ••• 38

Differential Thermal Analysis ••••••••••••••••••••• 39

Appa ra.tus •••••••••••••••••••••••••••••• • •• ·· ·•·• 39

Pr odedure •••••••••••••••.• • ••••••••••••••.••• 40

Discussion of · Differential Thermal Curves •• :. ,. . . ' . 40

X-Ray Diffraction Ana.lysis ••••.•••••.••.••.••••••• •:•'•. 47

Procedure •••••. .•• •' ••••.•.••••••••••••••••.•. t •. • • 47

Results of Powder Wedge Di.ffraction Analysis. 48

Further Investigation ••••••••••••••.•••• •·• ••.• 50

Investigation of Three Layer Lattice Minerals 51

Interpretation of -Electron Photomicrographs •••••.•.• 54

Conclusions ............................. · ·• •••••• •'•. 60

Bibliography ••••••••••..•••••••••••••••••••••.••••••.•. 61

Vita •••••.•••.••.•••••••• •. • •• • • • • • .. • • • • • • • • • •·• • • • 74

11

ACKNOWLEDGMENTS

The investiga.tor . wishes to express his appreciation

to:

Dr. O.R. Grawe, chairman of the Department of Geol­

ogy, Missouri School of Mines and Metallurgy, University

of Missouri, for recommending the problem and for many

helpful suggestions durlng his direction of the thesis.

The Mexico Refr~· ctory Company , Mexico, Missouri,

for supplying the sample of Mexico Plastic clay.

Dr. P.G •. Herold, Dr. T.J.M. Planje, and Mr. C.E.

Schulze of the Ceramic Engineering Department, Missouri

School of Mines and Metallurgy, University of Missouri,

for use of equipm~nt.

Dr. W.D. Keller, Dep8rtment of Geology, University

of Missouri, Colombia; Missouri~· f'or use of the differen­

t 1al therma.l apparatus and for general use of his lab-

oratory.

Mr. J. Afffleck, Physics Dep~rtment, University of

!~ss ouri, for making electron-photomicrographs.

111

LIST OF ILLUSTRATIONS

Plate Page

1. Particle Size Dis tr1 outit>n ••..•••.•••.•••••• ~ · .. 33

2. Differential ·Thermal Curves, A-E •••••••• .-...... . 41

3. Differential Thermal Curves, F-K............... 42

4. EJ.ectron Photomicrogre.ph- Minus 5u Fra.ction.... 56

5. Electron Photomicrograph- 2 to o. 5u Fraction •• 1. 57

6. Electron Photomicrograph- 0.2 to 0.05u Fraction 58

7. Electron Photomicrograph- Minus 0.05u Fraction. 59

1v

LIST OF TABLES

Table Page

1. Results Quantitative Particle .Size Distribution.... 32

2. Base Exchange Capacities •••••••••••••••••••••••••• 37

3. Interplanar Spacings for Mexico Plastic Clay...... 49

4. D1str1qut1on of Minerals According to Particle

Size in Mexico Re.fra.ctory · C6mpany's

Plastic Refractory Cl.a.y •••••••••••••••• :.: • .• :. :. 53

1

CHAPTER 1

IN!RODUCTION

From the rather modest beginning of the refractory

industry in ~llissouri prior to the Civil War, the industry

has grown to challenge those of other states as the third

tergest producer of re.fractory cla.ys and products in the

United States. As Roberts (1950) points out, the develop.­

ment of the rr;etallurgical and glass 1ndu~tr1es increased

the demand for high gra.de refractory materials. A promin­

ent factor in the development of the .fire clays o.f Missouri

was the discovery that flint clay could be mixed with tge

plastic or semi-plastic refractory cleys to yield an ex­

eellent product. Perhaps the most important reason many

eastern manufe cturers ·set up plents in M1ssot1ri is the

close proximity to high quality plastic, semi-plastic~

flint;· and d1e.spore- .cla.y deposits. Their rather shallow

depth permits them to be extracted by econmical open-

pit methods which replaced the inef.t'1c1ent u~derground

m1n1ng metnods of the early 1920' s.•-As the ref'ractory industry became· big business:,

it adapted the futuristic outlook of big business.

Common practice in the cla.y industry had been to

stockpile only enough clay for immediate needs,as the

cost of production included relatively high processing

costs and the cost of the raw materials has to be kept

to an absolute minimtnn. Cley deposits were dis·covered

·by examining outcrops exposed in stre~m banks and

2

roa.d cuts. Occe.s.ionelly, someone drilling for water

would discover a ge>od clay. Now extensive scientific

pros pecting methods · directed b1" technically tralned~ per­

sonnel are employed ( Bradley and Miller, 1942; W.D.

·Keller~ 1949, pp.45l-454).

While the importance of. the high grade clay de.­

posits of Missouri is generally recognized, the only

extensive investigation~ published to date he.ve been

concerned with the distribution and genesis of the de~

posits. Very little work has been done regarding the

detailed mineralogy of these clay$.

One has only to look at the works of Grim (1939a;

l939b, 1946).to get an appreciation of the importance

minor cla.y ccnstituents ha.ve on the properties o:f the

whole clay. For example,· mt>ntmor11lol\1.te leeds illite

and kaolinite, ill tha·t order, 1n properties of plasticityl

drying shrin_ln,ge, bonding power a.nd response to ex­

changeable bases~ . Even undetectable a.mounts of mont- .

morillonite or illite in a "kaolin" may catEe it to ex-. .

h1b1t .Properties not common to ke.ol1n1te,. Detailed in­

vestigation of these clays will help us to better under-

3

stand some of their ''Un.usua 1" properties,.

Results cf these 1nvestig8tions may also be used

· to correlate various clay deposits on the basis of their

clay mineral content a.fter more 1nf'orma tion has been

accumulated. Th~e is still la.cking in the liereture

e rough inf'orrnat ion on clay m1nera1. ·assemble ges to develop

uncontradi cto:ry . para genetic relations. In other words,

cla.y m1heral alteration seqeunces a.re still obscure.

With these conSiderations in mind, the Department

of Geology hes . set ~P a Clay llineral · PrQ j eet ~ the pur­

pose o:f · which is to irt·vestigate· more t mroughlt· the clay

mineral content of Missouri clays and shales.

This is the initial paper of the project. It

purports to study the methods of investigating clays,

to adapt standa.rd methods to the facilities &Ya:fj..able, and

to report the mineral content of a Missouri pls .. stie re.­

fractory clayr• It is hoped tmt this paper will stimu~ate

interest 1n Missouri clay~ •.

4

Sample Location

The clay sample studies was obtained through the courtesy

of the Mexico Refractory Company, Mexico~ Missouri, from

a. pit opened in the summer of 1950. The pit is lovate&

about · three miles from the plant. It is ·rather shallow,

going down to about twenty feet from where the pla.st1c

clay grades into a .sandy phase and then into sandstone.

The usable clay strata is about six feet thick. Above

the plastic clay is about ei~bt feet of a darker second

grade clay not now used by the company, but stock-piled

for possible future use,. The day is higher 1n iron and

alkalies tha.n the good plastic clay beneath. Above this

poor clay and exttmding ·to the surface is about eight

feet of glacial till, which ov~rlays the whole area·.

A very noteable point to mention a.bout this pit is I

that it does not possess a limestone cap so commonly char-

acteristic of ·plastic clay pits.

Hand Sample

The plastic cla.y is light gray and friable. On ex-

posure to the atmosphere_, cley at the stock-pile turns

to a yellowish white.

5

CHAP~ ll

REVIEW OF LITERATURE

Segregation of Qr Minerala·

Ever since the dis.covery by Hendricks e..nd F.ry (1930)

that montmorillonite, beidellite, and halloysite ( as

indicated by their x-re.y investigations) are common con­

stituents of soil colloids, soil chemists have become

1ncrees1ngly interested in detecti.ng minor e.ccessory clay

mineral components of soils. In most ce.ses a minor com-

. ponent must comprise :from 5" to 20,C of the actual sample

investigated 1.f it is to b~ identified. When they are

present in smaller amounts, it is necessary to concentre.te

these independent phases. Among ~ecent investigators,

Pennington and Ja.ckson (1947). and Drosdoff (1935) have

reported on the possible method's of separating the ingred­

ients of polycomponent colloidal clay~~ -They have evaluated

the following methods::.

(a) Specific gra.v1ty separation

(b) Differential .flocculation · (1)

(c) Differential electrophoresis (2)

(d) Size segregation _

(1), (2) Not investigated by Drosdofi' (1935)-.

6

Specific gravity separations are not particularly

amenable to the separation of clay minerals. Although

Volk (1933; pp. 114-129) was abl-e to separate qu..~rtz a.nd .

muscovite from the 2u to Oe3u f'raction of soil, Drosdo.ff

: (1935, p. 464) experienced difficulty with the method in

that his clay coagUla ted in tetrabromoethane. Other

heavy liquids could be used to eliminate this diffic\lllty,

but the method ha.s not been perfected to such a.n extent

that minerals with densities so close together coul.d be

sepa.rated fr·om one another •

. Differential llocculation

Differential flocculation as a. method for separat­

ing clay is theoretically sound in that the clay mineral

groups exhibit characteristic electrokinetic propertiea.

The theory acco~nting .f.or these properties can be deduced

from Grim (1939; PP• 475-477)

For the montmorillonite. group the charge on the lattice Tt+

is determined by the nature of the repla.cement of' Al in +.-+++

octahedral coordination and Si tetrahedral coordination

by ions of vel~nce of two and three respectively. This re­

placement by ions of lower valenc·e leaves the three layer

UU.it cell negativley chBrged. In. an attempt to establish + +

electrical neutra J.i ty, ca.tions like Na and Ca are adsorbed

between the three layer sheets (b•~ween opp~site silica tet­

rahedr8 ). If the cation bond between the three layer sheets

is not strong enough, ~0 is adsorbed between the sheets and

causes expansion and allo·ws it to clea.ve more easily. The

potentia.l set up between the particle and the dispersed

system is therefore ,· a function ;.,.p nnqo+1 -e• -..:a -. ~ -· .~ ....... -

7

valence bonds and in'creased surface energy of size re-

duct ion.

In illite, the excess charge created by the replacement

of s{+++ in tetrahedral coordination by Al +++, and Al +++

in octrahedral . coordim tion by Fe and Mg ++is satisfied

by large K+ ions. which prevent the lattice from expanding.

W1 th this property of non-expanding la.ttice, the layers do

not cleave readily and there is less surface energy assoc­

iated with illite particles· for ePch unit mass compared with

montmorillonite. The essenttal dif:ference between the nature

of tb.e montmorillonite charge and the illite charge is that

more of the montmorillonite charge is available as sur.face

energy.

Replacement 1 s not known to tal-\e place in the kaolin­

ite structure. The strong attre1ction between the 0 and

OH layers jDrevent it from· expanding and cleaving readily.

It has been shown by Johnson (1942, pp. 344-346) that the

charge on kaolinite is directly proportional to the sur­

face area ani can be essentially attributed to that fact.

Its ele ctrokinet1c properties a.re therefore lower than

those of illite and montmorillonite.

The object of di.fferentia.l flocculation is th reduce

the repelling force between particles in suspension so

that adhesion :}_nsteaci of rep'blsion will occur when they

collide. The individuals gradually floc cul.ate and settle

trow the syst~. One reduces the potential between .the

particle and the dispersed phase by adding· an a ~, propriate

electrolyte to the ~o~. This is the essence of Tyulin•s ·· ' . .

work~repeated by Atkinson end Turner (1944)) wherein they

settle successive :Cractions ·with different electrolyteS!'•

Since no m1nera.log1cal determinations of' the .fractions

were made it 1s impossible to evalua.te the merit.$ of the

technique. Drosdof'r (1935 p. 466), Robinson and Holmes

(1924), and Pennington and Jackson (1947) report no suc­

cess in separa.t1ng clay colloids by their own methods of

d1frerent1al flocculation. Invariably, mixed floes are

producedt •.

Differential Electrophoresis

If an electrical field is applied to a colloidal

sol the particles will migrate ·to tbe elec~rode opposite

in etE.rge to itsel:O• This technique ee.n be applied to

clay minerals • . The velocity of migratioh, as Jenny and

Reitmeier (1935,pp. 594-595) indicate for Putman cle.y is ' . .

proportional to the electrokinetic potential (zeta potential)

and the potential drop across the electrodes. It is apparent­

ly independent of the perticle size . and inversely proport~onal

to the concentration of the sol!. It would seem that the

clay particles with the greatest ehsrge would travel more

rapidly to the anode leaving the lesser charged particles

behind. The method he-s not been successful. because the

change in pH near ·the e?-ectrodes causes coagulation of . -

the different · pertielest. The method has been used for Sft·P-

arating proteins by Abramson, Moyer and Gorin (1942)·.

Size Segregation

Particle size diff'ere ntie_t ·ion as e. method of separat­

ing cla.y minerals is particu~ar.ly inviting. Properties of

expansion end cleavage;as previously described,are generally

characteristic · of ind1 vidual clay mineral· groupsi. nte

term cla.y is a standa!d t -erm in the .textural cless1ficat1on

of sediments ;indicating the finest ~rade to which sediments

are trituratedr. In a · study of. the weathering sequences of

clay sized miD:erals in soils; Jackson et al. (1948) indicate

that feldspe .. rs am quartz commonly occur in the clay size

fraction of soil · co~loids. Tbe minerals gypsum, halite,

calcite, dolom1 te, hornblende; olivine, diopside, · b.iotite,

glauconite, chlorite, ani antigorite ere not usually round

in the clay .fraction, f'or by the time they are reduced to

near clay size, the rate of alteration is so accelerated loY

tbe increase in surface area as to completely eliminate

them from the mineral a.ssemblage. Apparently, this process

continues into the cle.y size range and possibly among the

clay minerals themselves•,. A general. idea of the distribu­

tion of minerals in the clay size grade can be appreciated

:to

by .analyzing the de.ta-of' Grim and Bray (1936), who studied • ceramic clays, end Pennington end Jackson's (1947) work

with soils. We note tn.,t the relationship among the clay

minerals is indf.!Pe.ndent of' the -degree of' weathering. Kao­

lin and illite are coarser then the montmorillonite group.

Depe.nding upon the fineness of kaolinite·, montmorillonite

should occur in the next finest fraction. Intermed1a te

micas should occur in the finest fraction of kaolinite;·

but above that of' .montmorillonite. • desirable cut to

separate the feldspar from the clay and quartz is about lu.

Pennington and Jackson (1947)

· 5u to 2u qus.rtz, feldspars

2u to .2u Illite, quartz, kaolinite, very minor albite

.2u to .su

.oau

Mica Intermediates, remain­ing kaolinite; very minor quartz

Montmorillonite, very minor Kaolinite, minor mica . Inter­mediates;.

Grim and Brey (1936)'·

coarse (about lu) kaolinite . sericite (illite)

· fine (-O.lu) beidellite montmorillonite halloysite limonite amorphous QDgin1e matter'

quartz ma.y go down to o. osu •.

The first to study the finest fractions of soil were

perhaps, Moore, Fry, and Middleton (1921) e. rd Bradfield (1923):.

They obtained their samples with the aid o:f the Sharpleff

' 11

supeTcentri.fuge. Howeve~, their conception ·of the separ­

ated particle sizes was quite vague. It wasn't until Hauser

and Reed (1936) developed an understanding o:f the hydrody.~

:na.mic conditions that quantitative work was made possible.

By controlling the rate of .feed of suspension and R.P.M.

of the bowl, one can.prepare desired fractions accurately.

Because separation by particle size was best predicted

to concentrate the individual clay components and because

the Sharples supercentrifuge was available, it was decided

to base the investigation on the particle size segregation

method.

CHAPTER 111

MINERALOGY OF~ :MISSOURI FIRECLAYS

At the time wben research techniques in c1 ay miner­

alogy were limited to micros.eopic exam1na.tion and chemical

analysis, Wheeler (1890) reported on the first c anprehensi ve

investigation o:f MissoUri clays. He believed most Missouri

cleys were mixtures of kaolinite and pholerite. The

pholerite (2Al2o3 • 3 Si02• 4 HfO), he reascned,would

have to be present tOt,aecount· for the excess Al2o3 over

that of a pure kaolinite (Al203 • 2 Si02 • 2~0). The

flint clays were supposed to be pre~ominantly pholerite,

while the plastic clays were _supposed t_q be predominantly

kaolinite.

Ga.lpin (1912, Pl'• 330-331.). attributed the water in

excess of aaol1nite 1U flint C~- YS to pholerite or to

a mixture of kaolinite and bauxite. The minerals reported ·

in flint clay were kaolinite, muscovite, and hydrBrgyllite

(gibbsite).

Wheery (1917, p.l44)>was the first to identity dia­

spori te 1n Missouri clays~ Ries ~ ·Bayley et al. (1922) ani

Somers (1922~ PP• 294~297) reported a mica-like mineral,

b,t tRey designated it as hydromica, a mineral whose indices

o:f refr8ction and birefringence were intermediate between

those of kaolinite and muscovite. Tre amount of this mater-

ial was repol!ted as being very abundant. Kaolinite is report-

13

ed as being abundant to sc?rce. 0!.' the detrital minerals,

qua.rtz 1 s common, but rut·11e, epidote, Zircon, tourmaline

and titanite are scarce-. The last mention of pholer1te a_~

a constituent in Missouri _ el:ay· is by Ries (1927) who ques­

tions its presence end proposes · that beuxite may account

· for the high A1203 content. ' Q£ the more recent investigators, Allen (1935, p • .

7-9; 1936, p.60) described halloysite as a major con­

stituent of flint clays, ka.olinite being considered by

him as only a rr1nor constituent. The plastic and semi•

plastic clays, Allen reports, are. chiefly kaolinli te with

a lesser hydlromica or sericite-lne mineral present. Also

rep6rted were quartz; che;t, musootiwe, pyrite, tourmaline,

zircon, rutile;· titanite; and leucoxene·.-

Grim and Bray -(1936; p.310) fractionated a Missouri

flint clay arrl specifically indicated that they found !}&._

halloysite. X-ray · and optical methods were used to identi­

fy ka.olinite as the major ·constituent. On the basis or optical methods alone, Brim reported -the presence of boeh­

mite. He also reported the presence or a sericite-like

mineral present in- the -;ninus 0.1 fraction.

Allen's later report (1937, p.ll) also cast sane

doubt on the hallopsi te content o£ .flint clay.. On thfr

basis o.f -x-ray diffraction amlys~s the mineral content

wa.s reported a.s being either ha.lloysite or microscopic

kaolinite.

14

A new mineral 1~ a flint-like Missouri clay was identi­

fied by Herold (1942, p. 235) ·as .being boehmite, the alpha

form of A1203

• ~0. .The same ~ley · had previously bee·n celled a

diaspore clay.

In 1946, Keller and Westcott (1946, p. 1210) publ:llshed

am abstract o:f extensive work on Missouri clays by

meBns of differential thermal analysis. The flint clays

produced curves similar to typical ka olin1tes. The

plastic clays "t~rere like these · of kaolinite except ~ the

emotllermic ani exothermic reecti.ons occurred at a. slight­

ly lower temperature ( in ordsr of ·10 degrees). 8ome • plastic cla.ys were said to be dominantly kaolinite and others

possible mixtu r es of kaolinite and montmorillonite.

The 1B test a '00. t:l.os t extensive mine-ral ogicf-:11 invest1-

gations of Missouri flint and pla.tic clsys is by Burst

(1950) which came to the attentimn of this investigator

as this work was nearly completed.. Burst reports that

kai1n1te and illite are the domtnant clay minerals in plas­

tic and flint ·clays en.d- ~.that montmorilllonite is present 1n the

plastic cloy in minor amounts.

For a dis cuss ion of the distribution and geology of

Missouri Clays reference is made to McQueens excellent ,

repo:bt on the "Fireclay Districts of East Central Missouri•

(1943).

15

SHl-PTBR lV

PRELIMINARY EXPFRI:MENTS

· Discussion

The ultimate purpose of the clay preperation pr o­

cedure is to obtain assemblages of single clay .particles

whose sizes are restricted within predetermined limits.

The first step.· in the procedure is dd.saggregation. The

object is to destroy the bulk clay structure without chang­

ing the t'exture, that 1st . to sepe.rete .the individual clay

pe,rt~cles wi;thout reduction of size. Once this is accomp­

lishe~ an attempt is ID8de ·to keep the distinct clay par~i­

cles dispersed. ~ectionation then follows where actual

size grades are removed from the whole sampl~'•·

The problem of d1saggrege.t1on without destruction of

the individual clay particles is complice.ted by several

· factors·. Cementing materiel is commonly present in clays.

It may be Fe2o3 , NJ.2o31 8102 or eaco3 or organic nette~ •.

In any case, it must either be removed without dissolving

any of the clay minerals or its affect reduced if the parti­

cles are to be separated but not crushedf• Pressure often ·

indurates clays considerably. .Sl~~htly irxiurated clays

may be disaggregated by mechanical mixing, but sometimes

the sample has to be rejected if the compaction is too

16

intense.

Grinding as a. method or disaggregating is very often

used, but it is difficult to · see how the cJEy particle

. will not fracture til the process. It is also difficult

to see how grinding would separate par~icles cemented

together.

Excellent procedures· on disaggregation and dispersion

are given by Krumbein arXI Pettijohn (1938, pt. 1).

Once the mtdial is disaggreiated~· the problem is

to kaep th~ - · ·particles in suspension without allowing

them to collide and form mixed f'locs. The establis.hment

of a stable suspension depends upo:p. the ability to ad- ·

sorb ions on their surfaces. These .ions a.rt? of two kinds

which are primarily held by res.1dual valences and lattice

forces. The first group of ions are held rigidly to the

clay surface while other i ·ons . (opposite in charge) are

in part held to the first rigid ionic le.yer. The

pa.rt1cle a.nd 1 ts two ionic layers are called a colloidal

micelle. The theory follows "th at o:f Guoy and Freundlich

and carries their names. The charge on tre particle that

is responsible ror the repulsion is called the zeta poten­

tial. It is the potential between the rigid ionic layer

and a remote point in the dif'fuse ionic layer. According

to the Helmholz equation:

where " " "

Z-e--d-D-

17

zeta potential charge density at the surface thickness of the double 1ayer dielectric constant of the me­ium

Me.x1mum repulsion eught to result whe·n the surface cnerge

. and density and the,~ tpickness o.f the double leyer e=te

great.. Jenny and Rietmier (1935; . p. 596) have d:l,scovered

that the zeta potential for clay pBrticles depends upon

the nature of the adsorbed ion and its concentration.

· The zeta potentials developed .follow the Hoffmeister lye­

topic series: Li/' Na'J' NH4> Rb and Mg > Ca> Sr > Ba •

For ions of equal valence the· small est ions are ·· more high-

ly hydrated. These ions of large hydration develop a greater

diffuse ionic layer to which the zeta potential is

directly·relate~~

Flocculation values· G~mount · ot•· electrolyte needed

for the diffuse ionic :ibayer to become so c cncentrated

that it will c cmpletely neutr811ze the charge of the rigid

ionic layer .and reduce the· zeta potentia.l to cause co­

agu:I2 tion ) aJ:'e greater :for the ions higher in the series~

lending greater freedom in ver~e~'\tion of' electrolyte cone•

entration. These ions of higher hydration ere also easy

to remove and be replaced .by ioi\S of lower hydration.

Fractionatio~tt;tion presents the least problem-• Ad­

equate understanding of the Sharples Super centrifUge

exists (Heuser and Schachman; ).940.; ~lEer end Reed, 1936;

18

Norton a.n:i Speil, 1938) and it is not deemed necessary

for discussion here.

Preliminary Disaggregation

Before any prelimine.ry experiments concerinig dis­

aggre@a tion a rrl dispersion could be · carried out it _ was

necessary to bree.k the _ clay up initially from large clum:rs.

to small wo!kable aggresates so that. the material could be

adequately sampled. I

About ten pounds of' bulk cl-~y were broken d9wn by

hand to clumps of about one inch in diameter • . .a small

amount _of water was added to allow t-he clay to slake and

form a sticky slj_p. TQ.e slaking w~s helped along by man­

ual kneading. After all discernible clumps were broken

down, the cla.y wa-s ·allo"eQ. to a.ir dry whereupon it was easily

crumpled between the fingers to pa.as a 9 mesh s·ieve. The

material was then quartered . and stored in mason jars for

future use.

Determination of Deflocculation Method

The very light grey· calor of the clay indicated that

Fe2o3

and organic matter were not present in amounts

suff1en1ent mhinder dispersion. Treatment with Hf02 and

HCl indicated the absence of carbonates and organic mat-

erial.

19

Mechani.cal Disaggregation

A two per cent "suspension'' of··cla-1 :. ( 30 grems. of clay

plus 1500 ml. :920 :rn a 2 que.rt mason ja_r) was · allewed· to

slake for two· days; mixed >wi~h e mechanical. stirrer for a

half hour and then blunged (rotated end over end for twenty­

four hours). · The material which settled to the bottom 1

upom examination under tbe microscope, was _round to consist

ofdistinct quartz particles. other detrital minerals ani

clay aggregates which were not broken up by the action of

water and mixing. The aggregates required slight pressure

with a needle to bring about further disaggregation. This

who[e procedure was considered inadequate to meet the ·neess

of the problem.

Electrodialysi§

It was thought that ions of high valence and low

hydration might be responsible for holding .the e,ggreg2tes ,_

together. EJ£ ctrodlalysis is a recognized method for re­

moving these 1oE_s;.

The electrodialysis cell used was the same one used

by Mueller (l949,pp.32-36) It is a Mattson type cell

simila.r in design to that used by Johnson ar:d Norton

(1941, p. 55).

A 5fo sus pens ion. of clay (50 gr~ms and 1000 m]j •. o:f

H20 ) was prepared and treated in the seme manner as describ­

ed in the previous paragraph. The suspension was ple.eed

20

in the center, parchment-lined compa.rtment of the elee­

trodialyzer and, diluted to ca.paeity (4 liters). Distilled

water was added to both outer compartments a.nd to the level

cf the over-.flow. Two stirrers kept the suspens.ion~. : from

settling out while a · eurrent of ano volts a.nd 150 mill1•

a·mperes was passed through the suspension. Ph determin­

ations were made period!ica.lly 'with a Beckman Laboratory

Model G pH meter'-• Electrod1alys.1s is c cnsid~red. complete

when the pH anl the current density stop declining and

reach a constant value. With the clay used, the pH and

current density never varied from their initial values,.

The d 1alys1s was carried· ou~ for eight hours at which · -:

time tne pH was still 6.5... This 'indicates that the e:x.­

change never took ple.ce in the clay at all. The adsorbed

cations· were not removed from cle.y micelle and replaced ~

by H ( to give an acid. clay as · they should. One or a

combination of the rollowing factors were attributed to

thi4 misbehavior.

(a) The clay particles were so agglomerated as to

prohibit many ads orbed ions from being replaces;.

(b) The presence of a protective colloid on the partw

icles and/or aggregates inhibited exchange. ·

(c) Di or tr1val ent ions are adsorbed ·and strongly

held by the particles. These ions have low ionization

constants. and /are not affected ~ 'by the ele:ctric current·"

21

to the extent that monovalent ions are eftectedJ. ·

Hydrochloric Acid ·Leaching.

To remove .the r-1nterfer1ng substance ,the HCl leach­

ing method as developed by Grim, Bray'' am Kerr (1935) ·

was tried. The ·sample was leached with O~lN HCl to ree.. •

move all soluble materia.l and then dispersed with NH40H

to pH 9. This method proved successful in destroying

aggrega.tes am in dispersing· the clay:. When applied to a.

500 gre.m sample this method becomes unworkably slow~ IP}d

a considerable f'ine amount of material is lost through the

filter papert.

SodiUm PyrophosphatE Treatment

The success wiDh Na4P2o7•10.H20 for dispersing clays

r~ported by Vinther and Lasson (1933) and · by Loomis (1938)

prompted its investigation here e.s a. possible defloeculating

agent. Following the procedure ot Vinther and Lasson;

5•5 grams of clay were added to 210 ml!. of. water containing

o. 5 grams of Na4P 2o-7··10 ~0 and blunged for· seventeen

hours. The slurry was diluted to 550 ml. to prepare

it for mechanical ane).ysis!. Microscopic investigation

of settled particles revealea that fewer aggrega.tes were

le.ft. Better separation was desireq but the general·

method showed promise of being applied.

The line of investigation was then directed at per-

22

fecting . this method as 1 t applies to the clay being analy- .

zed. The e.f.fect of different concentr~tions of Na2:P2·o.r· 10 H20 on the defloc cula.tion of clay was determined by

a.na.lysis and by exeminatilon of the grades with an ele .. ctron

microscope. The lOu sample from eacn was examined under

tb e optical ·microscope am thEn dried and weighed. In I

determining the optimum concentr8t1on _o.f Na4P2o7 • 10 :820

. . ~.

t o be used, samples c on ta1n1ng 5. oooo grams of clay in

100 mls. · o.f sodium were used. The .c cncentrat·1ons ·eniploy­

ed were:

A--0.2~ B--0.4~ c--o~s?& D--o-.e,: E--1.0~

The suspensions were allowed to slake for two ·days. They '

were then mechanically mixed for one hour arxl then blun-

ged for twentyfour hours. After this blunging period

was over, they were poured into 10~0 ml. cylinders, dil•

uted to one liter and sha.kenr. vigorously .for . five minutes.

each. A standard pipette analysis (Krumbei-n and Petti­

john, _ 1938, pp. 167-169) was per .formed on ...eech to deter-.. mine which suspension was best deflocculated. Sa_mples

ccnta.ining parti~les less than 5u were also extract~

.from the s\Epension · so that the particles could be ex­

amined with the electron microscope. The anelY.sis in­

cluded examination of' particles .as Sllall as o.su •.

23

Optical examination of the larger particles revealed

'Very good di.saggrega.tion with concentrations of 0.6 to

1.0( Na4P2o7 • 10 ~o. With lower concentrations a few

lerge aggregates were noticed.

Electron-micrographs revee!led many individual plates ·

of kaolinite with straight ·edges indicating good aepara­

tion. Other particles appeared to be clumped· together.

It was impossible to determine f-rom the elect-ron -~~oto­

micrographs which sample was dispersed best.

Comparison of the f1 ve drif.ferent mechanical a mlysis

y.ielded only general results. In gen~ral the amount of'

fine material in suspension increa.sed e.s the concentra­

tion .of Ne,4P 2o7• 10 ~0 increased·. With three highest

concentrations 50 tq 52~ of material less than one micron

in size was present, with the two lower concentrations

only 45 to·47fo'of the material was in the ·less than one

micron size. At . th~ end of' two weeks, visual observation

indicated that a concentration of 0.8" Na4P2~· 19~0 produced -the best dispersion· for the least aroount of mate­

rial settled from the upper three em. of' suspension.

From the foregoing results it was concluded that:

(1) A solution of at least a 0.6;( of Na4P2~'• 10 ~0

was required to reduce the affect of' the bonding agent

holding particles together~ in d 1scern1ble aggregates:.

(2) That the sedime·nting s-uspension' (diluted sus-

24

pension) can have a concentration range from 0.006~

Na4P2o7 • 10 ~0 (0.6 grams/liter) to_ at least 0.01~

Na4P~Orr· 10 ~0 without a ·ppreciably affecting the sta­

bility or the dispersion • .

(3) That Na4P2o7 • 10~0 used in su.fficient concen­

trations can serve a dual purpose.J

(a) It can be used to remove the material hold­

ing a.ggrega tes together.

(b) It can a.ct as a good dispersing agent, .,ttf.

supplying large quantities of Na_ which~' as pointed out

previously, develops a. ~1gh zeta potential within a

compare ti vely large range of' concentrations,.

Stabilization of Cla:y

During fractionation, either by decai1tation or cen-

trifuging, cla.y· is c cntinua1ly being removed from the

original suspension a.nd redispersed aft.er ( s~ttl~.

Such a process will dedidedly reduce the concentration

of the peptizer to the point where flo<ICulation wlll

occur. More peptizer of proper concentration will be

required to keep the cla.y particles separated from one

s.nother. An acceptable measure of this concentra~ion

is pH. It was therefore desired to prepare suspens1o~s

.free of electrolyte to which varying concentrations . of

NH4-t ·will be added to give pH values from eight to twelve

25

e-nd · the relatlve stebility noted •.

F'i.fty gr pms· o.:tr clay were trea.ted. with 500 ml. o.f

0.89& Na4P207 • 10 H20 in t~e manner previously described.

The sus~ehs~on was .electrod1alyzed until the pH reacped ~

a constant value. In cont:raJst to the previous method

of d'ialys:11s, t'his time the pH ch enged from 10.1 to a

minimum of 5.2 -in twelve hOurs. The clay was permitted

t -o settle, the supernatant liquid siphoned off, and the

material allowed to air dry.

Nine l.Ofo suspensions of the dialyzed clay were pre­

pared by weighing 0.5000 gre ms of clay into 75 ml. test

tu[!es into which, 50 ml. of distilled wa'Oer were intro­

duced. The pH o.f these S ') spehs ions were prepared progress­

ing from 8 to 12 ip. steps o.f 0.5 pH values ea·ch by the

adcli tion of NH40H.. These su~pens1ons were pa eked into two

2 CIUart mason jars and blunged for twentyfour hours. They

were allowed to settle for one week whereupon the rela­

tive s.ta_bility of each was determined by noting the

cloudiness of the upper part of the suspension.

The stability 1ncrea.sed gradually ,t.rom pH 8 to pH

10.5, but suspensions of pH 10.0, 10.5 were much better

than those or· lower values. Suspensions o.f 11.5 a.:nd 12

values were not as stable. The most stable was at pH·

10.5, this being determined by hol111ng the samples 1n

26

front of ~- strong 11:ght to determine which was the most

opalescep.t.

Tota.l. .Prel1minary Conclusidlns

(1) The bulk clay contains interfering material

which prevent it from being deflocculated and eleetro­

dielyzed readily.

(2) The affect of this interfering substance ca.n

be eliminated ·by soe.king and aggitating the clay in a

0.8~ solution o~ Na4P2o7• 10~0.

(3) A- pH value of 10.5 obtained })_y .using NH40H;

produ'Ces the most stable suspension.

Procedure

CHAPTER V

METHOD A~;OPTED

27

Six hundred grams or clay (prepared as described on

page · 18) w.ere added to 9 l:_iters of 0.8~ Na.4P2C,•101f:e0

solution and distributed .in six; 2 q\18rt mason jars·. Arter

the slip we.s a.llowed to slake for three days~ each quar-t

s~ple was mechanically mixed for one hour and blunged for

twentyfour hours. The slip was then poured into a large

bottle (20 liter capa.city) and diluted to fifteen liters.

This suspension wes then divided by sedimentation into two

fractions, one containing particles greater than 2u ana one

c mta1n1ng particles sme.ller than 2u. The less than 2u sus­

pension was further fractione.ted with the Sharples super­

centrifuge. The greater than 2u suspeBsion was fraction­

ated aga1n .by sedimentation. The initial separation into two

quart, mafor fractions was accomplished 1n accordance with

the following procedure.

After dilution and 14 hours of settling, the top 20 em.

con*aining. less than 2u meterial was siphoned off into a

large jar. The material. that remained was poured into 4

liter beakers to increase the height of the sed1ment1ng

column and to keep: the volume at a mintmuD. At the end of

14 hours; the top 20 em. in the 4 liter beakers were siphon­

ed off and added to the 2u suspension. The me.teria.l that

remained was resuspended with water em. its pH mainta.ined at

10 with NH40H. This process of resuspending and siphoning orr

28

the -2u material . was continue& until the superne.tant

liquid was free of the -2u grade.· .A battery- of several

suspensions W8S used to ha.sten the process. The pH of'

ell suspei:,lsions was kept at lO e.t all times·.

The plus 2u .fraction we .. s subdivided into -t-20u,

20u to lOu, lOU to 5u, and 5u to 2u by the same process.

The settling time for each size we.s determined from Stokes •

Law. Preparation of a time vs. particle size gr~ph for

·various temper~tures greatly facilitates .determining

settling times and is a. valUB.ble reference.

All size gredes were examined under the .optice.l

micr0SCOlJe. Aggregates were not observed a.m classifica­

tion e.ppee.red ·to be very good:.

All -2u particles were graded into the· following

cla.sses: 2u-o. 5u~ o. 5u-o. 2u~· o. 2u-O. 0.5u and -o. 05u, by

use of the Sharples supercentrifuge. Very good theor•

·etica1 discussions are g~ven by~ Hauser · and Reed (1936, ·.

pp. 1169·1182} and by Hauser and ,· Schacbme.n (1940; p.584).

An excellent general discussiOn ;'including procecl1me.;1s

given by Norton a.nd Speil (1938, PP.e367-380).

B'or separation of" particles from 2u to o.5u, the

supercentrifuge was run a.t 5000 r.p.a. while 30 liters

of -2u suspension were introduced . at a rate. ll.O>'ml! •. per

minute in 5.ccorq.a.nce- .with Norton- ani Speil(.l938,p.3.68)f~.

29

The me..ter1al that settled out on the liner of the

. bowl contained perticles ra.nging from Oe5u to 2u, but

"contaminated" with pa.rt1cles less than o.su. The sus­

pension the.t passed t -hrough the bo1Vl antained particle~ .

less than Q.5u. The "contaminating" particles were re ..

moved from the o.su to 2u fraction by repeatedly red1spers-

1ng end cEiltri.fuging, ·a.lways maintaining the pH at 10.5 .•

It required thirteen runs to obtain a fairly cle~tr over­

flow suspensiop. The overflow in most c~s~s was retained

far separating the next fractio~ •.

The same procedure was used for obtaining the finer

fractions. The 0.5u to 0.2u fraction was ext.racted by

running the centrifuge at 12;'500 r.p.zrt.. w1 th e. rate of

flow of 100 ml:./ minute; the o.2u to Q.0.5u fraction at

25~· ooo r.p.m. w.ith a rate of now of 27 ml./ minute; and

the -0.05 fraction was obtained by f'locculating the nearly

clear suspension with HCl at a pH of ~~

This whole ·procedure took one month to complete.

Harman and Fre.ulini (1940~ p.253) reported taking nine

months to complete a similar fractionation.

CHAPTER_. Vl

QUANTITATIVE PARTICLE SIZE ANALYSIS

Methods

The method chosen f'or quanti-tative particle size

determination was the Andreasen Pipette method. It

;30

is a; refinement over the ordine.ry . pipette .method 1n

that the pipette is always in a fixed position, being

fastened .to a ground glass stopper that fits into the

top of the cylindei'i. Tire pipette extends 20 em. below

the depth of the suspension to a point 4 em. !tbove

the bottom of the cylinder. The 10 ml. pipette hes

a three way stop-cock to facilitate dr~1nil\g the

sa nple into a beaker,.

The pa.rticular advantage of this apparatus over

the ordinary pipette method is that:

(a) The suspension is not disturbed by the intrQ­

duct.ion of the pipette to remove aliquot parts.

(b) The suspension dows not have to be re-

shaken to initiate- a new cycle of settling for removal ·

of the next finer size.

According t .o Steele and Bra.dfield (1934); the sus­

pension ca.nnot be sampled accurBtely if it is withdraWn

be-fore a. lapse of four minutes a.:f;,ter the Qtl1nder he.s been

shaken, nor can it be sampled accurately if its size is near

the colloidal· range because Stokes· Law .does not applY'•

The 11mi t generally is · a.bout. o. 5u.

A description and procedure _f'or using the Andreasen

Pipette is ·given by Loomis (1938)i.

ProcedUre

Five grams of clay were added to -100 ml. of 0.8"

Ne.4P2o7 • 10 H2

0 a rd allowed to sla.ke for one week.

Mechenical mixing for one hour was followed by blunging

for twentyfour hours. The suspension was diluted to· 400

ml. and mechanically mixed for one more hotir. The resulting

suspension was ·added to the Andreasen Pipette,· diluted

to the 20 em. mark (550 ml• at 20 degrees c.) e.ni

tumbled by hand .for f'ive .minutes to e.llow for thorough mi~ing.r

At predetermined intervals, 10 ml. of' sample less than.

a given equivalent diameter were drawn from the suspension,

dre.ined into a pre-weighed 25 ml. beaker ani evapora.ted

et 110 degrees o. Time of sample removal for material

less thm the indica.ted size is given belo~ •.

Size \di'a.meter)

sou 15 10

8 6 5 2.6 '

Colulml Height (em)

20cm. 19..6 19.2 18i.8 18.4 18.0 17.6

·Time of Sample Raoval.

8.4 minutes ·14.7 It

33.2 " 49.2 .. 1:.425 hrs. 2.025 " 7;.4 "

32

2.0 17:.2 12.02 brs:. L.5 16 •. 8 20.6 .. 1.0 16.4 46.7 .. o.e · . 16.0 69 •. 5 .. 0.6 15.6 124.9 .: ~

o.s · 15.2 171! .• ~- tt

Results we~e computed after. the method of .Krumbein

and Pettijohn (1938, pp.l67-l68) and corrected for the

weight of dispersing agent.

Several prelimina.ry samples bad been run to develop

a fa.miliarity with the method. After thi·s ;· four analysis

were made, two a.t a time; which agreed within 2~~ Values

· given are the average of those results • .

· TABLE-:.t Tabula.tion o:r Results

Size ( equivalent di~.meter)

20U 15u lOu

8u 6u 5u 2.6u 2.0U 1.5u l.OU o.8u 0.6u o.su

$ Finer Than

96.4 96.0 Q3.5 92.2 88 .. 2 . 85.1 -73.3 67·.4 61.8 52.6 48.6 41.7 39.5

~ Q) +­Q)

E 0

"0

c Q) > ·aa c 0

.s::. +-

PLATE I

100

I :

1--·~

I ~

I

9~ : ~ ~

I

:r '

80.: I

I

I• I I . :

,. i#H+H+ltttttttttHt !!•

I : t''

! I ' 'I

l :

7.0 , I I 'i

I I

I

! I

+Hfttttttltlt IJ

f+H++HttH+Hfit- ~

60 II "' I u I! I 1/

.· ~ . !, I

I II I

5o,::· I ltH IH+!f- ftttttttttltttttfttttt-

·:;1 ' i . ji ll '\ I (I q· I 1;:; It II I I

II , I • i !',

I I I ' I

4 0 ! !! I I I

,•II i I

II+!HlW ;,

IHttH+ f-H-1++1 I ·!

ltttttttttlt .

I, ! _! : : : 1: I " !

'I l '!:, I ' ! ~ : II

~ l i ! : ~

!;

O.h 1.0 2.0 5.0 1'0 Equilevent spherical diameter in p

PARTICLE SIZE DISTRIBUTION

3,3

-r .

~~~~~

I

I

· i

15 2jt>

CHAPTER VII

BASE EXCHANGE CAPACITY

The general theory regarding the ability of' clay

minerals to adsorb io~s has previously been discussed!·.

This ability can· be mea.sured e.nd the quantit_ative term

used to indica.te this is called base exchange Cftpa_.city.

The standard method of ~eporting it is ·in milliequivaJ.ents

of' electrolyte per 100 grams of' clay. I

Methods o:f determining base exchange capacities

have been investigated most prddigously by the soil ,

chemists and to a lesser degree by the ceramists. Very

good discussions are given by Che..pman and Kelly (1930);'

Schollneburger and Dreibelbis <1930) and Graham and

Sul1i van ,. (1938). ~e1ly (1939; PP• 45•-465) has written

2 paper or interest to the geologist.

, Two methods of' determining total base exchange

capacity are in. common use. One emplQYS electrodialysis I • +

to replsce the adsorb . .a ions with ~o __ in ordel'-to- produce ;

an,··a.c1d clay. -~ Titration of this · d 1alyzed cle7-against

Ne.OH produces 8 curve similar to that of a weak acid:.

(.O.E •. Ma.rshs.ll, 1949, PP• 107-ll9)~. The inflection

point of the curve (Graham and ·Sullivm, 19:38; p-• . 178)

can be used to determine total exchange ca~city. The

point on the curve corresponding to a pH of 7 (Meyer;

1934, p.214) is also used to give· the pH at neutralitY!•

35 .

The difficulty with this method is the long period

required f'or complete removal of adsorbed- ions. There

is also the possibility that p~olonged eiect.rollialysis

mig:ht destroy the lattice st~ucture (ThaHla~ 1945~ pp. ·

137-145; Roy~ Rustrum, 1949~ ,,pp.203-20.).

The second and preferred method of determining. total

exchange CB.pacity is the leaching or ba.tch method--.­

depemding upon whether· filtration or centri~ation is

employed!,. The clay 1n this process is .. converted to an

NH4

clay by saturation with NH4C2H~02 • ·The clay is

washed free . of excess NH4

C2Ji302 w1 th alcohol;. The ad•

. sorbed NH{ is · then determilied by the ste.ndard Kjelde.hl

method:.

A modification of the ba.tch method was used in this

procedure although the first method wa se•iously con­

sidered. It was decided to use. the batch method when an

Interne..tional #2centrifuge becPme available to the 1nves•

tiga .. to~. This procedure should be · used, if possible,

because more .determ1na.tions by this me.thod are to be fotmd

1n the literature:.

Method

Although most of the salts in suspension shoul~ heve

been removed by the fractionation process, all fractions

smaller than 5u were electrodialyzed for 10 hours.

. . . . Saturation of the clf.ly · .with NH4· was accomplished

by-· s .he~1ng 2 .• 0000 grams of clay plus 75 ml· • . of 2 N

NH4C2~02 in 100 ml:. test tube for 15· minutes • . ·. The

suspensions ~ere allowed to stand for a. half hour before . -

they were· centrifuged in an · Interrult.itbnel # 2 long•

ar~ centri.fuge. The supernata.nt liquid was poured off and

the process repeated except that now the suspension waf!f·

allowed to sta.nd overn~ght .before centr:tfugin€1~. The

clay wa.s satura~ed for the third time~- ·centrifuged, and

the liquid poured offt•

The exces·s NH4~~o2 we.s removed by wa.shing three·

times with. absolute alcohol!. : .In· order to preserve the clay;·

the NHt was replaced by ett .. +,-·wi th fonr washings of a. 51\r

. CaC12·• The supernatant CaC12 . solutions were saved and

quantite.tively analyzed for NH.3 by the -Kjeldahl dis­

tillation process.

Distillation

Fifty ml. portions of the CaCl2 S·b~ut1ons ccntain··

ing the exchangeable NH! were used 1n the NHtl· d~~n. · at1ons. _Ammonia. was distilled from the solution by the

addition of ioo mll'e- of 10 N NaOH e.nd pe.ssing st.eam

through the sample". The ~- was caught 1n .a standard

0.02 N,Hcl solution and back titrated with standard

o. Ol N NaOH . (Reimsn, . Neuss ,. and Naiman~ 1942; pp. 162-166 >·· Determinations were made in quadruplicate. Results are .

37

.., reported in milligram equivalents of NH4 p~ 100 grams

of clay.

Results

Clay

Whole Clery

-5u to 2u

2u to 0.5u

0.5u to o.2u

0.2u to o .• 05u

Discussion

+ NH4 Content mg.eq/100 gm. elay

1 •• 3

11.8

14i.6

18.3

35.8

. As was e?Cpe_cted' -the base exchange ca};ec1ty increas­

ed 1tt th decrease in particle s-ize or in 1ncrea.se in

surface area,. The base exchan~capacity of the whole

clay is grea.ter than that of the 5u to 2u .fraction beca~e . . .

that fraction constitutes only 17·. 7fo of the whole clay.

The whole clay contains 67•4fo material less than 2u,

therefore, its base exchange capacity should be higher

than the 5u to 2u.

Ba.se exchange capacities of the .. clay minerals are

usually within the limits given by Grim (1939, p.472):

Montmorillonite_ 60-100 mg:.eq./100 gms. cla.y

Illite-

Kaolinite-'

20-40

3-15

.. " " .. "

38

OccasionalJ,.y the bese exchange capacity values

exceed these :J_imits, as for instance, the Holtzhauser

Kaolinite repDrt has a base exchange capacity of 20.2.

Y.ontmor.illonite may vary from 8.5 to 160. The Eureka

Ha.lloysite has a base exchange capacity of 70.4.

(A.P .• I~ report 49, Preliminary report # 7 ~ pp. 93-96).

Conclusions.

Results of base exchange capacity data indicated

that fractions between 5u and o.2u J'robably are k~ol1n1te •

. The less than 0.2u deserves special attention 1n th~'t it

probably contains another type of clay minera.lt•

39

DIFFERENTIAL THERMAL ANALYSIS

Differential th~rmal analysis aa a.pplied to m1neaal-

ogy is a splendid tool for mea.suring the thermal cha.racter­

istics of minerals although its limitations must be respec­

ted. The method bas as its basis the measurement of exo­

thermic and endothermic reactions of the test ~ample with

respect to another substance tbBt does not exhibit lhese

changes while both are heated toge~her at a a:> nstent rate.

It is this diff~rential flow of heat to the thermocouple;

one terminal of which is in the test fl~llple a.nd the other

in the inert substance that :the differential eft'ect is

obtained. The temperature at' which. the reaction ta.kes place ·

is measured 't\ii th another thermocouple placed 1n the center of

the sample holder.

Apparatus

The differential thermal apparatus is the same instru- '

ment usedl by Wescott and Keller (1948~· p.l.Ol) • . It is built

after the design of Berkelhamer (1944) except the apparetus

is equipped with an automatic 141crolll8X--ectuated recorder

that measures the temperature of the s~mple block at 50 de­

grees c. intervals. The rate of heating varies for 10

degrees/minute to 12 degrees/minute. A variable resistor

40

is connected in series between the Chrom~Alumel di~ferential I -. • '

thermocouple and a mirror ·a,aivenometer. By ch~ng this

resistance, the sensitivi-ty of the instrument can be reg­

ulated.

Procedure:

All samples were dried at 65 degrees c. and ·passed

through·; a 60 m~sh sieve. While pecking the cley in the

sample· holder, care was taken to peck both the ·inert m8t8-

rial (calcined A1203), and test sample with the same amount

of' pressure. The smooth ·end . of e. gla.ss stirring rOO. was

used:; The sensi ti vi ty of this instrument was edjusted·

by means of a variable resistor in an attempt to keep ·

each curve on the recording paper. Sometim·es this he.d to

be S8cr1f1ced so that minor undule tion in the curve could

be tm gn1fiedt.

A resistance of 800 ohms .was used on the first test

sample of the whole ·clay so tha.t a complete curve could be

recorded and compared with Keller a:Qd Westcott's w·9Jrk on

Missouri dlays (1948, p.l02). T~ remaining samples were

run a.t increased sensitivity to bring out any 1ntere.st1ng

minor features.

Discussion of Differential Tqe.rmal Curves

The analysis of the whole clayc· imple ~t}!'riOO '"'ohms

does not suggest the presence of any other mineral than

kaolinite. Its well characterized endothernd.c· p~ak at 600

AI

C I

E I

I 100

I 200

WHOLE ' CLAY 800 OHMS

WHOLE CLAY 200 OHMS

5.0 JJ TO 2.0p 200 OHMS .

2.0 II TO 0.5 J.1

400 OHMS

0 .5 J.1 TO 0 .211 200 OHMS

I 100

I 200

PLATE II

DEGREES CENTIGRADE

I I I I I I I I I 300 400 500 600 700 800 . . 900

. I

3bo 1 4bo 1

5oo 1 sbo 1 1bo 1

8!o 1 9~0 DEGREES CENTIGRADE

DIFFERENTIAL · THERMAL ANALYSIS CURVES

A:l

\

\

F

I 100

I 200

0.2 J1 TO 0.05 p 200 OHMS

I 300

PLATE III

DEGREES CENTIGRADE . I I I I I

400 500 600

G1~•

H

J

K

I 0 .2" TO 0.0!5"

200 OHMS

I .J-..........• I /1 / 0.2~0Sp

100 OHMS

GEORGIA KAOLIN

800 OHMS

GEORGIA KAOLIN + No4P2 07

400 OHMS

I 100

I 200

I 300

I 400 500 .JOO DEGREES CENTIGRADE

I roo

I 700

I I . I 800 900

. I lOG

I ,

I . toO

DIFFERENTIAL · THERMAL ANALYSIS CURVES

I ,

I 1000

degre~s c. end exothermic peak near 980 degrees c. are well

repnt;IJt~mted. However, when one compares the curve of the

Mexico Refractory Comp~Icy"'s clay (curve A) with well cryst­

allyzed Georgia J{aolinite . (curve J) it is noticed that ,--

the intensity and the sJtra.l!Pness of both peaks of the

former are poorly developed in c'ontrast to those of the

latter.

This same type of supJ)ressed and rounded curve repre­

sented by . the Reh'actory Company's. plastic clay ·also ·is

. found to a.ppear in th-e very fine gra.de of- a fractionated

Georgia kaolin (Speil et al;. ;. 1945~ p. 22). . The coarser

grades gave (20 -0.2u inclusive of Geor$.1a Kaolinite) peaks

which are exceedingly sharp.: · In contradistinction to these

s~rp peaks, a sudden cha.nge occu,rs ,,below 0.2u9 The peaks

become notably rounded and less intense, particularly the

exothermic peak at g·ao degrees o. The temperature a.t which the

exothermic and endothermic reactions take place also are re­

duced by as much as 50 degrees a. hduct1on 1n intensity, sharp­

ness and temperat~e of the reaction, for the fine fraction .. . :::_

indicate that less free energy is released in the reaction •.

A lower tmergy structure far the less than ~2u crystals

than for the la,rger crys'tal.s is therBfore thought to exist.

This lower free energy ma.nefestat1on is thought to repres.ent

a disorderly superpositidan of kaolinite layers. Kerr and

Kulp (1948, p. 397) go so far as , to sa.y .tbat the de-

gree of. orderliness in the superposition of kaol1n1te

la ~!ers d_ecreases in -~rder_ of decomposition tempera. tu.re

from dicktte thr r.)t, g h kaolintt·e to halloys~te.

Through e.n increase in seP..sitivit.y,· curve B b~ings out

two undula.tions at 140 degree.s C. and 200 degrees C .• nOt \ . . ·

record~d by .- eurve IJ. The curve has been so . magni~ed that

the majot- endothermic and exothermic p·eaks . extended beyond

the limit of the recording p~per. linor endothermic reactions

developed in t~ 14--2()0 degree re.gion may nave_ .their origin

. ·in neither; some; or all of the following similar oc·curle~eal.•

(1) Fine .fractions of' ka.olinite (Spe11 et a:L. 1945, p.2-2)

(2) He.ll~ysite . (Grim and Rowland, 1942, p.753) (A.P.I·. /h, fig. 8)

(3) Kaolinite and illite mixture (Grim and Rowland;· 1942; p. 896)

(4) Kaolinite and montmorillonite (Kerr and Kulp_~ 1948; :rG 415)

Speil am his associates ~powed that very fine; poorly '•'' ! • ~ ·.! . . .

crystallyzed. kaolinite yields . an: emothermic- peak at '150

degrees o. wh1~h ' they attribute . to the evolution.\~ of ads_orbed

wa.ter. This new type of curve for the minus o.2u kaolin-

ite 1s very lJ1111lar to that obatined .from halloysit.e. Assym­

metry of the major 5so:.socr de~e.e ~tnttttbera1c· 'i ) J -, ts ·: aeteic)j-et~-· , :~: . '. .. .. ,., .. ··. . . .

in the- :tine :k:aolihite ~ to ' tfte ._ , ,l>o ·1n'ti--~~)~.bere one cannot_ distinguish

1 t from halloysite_. A mixture of 25~ montmorillonite or

10,: 1ill.te, ·with well-crysta.J.iyzed (orderly stacked)

kaolinite will give a similar curve.

A very slight undula·tion at 75 degree c. may be due

to the presence of ·montmorillonite or illite or both.

Curves C,D, and ~- are fairly s1mila.r exeept minor

undulations at 750 degrees c. anp. 900 ·degrees c. 1n curve

E are most evident in curve E. No explanation is of'fer­

ed here.

Curve F was the first curv~ ;' in the 0.2u to o.o5u grade

to be analyze~. ·. It cont,a1ns an exothermic peak at about

280 degrees, but no endoth'CP.mic peak in· the 140-200 de­

gree c. _range. The 280 '·degree c. exothermic peAk is the

result of oxid~tion of orgenic matter that had concentrated

in the o.2u to o. 05u grade. This Wf)~ established by

viewing aggrega.tes under the microscope immersed 1n hydro­

gen pyroxide. Poor packing in the sample holder might

c account for the failure of the 170 - 200 degree •

endothermic dips to show.

G and J curves are both very similar except that the .

endothermic dip a.t 200 degrees c. is more pro~ounced with

greater sensitivity. The exothermic peeks at -225-300 de­

grees c. are attributed to organic matter as previously

proven. The bimodal. nature of this curve is apparent and 0 •

adds c cnsiderable difficulty to its· interpretation. No 'r ..

expl mations for this type of curve were fo\md in·~ the lit-

erature~ but similar b imodel endothermic peaks have been

published •.

46

In sample K , Na4P2o7 • 10 ~0 was added to the Georgia

kaolinite to determine whe.t ,her any Na4P2o7• 10 ~0 that

had not been romoved from the c Jay wQl;lld give anom8 1ous

e.ffects~ None was obta-ined. ~ppa.rently Na.4P2o7 • 10 H20 .

h ro been removed •

4'7

CHAPT:ER IX

X-RAY DIFFRACTION ANALYSIS

In clay mineralogy no single method · of analysis is

completely sufficient to entirely .determine the clay

mineral constituents. Ea;ch method -gsually.· 1·s supported

by a mther. In this investigation, x-rey analysis seemed

.to offer the most conclusive · evidence reg8rd1ng the clay ·

mineral canposi tion of the Mexico Plastic Fire Clay a.nd

helped to explain the r esults of t ·he foreg·oing e'rialys••·

Procedure

-A General Electric XRD-type 1 x-ray unit was employ­

ed to obtain x-ray diffraction pa.~ten-ns of all .u.mples·.

' unfiltered Fe radiation was used. Calcium-glycerol sat­

urated samples· were prepared after the meth~ of Jeffries

and ~ackson (1949, PR•65-67) ~o enable one to establish

the presence of ,montmorillonite or ·illite. The .)powder

wedge method of mounting was used at first to obtain

patterns .of all samples~ but m041ficat1ons were made

as will be discussed 1n the ensuing discpssions•

The Strauman1s technique of film calibration could

not be adapted to use with the circular cameras ava1labl~ • .

All measurements then required~ consideration of the .

ca.mere radii. Film shrinkage wa.s 1gJ?J.or·eQ!._.

48

· ·Results of ·Powder Wed.ge D1.ffraction Analysis

The diffraction patterns of· t·he 20-2u grades re-

v.ealed a. progressive; decrease in quartz c <ntent down to 2u.

The first Qom:tna.nt cl:y lines to show up 1n the· 20 to lOU

gradecorrespond to 'tnterp1anar spacings of 7 .la~· 4.39~ e.nd

3.56. Aqsstrom ~its. ·.In the l0-5u grade the .. 1 • . 48 line appear­

ed most strikingly. The 5-2u grade was essentially the

same as the l0-5u fr8ction •• Below 2u the quartz lines

suddenly diminished in· 1ntens1 ty to where. they became

ha-dly detec~able. The o.Su to o.2u and 0.2u to Q.05u

fractions offered the best patterns from which to make

diffraction measurementsr. The lines wete · not as diffuse

as tbose:·: of the o •. osu material~ nor d 1d any quartz lines -

complicate· the filtn •

. On page 49 are listed the interpla.nar spacings along

with the respective relative intensities. Intensity meas­

urements were made without the aid of a densitometer;· and

are therefore indicated qualitatively as bei·ng very st~ong; '

strong, weqk etc. instead

These 1ntarplanar spactngs and intensities are in

good agreement with kaolinite in the 11 terature. {Hen­

drick~ and Fry fl930J Gruner Cl932-:J. Halloysite is

easily.excluded because too many lines are present (Nagel- ·

schmidt Cl934J~ lt\tbmel Cl935J; Ross and Kerr /3 193,+1-J.

49

TABLE· III

NUMBER !NTERPLANAR SPACINGS INTENSITIES

(1) ' 7.18 . V. St.

(2) -4.39 ,v.st.

(3) 4.14 w (4) . 3.90 .' M

(5) 3.56 v.st. (6) 3.35 M

(7) 3.03 M.W.

(8) 2.'82 M.W~

(9) 2.73 M.W •. .

(10) 2.55 . St..

(11) 2-.49 St.

(12) 2.38- }4: . . '

(13) 2.33 St.

(14) 2.27 · St.

.(15) 2.20 St. -

(16) . 2.07 w

(17) 1.97 w

(18) 1.88 w (19) 1.83 w

(20) 1~78 w

(21) 1.68 w

(22) 1.65 w

(23) 1.63 w (24) 1.48 v.s11, ..

5{)

• ·

Further Investigation

The presence o~ lines corresponding to -18, 15, 10,

B, ahd 7 :Angstrom units -on the preceding patterns were . . / .

·notices ble. Correct interpretation of' these lines is crucial . . . .

if illite and montmorillonite are to be identifiEd. These

lines ~nc~eased in intensity and sharpness as the quartz

content be·came higher; being extremely diffuse and less in­

tense in the finer gredes. A pure quartz sample produced ·

sharp and intense lines.

It is common knowledge that x-r8y film preferentially

absorbs dif'ferent wave lengths of x-rays. The ab~orption

edges for silver and bromine are located at about 0.5 and

0.9 Angstrmm units ~espectively. The general radiation

emmited by the target a.t high pote.ntials includes these

wave lene;ths. This would account. in part for the apparent

low angle diffractions observed on the film •• Clark,

Grim, and Bradley (1937, p. 322) propose ~hat these lines

may also be caused by diffraction of· general radiation

by prisma.t1c . planes of clay minerals or .. by (101) planes

of quartz.

An effort· wes thepe.fo:ee made to distinguish the

absorption edge from illite and montmorillonite lines.

Sisson, Clark, and Parke~ (1936; p. 1637) have shown that

these absorption edges can be reduced to a general fog

by backing the film with a flurPzure screen, or they can be

5i

· dist.tilgui,shed f'rom true diffra,ct1on 11ne.s J i.ft tb~y remain

in the same positi~n on the' filni~ when the radiat:i.on is

chcrnged. Before ch8nging ·the target, standards of kaolin,

illite a.nd montmorillonite were made;. both 1n the unsat·· ·

urated ·and glycerol · saturated stat~. Diffract~on patterns

of oriented ?ggreg~rtes also were· made with iron radiation.

Investigation..of Thre~ Layer Lattice . N-inera.ls

Cl?.rk, Grim, and Bradl:eY (1937, p. 322000(324) have de­

veloped· a technique whereby clay pa.rticles all expose

the same 001 plane to x-rays so the intensity of the

diffracted lines·will be very much. greater than when the

particles are oriented . ha.phazardly as i~~ the powder wedge

methods • . If clay particles are allowed to settle .from

suspension on to a glass slide,· their ba.sal planes become

parallel to the glass slide. . Once - ~'~his is ·dried a.nd

scraped off with a ra.zor . blade, the plate~l~e aggregates

can be rolled around a glass fibre~ The ~ample is mounted

and rotated in the x-ra.ys beam so th~rt · 001 pla.nes are

. continually exposed. Glycerol was used here 1n bulk form

both as a mounting agent and fetr causing the montmorill- ·

onite lattice to expand to 17.7 Angstroms.

MacEwa,n (1946,p. 288) repor..ts~~that he has detected

as little as lfo moutmor1llon1te with this method.

Results of the oriented aggregate diffraction patterns

revealed a medium, very diffuse diffraction line at 10.2

Angstroms which persist-ed a.fter being heated to 110

degre.es. It resembled none of the absorption edges. 'I'here

occurred a faint darkening near the · 18 Angstrom region . .

but not characteristic- enough to be e d1ffr~~t1on line.

One fa.:ti.tor hindering the ·1a Angstrom. determination is that

the largest interp:tanar spacing obtainable with -this

camera is about 20 Angstroms using_ Fe r8d1at1on. In a.n

effort to sharpen these lines am to ·determine wbetther

t.he low angle reflections were interferences, a Cu tube

was 1nst8lled along w1 th a nickel filter to gfve mono­

chromatic radietion. A Laue camera was used with a. very

small _lead stop to eneble ~ small angle reflections t"o be -

recorded. Results were not very satisfactory with this

procedure as no good mean~ of mounting oriented aggregates

were available. ·Regular powder samples had to be used

and no lines that could be conclusively attributed to

montmorillonite were discernible.

X-ray analysis indica ted that quartz, kaolinite and

illite are present a.nd are distributed among the grades

in a.ccordance with the results given in the following

table.

53

TABLE IV

. DISTRIBUTION OF MINmALS ACCORDING TO PARTICLE SIZE . - _.-;-........~...........,_..............,_

IN MEXICO REFBACTCRY COMPANY'S PLASTIC FIRE CLAY

GRADE

20 to ·lou .

10 to 5u

·s to 2u

2 to.5u

• 2 to.05u

-0.05u

MINIRALS PRESENT

quartz and kaolinite

" " • "

very little • ?. • ?. ..

..

illite!

1111te

illite

54

INTERPRETATION OF ELEC1RON PHOTOMICROGRAPHS

Plate 4

Photos o;n Plate 4 are . re·presentet i ve of the lE;lss than five

micron grade of sample-J?,pa.ge ~29 used in the sodium p~o­

phosphate trea.tme,nt. The lath-like particle in photo A

can be interpreted either as a.n ha.lleysi te crystal . or a

latteral view of a. kaolini'te plate.

~hoto B reveals goo~ plates of kaolinite which are

lacking ~ n the hexagona.l outline cb~racteristic of well•

crystallized kaolinites • . Random growth of the crystals is

indtcated by the m.a.ny ~etreating prisme.tic faces·.

Plate 5

Very thin, transparent sheets 1n both pictures give

good indication of being illite, but this fact is not support­

ed by x-ray data for the 2 · to 09'5u fra.cticbn.

Plate 6

Both views on Plate 6 show how well the particle size

segregation was· made. Low ma.gn1ficat1on revee.ls sharp

edges a,nd transparent particles, indicating that particles

in this range were fe.irly well diSpersed and not composed .

of mny finer particles.

Plate 7

Resolution of the finest fraction 1~ made ~ere. At iow

55

magni.fication (B) minute lath-like structures are noticed,

suggesting the. presence of ·l&llloysite. Higher ma.gnifice,­

tion of' another view (C) _brings qut the columnar charac~er

of these crystal~'• This . particle is interpreted as being .'!\ -,

halloysite. P.ic~~ed _in A 1_s:, some. material too fine to be

resolved. Organic mat,er,· ·has been concentrated in this . . .

frpction and probably comprises the - ~m. jor portion of' the

view.

Platre 4 Electron Pho 'bomiaro-gr ph~F

- 5u :X 6. 500

56

Pla-te 5 Electron Photom1crogre:phs-

2-0.5u X 6,500

ttl (A)

(B)

5J

Plate 6 Electron Phot omicrographs

0.2u - 6.05u

lu X l'3~:UCD'C>

( B)

58

Plate 7 Ele c t ron Phot omi crogr aphs

- . osu .

~ 11,400 (A)

lu X 1 9 ,000

(C )

59

60

CONCLUSION

From combined analytical methods the c.lay mineral- ·

ogy has been determined•

Kaolinite crystals oecur in every grade from twenty

microns down to ana including less than 0.05 microns. By

means of the orfent~d aggre@a.te- technique, -illite has

been identffied a~ occnrr1ng in the ~ess tre.n 0.2 u

fractions. There is a possibility that · montmorilloni~e

is present in the finer than 0.2u fr .retiqns, but it would .

be hazardous to defi~itely est?blish its_ presence. Elec­

tron photomicrogrr phs give good in:d icat1on that micro..o

lttes of halloysite are, di~tributed throughout the less

til ?!'l o. 05u frection. I

Of the detrital grains~ quu=~rtz is by far the most

·dominant. It constitutes all the coarse fr e ctions, but

tourmaline, z' rcon, and rutile are distributed in exceed­

ine:ly small 'quantities.

BIBLIOGRAPHY ··

Abramson, .Moyer, and Gorin,

Electrophore'sts o,f Proteins: N.Y. Reinhold, 341 pp.-' ~:::

1942. .. . . v Allen' ~ T.

Mineral ~ompos i tion a.nd Origin . ·or Jdissour:i Flint am Diasppre . Clys: Mo. Geol!. Surver and Water Resources,

• • • w . •

Appendix 1 V, 58tb Biennft.l Report·~ pp.l-24, 1935.

Allen~- v. T,

"'- Cheltenham Clay of Missouri:' :.,. Mo. Geol. Survey and

Water Resources, Appendix V, 59~h B.:tenn1al Report,

1937.

Alexarner~ A.E .• , and Johnson, . P.

Colloid Science: Vol. l and 2, Lot)don, Un1v. Press,

837 pages.

Atkinson, H.J., and Turner; R. c.

Soil Colloids 11. Separ~ tion. by Peptization: Soil

Sci., 57, pp.233-2 40, 194~.

Baver; L.D.

Soil Physics: . John Wtley and Sons, New York, N.Y.

398 pp. ' 1948' •.

Berkelhamer, L.H.

Am Apparatus for Dirfertial Thermal Analysis: u •. S •. ·

Bur. Mines. Tech. Pa.·per, ·664, _p.33-55~ 1941.

Bouyoucos, G.tT.

Hydrometer Method .for Making N.ecba n_ical Ane.lysis

of Soils: Bu J..l. Amer. Ce~. boc. 14 (8)-, pp.259-2E.2, · .. .. 1935 • .

. s Bradley, R •• , a.nd Miller,- B.K.

Pro_specting, Developing· and _Mining. Sem1..;.plattic F1re­

cl8.y in Missouri: Am. Inst •. Mlning and Met. ,Engrs. Tech.

:Pub. No. 1328: Mining Tee. 5 (4) ~pp.; Ceram. Abs.

Nov. 1941, 1941 •.

Bradley, V'(. F •

. a. · · N1.olecular ~sso f: iat+.ons between Montmorillonite< and· ·some

Po;lyfunctional Orgfrnic I4quids: Jour • . Am. Chem. Soc. ·

67, pp.975-98l, i945.

b. Diagnostic . Criteria for CJB y Minerals: .Am. Min. 38,

pp. 7 04-713 ,· 1948.

Bradley, W.F. a.nd Grim, R.E.

Colloid Properties of _ .La.rger Si11ca.tes: Jour. Phys.

Chem. 52 ( 8), PP• 1404-1413 ,· 1948. f·:

Bray, R.H • . , Grim, R.E. and Kerr, p:·F.

Applica~ions of Cle.y Minere.l Technique to Illinois

ClC~y and Shale: Bull. Geol. Soc. A. 46,· pp.l910-1926,

1935· •.

Brindley, G. W. and Robinson,. K. ·,.

-Randomness 1n the Structures o:f Kaol1n1t•c Clay Miner-

als: Faraday Soc. Trans. 42B, pp.l98-2051 194& •.

63

Burst, J .Fr.

The . Clay Mineralogy of Two Typ:l>e.al Missouri · Fire­

clays: Unpublished Thesis, Univ. of Missouri, -1950.

R Clerk, G.L., Grim, .E~ _ and Bradley, W •. F.

Notes on the Idenf1!'1cat1on' o:r :Minerals in.Ciays by X­

ray ·Diffraction: Zeit. Krist • . 96, pp.322-324; 1937. ·

Ctrnpman, H.l. and -~elly, I.P. ~ .,.-

Tre Determination of the Repleceable Ba.ses and the Base .

Exchange Capacity of Soilst Soil Sci., 30, p.39l, 1930.

Davis, tl.w., et al.

Electron Mj_ crogr~' phs of Re.ference Clay Minerals: Am.

Pe:tr. Inst~ Proj., Clay Mineral Std·s. , Prel. Rpt:.

#f?, 1950.

Drosdoff, M.

The Separation and Identification of the Mineral Con.­

sti tuents_ of Collo1 dal Clays: Soil Sci., 39, pp. 463-

477, 1935.

Edelman, C.H., and Favejee, J.Ch. L.

Dn the cr,stal Struature of :Montmorillonite and Halley­

site: Zeit. Krist.·, 102, pp.417~431~ 1939.

Endell,·K., Hofmann, .u;, and Wilm, D_.

ffa ture of Ceramic Clays; Ber·. Deut. Karam. Ge~. 14,

,(10~, pp.407-438; 1933.

Galpin; s.L.

Studies of Flint Clays and Their Associates: 4m.Cer,.

Soc. Trans. 14, pp.306-338~- .1912.

Giesking, J.».~ . · Mecha.nism or C8t1on Exchapge 1n the Montmorillonite -

..

be1del11te-nontron1te Type of Clay lfinerals: ;Soil

Se-enee, 47. (l);· pj•l-14, , 193~. · . . .

GrahlPI!; R.P. and Sull1ve.!l;· . Ji•lt~-

Cri tical study of .. tllods of J)eteltnining Exche.rigee.ble

Bases 1n Clays: :.Jourj; .. ·•· ·tEJrr~ ~(jc. 21;. J>P:• 176•

·183~ 193fle

· Grim, . R ••.•

a. ;l·el at1on of Composition to Properties _at Clays: Jo~.

Am. Cer:. Soc. 22 · (5), pp~ .14l-l5JJ. . . 1939..

b. P~opert1es 'Of. Clays; 1n Rece~t' Mar~ ·S~iments: .Ill~ •, .

As-soc. Pet·• Geol.(. ·, .. Tul~J, Ok:~., , pp.466-495, l939e ~' ~ ~'i · j , ·,

Grim, .R.E., AllaJtay~ Wl H. and Cuth~t. E.lt. . ~~

React~ on of Di.fferent c:lay K1ner~als . with Some Organic . r

. ·Cations: Jour • . Am. Car: .• Boo. zo·~ PP• : 137~142; 1.94'11.

Grim, R,.E. a~ Brad.ley, ~.E:.

Investigation of the Effect of .Heat on CJ.ay Minerals.; ; '

Illfte, am •o~tmer1~on1t~: Jo~: .Aa. Cer • . Soc• .83.~

pp. 242-248; 1940. • .

Rehydration and hhydratien ~t Cll~·· Mineralsi . Am. lWl~·

33 ~· PP• so-sa; 1948.

Grim~ R-.E. and Bray, R.H.

TJ:e llineral Constitution of Various Ceramic Clays: JC)~

Am. Cer•Boc • . 19, pJt •. 307-315~ ·193a. .

Gr~; R.-. s.m Rowland; R-.A.

Differentia~ Thermal Analysis o~ Clay lamerali .~ Other

6_5:.·

(.

Hydrous_ Materials: - Am~ ¥1n. 27, pp. 746-761, 801-818: . . . .

Ill. ·Geol·. Surv. ·.Rept •. Iri?. 85, .1948. -. . .

·. Differential The~al/' Analys1s · of Clays and Shales · . ' . .. :: .

- ~-- ~ontrol and Pr.ospe·.~tini·~·. :Jieth~' J ouxf . .. Am. Cer .• ,.. . . ., . ~ . . ..

Grun·er~· ·J ~ w. Tre Crpstal Struc~ure. of ·Kaolinite: Zeit·. Kriir~. ez; pp. 75-78, 193~. I

' . . . .

Ha.rman, C. a.· ~nd Frau11n11· FeliX . · .. . .

Properties of Kaol~ilite as·a Fur:}c~1on of . Particle ·

· Size= Jour. Am. Cel'. Soc. ·.2a; . p .• 253; ·:J-,940.

E ~user, .• A.

Colloidal Phenomena: MeGraw-H111; N.'!• 294 pp. 1939.

Hay.ser; E.A •. anci Ree~,v<?•.~~

Development of a NQ: lethod for Measuring Pe.r.t1cle­

s1ze D1str1@ut1on in Colloidal Systems: Jour • . Phys~.

Cb~ 40·: PP• 1169-1182, 1936.

Ha:user E. A • . '~nd leb:~cbman .' ·'1 .. 1

Particle Size De1;erm1nat1on of Colloidal ·aystans by

the Superc.ent~i!'Uge: :Jour. Pbys • . ehern • . 44;. pp. 584-5~1•

1940 •

. Hellman~· N.H., Aldrich~ D. G. and Jackson. M.L.

FUrther Note on an X-ray D1ff.ract1aa Procedure for the .

Pos1 ti ve Differentia t1on of Montmor1iloA1 t .e from

. llycirous Mica: Soi~ Sci .• . Am •. Proa. ~ pp • . 194-:-'20Q'• 194~•

Hendr1 cks , s. B·.

On the Crystal StructUre of the Clay Jttnerals; Dickite_,

·-·Halloysite; and Hydrat~ rlauoys1te: ~-• . Min . .. 23, PP• . .

-295-301;· 1938~

Th~ Crystal Struetilre- - ~r '.,e.'erite ~d the· Po;J.ymorph1sm· of

the Ka.ol1:r::t Mi~eae.ls· _: :z~it. - ·_Kris'b. _.1oo; PP•509~5la;l939. Hendricks S.;B • . and FrY,- W •. ft~ :>~

The Results or X•ray and :M:tcrosot • ·ic. Examinations of . .-.t. ~.. '

Soil Colloids: Soil-... Saj{ •. ~- ~9 ;; Pii• 457 ~48_0, 19~0;.

Herold; P.o.

Mineral Chara.cteris~_1cs or Ce~tral' 141s~our1 Clays;Chap.

Vl, Fireclay Districts · of ~st Central Missouri~ :UC, •. ~ . . . . . . .

. . Geol:. Survey and Water Re~;c~~~f· vol.. 2a; 2nl series

194~·

Hofmann~ U•. Endell, K. an<1 Wiim. - !!~

Kristallstructur and quellung von m-ontmorillonite: Zeit • . · - ,

Krist. 86 (5-6) PP• 340;..348, Ceram Absi. 14 (4), p .•

1oo: 193~ ..

Humbert~ ;~:.R~.amd Shaw; B~ ; •. J .

Studies of Cla.y 141neral Partieteaf w1:bh the ·EietrOJl

Microscope J.t · Shapes ~fba,y" Crys:'l;a];sl. Soil Set<. 52 1 • A- ~ ~ ' : .:

pp. 481-487 ~· l94J.r.

Jackson; M.L. end Hellman~ N.N.

X-ray Difb.a.ction pr-ocedure for Positive Differentiation .. of Montmor1lloni te from-~ Hydrous !ttca Soil Sci!~ Am~

• 1

Proc. pp. 133-145; 194~•

Jackson et. ·s~.

Weathering Sequence o~ ~lay-Sized Minerals in Soils

and Sediments: J.t. Fundamenta~ Genere.llzat1on8: _eJour. . . ·pp,.s, Chem. an~ Coiioid Chem. ,. 52~ . PP• 12a7-1259;1948e

Jeftries; C.D. and Jacksfl>n, . M.L.

Mineralogical Analysis o:r·· Soils: . Soil Sci·., 68, pp~ 57- .

73,

Jenny~· H.

Studies on the Mechanism .or Ionic ~cbange .in Colloidal

Aluminum Silica .. tes: Jour. Phys. Chem. 36 ; PP• 221'7-

225& •. .

Jenny, H. and Reitme;ter1 R.F. ·

Ion Exchange 1n Relation to the Stability o:f Colloidal

Systems: Jourl Phys. Chem. 391 pp •. 543-604~ 1935-.

Johnson, A.L.

Surface Area. and its Effect on Exchange Capa_city o:f

·-" Montmorillonite: Jow. Am. Ce:r. So~ •. 32;· PR• 210-2l4f; l949e.

Johnson Ai)-· a.nd Norton~ ~~ H.

a• . F\mdemental Study of Clay; 1 Preparation of a .Pnrified

Kaolinite Suspensfon: Jour .• . Am. Cer. Soc. 24~ pp-.64~9 ;

1941.

b. Fundamental Study of Clay; ll !59chanism of Defiocculation J ..

1n the Clay-water System: . our-. Am. Cer •. Soc. 24; PP.:•

189 ... 203, 1941.

Johnson, A.L. and Lawrence; w.a •. Fundamental study of Clay; 1 t "Surface Area and 1ts Eff'eet

on Exchange: Jouri Am. Cer• Soc~ 25, pp. 344-:346~ 1942.

Keller·, W.D • .

The Geology of Missour'---the Clays ·or Jttssour1: Univ.

of Jlq. Studies 19; (3), pp. 376-384~ 1944. . . ...

. Evidence of Texture on~ thEi Origin' of the . Cheltenham

Fireclay of ~sso'ur1 and Associated Shalesi Jouri·· ~

Sed. Pe~• 16, (2), pp. 63-71~ 1946.

Keller, · W.D., and We$tcott, J.F.

· Differential Thermal Analysis of Some Missouri F1re­

cl~.ys: Jourle. Am • . Cer. Soc. 31~ pp.100-l05, 1948.

·. Hig tsr Alumina Content of Oak Leaves and Twigs Grow ...

ing Over C_:Ey . Pits: Eco. Geo.. 44; No •. 5·, 1949r • .

Kelley, W.P.

Base Exchange in Relation to Sediments in Recent 14arine

Sediments: Am. Assoc. _ Pet:. · Geo:L.; Tulsa, pp. 455-4651

1939.

Galcula t1ng Formulas for· Fine Grained Minerals on the

Ba.s1s of Chemical Analysis'' Am.Mtn. 30; .pp.l-2o, 1945.

Kerr, P.F •.

A Dec~de of Research · on the Nature of Clays: Jo1m • .Am.

Cer. Soc. 21·;· p. 285~ 1938.

Kerr, P.F., and Kulp= J.L.

Multiple Differential Thermal Analysis: Am. Min~ 33~

pp. 387-419, 1948.

Kerr, P.F., Hamilton, P.K. et al • .

Analytical Data on Reference. Clay Minera·ls: Am. P•tr.

Inst • . Prolf• 49 ~ Clcry !.JI1ne£~~ lite mardS:f Prel1m. Rpt. _ 1

II /! ,· l95o. __

_ Kerr, P.;F., · Kulp, J.L. ·am - Hamilton~ P;K.

Di:t:t'erential Thermal .nalys1s or Re.fe:rence Clay Minere.l ,_­

Sp~imenB: Prei1JQ;.. Rept ·. ll 3•: .Am. Petr. Inst. ProJ. 1· · --

49~ Clay Mineral Stema ms; 194~~ Krumbe1n,· W.C. and Pett1l.o~~ - - ~~Jt.

~ual of Sed1inerita.ry . Petro~ap.hp: N.l. ~. Appleton

Century end Co.· Inc., 1936.• 549pJ». _

Ksanda, C.J. a.Q.d Barth; T.F.W.

Note on the Structure of Dickite and other Clay Minerals:

-Am. -Min. 2o.; PP• 6:31-637; l93a.

Loomis~· G.A.

Grain Size of l•hiteware Clays ·as Determined by the And;;.

reasen Pipette.: Jolll'i. Am. Cer. Sec. 21• - pp.~9~·399;193~ • .

McQueen, H. s. · Geolo_gy or the Flrecla.y Districts of East Central Mo.:.

Moe Geoli. Survey arid Water ·Resour·e]es, vol. 28~ 2nd s,er1e•:t .

1943·.

MacEwan, D.M.c.

The Ident1.f1ca .t1on and Estimation of the Jlontmor1llon1te

Group of Minerals -with Spe~ial R~terenee to -Soil -Clays:­

Soc. CheBt. Ind. Jourt • . 6.~~, PP• 298-304, l94q• - \·1

lla.egdefrau, E. and Hormann, u.

Crpstal Structure ot Jlontmor1ll_on1te: Zeit. Krist~. 98;

PP• 299-323; cer8JI. Abs -. l8 .(2), .. p.ss~ l.93'1t.

Marshall;,· C.E.

7r0 ·. a:. ..~:eNew .J4e.tbod ot , Determilling t _be · Dis-tribution ·. Curve of Poly-!-

. . .

i26A (802) ; - pp.· 427-.43i~ 193q.

b,. T~e' ~1entat1on- o:r an Is.otropic P~rticle in an Elea.

; Field:

St\JI~es ·1m tne·· Degreft ot :Dispersion o:f the Claysf JJ; No~e~i on the Technique am Accuracy o:r the lleehanieal

A~lysis Using · t~e Cen~riguge: JG~. Soe1. CheDt. Ind. ·

sm·; PP• 4414-450 ·; 193lf.

llehJJel ; Jl.

·U)er die strUktur 'Von Halloysit unci lletehal.loys1t: Ze1-.

ICristte ·g.o-;· P:P• 35-43\_;; 1935.

:Meyer; .•• W.

Clay Co·lle1ds and Belated Properties: U.&. B~. Stds:•

Jo~• R.e$eareh~· 13 ~ 147; 1934i.

Moor•: J. ~- . ~y; W.H ••. and Jlitdleton~· R.B. Methods ot ~term~bg - the Amcnmt et Col:to1dal Material

.· ; -

in Sells: Inci~ Eng• Cb- 13·;- P• . 527'~ 192:L·.

lluelle·; James ;D. &. Stlldy of the. _Gelation· of ~.ir Sf)tting Re:tractory Mor~a.rs ·:

Thes·ts~ phP.Ittssour1 School o:f Mi~s am Metallurgy; Un1v..

o:r Missouri ;· 1949.

Nagelsebmidt·; G.

R.entgenogra_p~sebe Untersuc;b1ngen an Tonen: Zei'ti• ~istl. ·

8'-~ Pll• 120-~45, 113~•

Norton,· F.H. ;. and SpeU, ~.

a. The Measurement of Particle Sizes in Clays: J~. Am .•

Cert~ Soc. 21~ ~•· 89~97· , ·19za. b. A. Fr_aet1ona.t1on o:t Claf into Closely 14onod1spersed Systems

Jo~• ADI'• Cer. So~. 21, pp.367-37Qj 193 ••

71

liutt_1ng; P. g. . .

The Action or Some .Aqueous Solutions en Clays of the ·

-MOntmorillonite Grolip: . u:l. (fe~l-.Survey Prof. Paper

~98-E,: 1943! • . '--

Pe_nningt:O$, R.-P. and J~ckson, ll.~. _-

Segregation of Clay Jllinerals of Polyeomponent Soil

c1ays: 8~11 ·sci .• Soe. Am. Assoc. 12, p. 452- 1 1947;.

Reiman.;··. w. ,. Reuss~ &l'el). and Naiman, :&.-

Q.us.nt1tat1ve Analysis; a Theoretical .Approadl: Jlc Graw

Hill;' If. Y. pp~. 162-168, 1942.

_Ries, Bayley, and Others

High Grade Claya o.r the -Ea~ter~ · U.l.: :Bul.l. U.S..G.S. /

II !08·, 1922.

Roberts)' C .• N.

A. History of the Firebrick and Refi-a etory Industry or Miss cm-1: 13llll.l. Un1 'V'. o:r Me. School ot Kines and 14etf • .

Tech• Series. II 75, . 1950•

Robinson; W.D_. , . and. ·Holmes, R.S.

The Chemica.l Composition_ ot Soil Colloids: U.L. Dep~.

of .A.gr. BuU. 13ll, l924.

Ross; q.s. and Hendricks, S.B.

Jlinerals of the Montmorillonite Group: u.a. Geol:-. Surv .•

Pro:r. Paper 205-B,· PP:• 23-79, · 19441.

R:oss; C.L and Kerr, P.F.

The Aaol1n lttnersla: U.s. G. s. Prof. Paper 16!?-E, ppj.

151-176, 1931.

72

· Ross. ~. S.· and ·Shannon,. E. J. The ~erals of·. the . . Bentonite a.nd R~18.te.d Clays .and their

Physical Propertie~ ·:. ·. ;~our .• AJn. der. Soc. 9; PP'• 77-96~

192&.

Roy, Rusti-um

Decompos1t.1on and ~·.S;ynthes1s o:f .the· 141cas: ~!our .• w,·s . ... .

. Ceram. s .oe.. 3!~ 202-209, 1949 • · .. . • . 't,

· scbGllenber~·~ and Dp·e1b,lb1s

.balytical :MeUtods 1n ~se Exch?. nge Inve·stigations:

Soil Sci·. v.ol ai,p. 1Slji73, 1930. ' ~ ~ -

Sisson,·. w.A. ,. ·Ci~"rk~ . G.~· · a~ Parker; E.L

A~sorbed Edges 1ft the X-ray Patte~s of .!atur' ~ Mercerized Cellulose: Am. C.bem. Soc. Jour. 58.· PP• . t

·., 103.5-1038 ~ 193& • . 1.

somers, R.L

141~roseop1c Study of' Clays: U.S .• G.S. Bul.l. If. 708~ p~··

294-299; 1922'.

Speil, ~., Ber-k~lbamer~· L.H • .et al.

D1fferent1al ·Themal Analysis, its Ap plication to Clays

and other AluminOus Jla terd.el·s: U.S. Dept.. of . Interior

Bur. 0£ Mines• Tech •. paper 664; . U.~. govt. Printing .

O.tf1etti 19~

Steele, .J.G. ant Bradrield~ . · R.

Sign1f1ca:nee of Size ·Distribution 1n the Clay Fraetion:

Am~ Soil Survey Assoc.B~l. 15~ pp.88593; ·1934.

Tha itl.a ·~

Electrodialysis of Mi~eral . S111cetes-an Experimental.

73

· et~y of Rock Weathering, 'Min. liag~ 27, 137-145; 1945 .•

V1nther and Lasson

Uber. KorngrGssenmessungen un Kaolin und Tonarten:

Be~. Deut~ch. C.eram. Ges. vol. 14, . pp. 259..:.279, 1933.

Wheeler; A·.A .•.

Clay Deposits: Mo. Geol. Survey, 11( lst series)

PP• 186-187; 189&.

VITA

John Edward May -was born in 1927 in Bro.oklyn; New

York. He attended the Strauberimtiiler Textile High

School wh~re he majored in chemistrY:• · Upon graduat1on in

1945; he ·entered the City College of New York and: majored

·1n geology and minored in chemistry. He received his

B.s. degree in the summer of 1949 arxl enrolled as a

graduate student 1n the Missouri .School of Mines and

Metallurgy the following FalJJ.

As · a graduate student; tte majored 1n geology, but his

courses contained work 1n ceramics 1n which he developed an

interest.. .During his last term at Mis.souri Sd.1 ooi . of

!anes, he received a ·. graduate assistantship· under })Jf. a. R. Grawe-.

At the completion of graduate work he w111 ent·er

industrial research 1n crystallogr.aphy.

74