mineral composition in relation to particle size for a
TRANSCRIPT
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
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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 [email protected] 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.
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Appendix 1 V, 58tb Biennft.l Report·~ pp.l-24, 1935.
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Burst, J .Fr.
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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$eareh~· 13 ~ 147; 1934i.
Moor•: J. ~- . ~y; W.H ••. and Jlitdleton~· R.B. Methods ot ~term~bg - the Amcnmt et Col:to1dal Material
.· ; -
in Sells: Inci~ Eng• Cb- 13·;- P• . 527'~ 192:L·.
lluelle·; James ;D. &. Stlldy of the. _Gelation· of ~.ir Sf)tting Re:tractory Mor~a.rs ·:
Thes·ts~ phP.Ittssour1 School o:f Mi~s am Metallurgy; Un1v..
o:r Missouri ;· 1949.
Nagelsebmidt·; G.
R.entgenogra_p~sebe Untersuc;b1ngen an Tonen: Zei'ti• ~istl. ·
8'-~ Pll• 120-~45, 113~•
Norton,· F.H. ;. and SpeU, ~.
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Cert~ Soc. 21~ ~•· 89~97· , ·19za. b. A. Fr_aet1ona.t1on o:t Claf into Closely 14onod1spersed Systems
Jo~• ADI'• Cer. So~. 21, pp.367-37Qj 193 ••
71
liutt_1ng; P. g. . .
The Action or Some .Aqueous Solutions en Clays of the ·
-MOntmorillonite Grolip: . u:l. (fe~l-.Survey Prof. Paper
~98-E,: 1943! • . '--
Pe_nningt:O$, 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
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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