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DEPARTMENT OF THE INTERIOR

UNITED STATES GEOLOGICAL SURVEY


GEORGE OTIS SMITH, DIRECTOR
N 388
THE COLLOID MATTER OF CLAY
AND ITS MEASUREMENT
BY
HAERISON EVERETT ASHLEY
WASHINGTON
GOVERNMENT PRINTING OFFICE
1909
CONTENTS.
Preface, by A. V. Bleininger................................:..............
Introduction.............................................................. 7
Colloids inclays.......................................................... 9
Sources of the colloids................................................. 9
Hydratedsilicates................................................ 9
Gelatinous silica................................................... 9
Ferric andaluminum hydroxides.................................. 10
Organic colloids................................................... 10
Artificially addedcolloids......................................... 12
Summary ......................-----.-------.----- --------- --- 12
Aginganddryingof clays ............................................. 12
Air drying....................................................... 12
Dryingunder pressure............................................. 13
Weatheringof fire clays........................................:.. 13
Agingof feldspathic bodies........................................ 14
Forms of colloids....................................................... 14
Sols andgels...................................................... 14
Coagulationandsetting............................................ 15
Examples of set gels............................................... 15
Formationof sols.................................................. 17
Electrostatic charges insols.................................... 17
Ionic reactions............................................... 18
Nature of gel formation............................................ 18
Stability of clay sols andgels...................................... 19
Protectioncolloids................................................ 20
Properties of colloids..................:.............................,......, 20
Viscosity............................................................. 20
Viscosity of clay slips.............................................. 20
Plasticity. ....................................................... 21
Actionof electrolytes.............................................. 22
Exchange of bases............................................ 22
Organic colloids................................................ 24
Mellor, Green, andBaugh's experiments. ...................... 24
Laws of coagulation................................................ 27
Absorption............................................................ 27
Lack of definite relationof absorptiontotemperature............... 27
* Relationof absorptiontoplasticity.................................. 28
Distributionof absorbedwater amongconstituents.................. 28
Volumes of clay gel invarious salt solutions ........................ 29
Distributionof salts ingels......................................... 30
Adsorption........................................................... 31
Statement of theory................................................ 31
Cellular structure of gels............................................ 31
Partitionbetweenimmiscible liquids................................ 32
Partitionbetweena liquidanda gel................................ 32
4 CONTENTS.
Properties of colloids Continued.
AdsorptionContinued.
Partitionbetweena liquidanda gel Continued. Page
Silk andpicric acid........................................... 32
Gelatine andtannin............................................ 33
Hagerstownloam andgentianviolet. ............................ 34
Quartz flour andgentianviolet................................. 35
Klingenbergclay andbarium chloride........................... 37
Silver iodide andsilver nitrate.................................. 38
Silver iodide andpotassium iodide............................. 39
.Tennessee ball clay andmalachite green......................... 41
Summary...................................................... 41
Determinationof plasticity................................................. 42
Dependence oncolloids................................................ 42
Adsorptiontests of clays............................................... 43
Adsorptiontests with brilliant green................................ 43
Comparisonof brilliant greenwith malachite green.................. 45
Quality of water used.............................................. . 45
Malachite-greenadsorptionandphysical properties of clays........... 46
Methods of testing..............................;............. 46
Results of tests............................................... 47
Malachite-greenadsorption..................................... 50
Physical properties of clays ................................... 50
Plasticity............................................................ 54
As determinedby malachite-greenadsorptiontests. ................ 54
As foundinpractice.............................................. 55
Miscellaneous applications of malachite-greentest. .......................... 56
Efficiency of grinding................................................. 56
Fuller's earth......................................................... 57
Paris whites.......................................................... 57
Future work.............................................................. 58
Summary................................................................ 59
References................................................................' 59
Index.................................................................... 63
ILLUSTRATIONS.
Page.
PLATE I. Apparatus for colorimetric test of adsorption..................... 46
FIGURE 1. Adsorptionof tanninby gelatine................................. 34
2. Adsorptionof gentianviolet by Hagerstownloam. ............... 35
3. -Adsorptionof gentianviolet by quartz flour...................... 37
4/Adsorptionof barium chloride by Klingenbergclay............... 39
5. Adsorptionof potassium iodide by silver iodide................... 41
6. Adsorptionof malachite greenby Tennessee Ball andSagger Clay
Company's Tennessee ball clay No. 3........................... 42
7 . Structural formulae of malachite greenandbrilliant green. ........ 46
8. Adsorption of malachite green by Potters' Supply Company's
Tennessee ball clay No. 3.................................... 50
9. Surface concentrationandspecific air shrinkage of clay colloids as
relatedtodeformability....................................... 52
PREFACE.
By A. V. BLEININGER.
The UnitedStates Geological Survey, incarryingout the provisions
of the act of Congress approvedMay 27 , 1908, which authorized"the
continuationof the investigationof the structural materials belonging
toandfor the use of the UnitedStates, such as stone, clays; cement,
andsoforth," has establishedat Pittsburg, Pa., as part of its testing
stationthere, a plant for the investigationof various problems bearing
onthe selection, preparation, andtestingof clays andclay products
for use in the building andengineering constructionwork of the
Government.
The work now beingcarriedonat this plant falls intothree groups:
(1) The testing of such clay products as common and pressed
brick, paving brick, hollow tiles andconduits, enameledbrick, fire-
proofing, terra cotta, fire brick, glazedtile, floor androofingtile, porce-
lain electric insulators and other building ware submittedby the
structural bureaus of the Government. This work includes the work-
ingout of technical specifications of the various materials for use in
government construction.
(2) The development of specifications and methods of making
tests of clays andclay products todetermine the purposes for which
they are best suited, andthe applicationof these tests tothe valua-
tionof deposits of clay or glass-makingandother structural material
onpublic lands.
(3) The study incidentally of problems of manufacture, the solu-
tionof which wouldmeanthe eliminationof much loss or wouldtend
tothe makingof a more efficient product, better suitedtothe needs
of the Government, such as the proper physical structure of fire brick,
partitiontile, floor tile, andterra cotta indifferent forms, of other
heat-resistingmaterials, the dryingof those difficultly dryingclays
that are foundinmany localities where there are noworkable beds
of better clay, andthe proper heat treatment for various clay products.
The topic discussed in the following bulletin comes within the
secondof these three groups.
The most characteristic property of clays is their plasticity, on
which depends their use inthe arts. Yet this peculiar functionof
clay has beenthe most difficult toexplainandtomeasure. Hereto-
fore nocriterionhas beenfoundwhich wouldenable the clay worker
5
O PREFACE.
tocompare with any degree of accuracy the varyingdegrees of plas-
ticity found in the clays employed inindustry. In this bulletin
Mr. Ashley has made an attempt to explain the character of the
plastic constituents of clay inthe light of recent researches inthe
fieldof colloids, andalsotooffer a methodfor the comparisonof the
different clays with respect tothis property. He is dealing, therefore,
with "a subject which is of fundamental importance not only tothe
scientific investigator but alsotothe manufacturer, for the success
of the practical operations of shapinganddryinghinges largely on
the character andamount of the plastic matter present inclays.
These studies by Mr. Ashley were for the most part incidental to
his investigationof clay products, but the defects inclay products
purchasedfor the use of the Government shouldbe much improved
by the placingof such informationas this paper contains inthe hands
of the manufacturers.
THE COLLOID MATTER OF CLAY AND ITS MEASUREMENT.
By HARRISON EVERETT ASHLEY.
INTRODUCTION.
Scope of paper. Inthis paper a definitionof clay is givenwhich is
inaccordance with the colloid theory and is sufficiently broad to
include all substances workedas clays. The colloidtheory is then
appliedtoa descriptionof the properties of clays. The result repre-
sents several months' searchingof scientific literature, inthe course
of which the endeavor has beenmade touse sofar as possible only
studies onclays, avoidingstudies onother colloids, such as gelatine,
albumens, metallic sulphide suspensions, andmetal suspensions.
Special attentionis given to adsorption, that property, so well
developedincolloids, of takingother substances out of solutionor
suspension. It is finally shownthat the adsorptionof certaindyes
by clays furnishes a means of estimatingthe colloidal matter present,
andthat whenclassifiedaccordingtocolloidal content the clays are
also classified approximately accordingtoplasticity. Some of the
results of this latter investigation, undertakenwhile the writer was
in the employ of the Homer Laughlin China Company, Newell,
W. Va., are included herein by permission of the company, with
further studies alongsimilar lines now beingcontinuedinthe clay-
products laboratories of the UnitedStates Geological Survey. The
present is a preliminary report.
Definitions. Solids were formerly definedas crystalline andamor-
phous. The term " colloid" now comprises everything formerly
knownas amorphous. Inthis classificationorganic structures are
consideredas representingthe highest type of crystallization. Clays
usually present the amorphous or colloidal appearance, any crystalline,
matter present beinglargely maskedby a coatingof colloidmatter.
Clays may be definedas mixtures of minerals of which the represent-
ative members are silicates of aluminum, iron, the alkalies, andthe
alkaline earths. The hydratedaluminum silicate, kaolin(Al2 03 .2Si02 .
2H2 0), is the most characteristic of these. Some feldspar is usu-
ally present. The grains of .these minerals may show crystal faces
(especially inthe case of kaolins), but more commonly they are of
7
8
COLLOID MATTER OF CLAY.
irregular shapes.- Uponmost of these grains is anenvelopingcolloid
coating. This is mainly of silicate constitution, but may consist
partly of organic colloids, of iron, manganese, andaluminum hydrox-
ides, andof hydratedsilicic acid. Quartz grains, which are generally
present, andmica, which is frequently present, donot have the colloid
coatingor have it inmuch less degree. Almost any mineral may be
present inclays andmodify the properties somewhat. The combi-
nationof granular materials andcolloids is insuch proportionthat,
whenreduced tosufficiently fine size (by crushing, sifting, washing,
or other means) andproperly moistenedwith anappropriate amount
of water, plasticity is developed. If the colloid matter is inexcess
the clay is consideredvery plastic, fat, or sticky, but if the gran-
ular matter is inexcess it is calledsandy, weak, or nonplastic..
Isolation of colloid matter ~ b y ScJiloesing. In 187 4 Th. Schloesing
(1 a) made a careful examinationof a number of clays, removingcar-
bonates by weak hydrochloric acid, washing, andthenexaminingthe
separatedportions which settledwith different velocities inslightly
ammoniacal distilledwater. Kaolinwas allowedtostand24 hours
before decanting. The settledmatters were fractioned, alsothe 24-
hour suspension(secondlevigation).
The followingtable shows the results with 40 grams of kaolinfrom
M. Demondesir (Manche):
Fractionation of kaolin.
Water (H2 O). ........
Alumina (AhOs) .....
Magnesia (MgO) .....
First levi-
gation.
Sand-free
portions: A,
31 grams.
13.7 3
46.28
39.92
.09
.28
Secondlevigation.
(a)
1 day
4.35
grams.
13.93
46.55
40.05
.04
.04
(6)
Iday
2.49
grams.
13.92
46.20
39.85
.22
.06
(c)
5 days
0.7 2
grams.
14.28
Lost.
(A)
27 days
0.30
grams.
12.7 0
48.57
30.46
1.36
1.03
T (e)
Insus-
pension
0.59
grams.
10.30
49.57
32.32
1.98
1.29
. 4.25
AlsO3.2SiO2.2H2O
13.91
40.63
39.46
Most of the fracl ons thus approximated the composition now
ascribedtokaolin, Al2 03 .2Si02 .2H2 0. Owingto the unsatisfactory
state of analytical chemistry 35 years ago, tooimplicit reliance can
not be put on" the figures of column e. On precipitatingthe 0.59
grams of material thereinit occupied, after standing24 hours, a vol-
ume of 146 cubic centimeters; this is five times as bulky as the pre-
cipitates of ironandalumina obtainedinchemical analysis. This
matter (e) was filtered, washed, put intoa porcelaindish, anddried
over calcium chloride. It became a brokenfilm, horny, slightly trans-
oNumbers refer to"References," pp. 59-62.
SOUECES OF THE COLLOIDS.. 9
lucent, adheringstrongly tothe porcelain. There was nocohesion
inA, very little ina, I, c, or d; a great amount ine. There was no
gradual change, but an abrupt difference in properties between d
ande. Schloesingconcluded, "From these characteristics I consider
that the clay e is colloidal."
COLLOIDS IN CLAYS.
SOURCES OF THE COLLOIDS.
HYDRATED SILICATES.
Many investigators, observingthe adsorptive power of soils, have
sought tofind out towhich of its constituents this quality is due.
AccordingtoWiley (12), Way
passeda solutionof ammonia through tubes containingpure sand, andfoundthat
it came through apparently unalteredfrom the first, while a soil treatedinthe same
way removedthe ammonia for a considerable time. He concludedfrom this that
the adsorptive power does not exist inthe sand. He next oxidizedthe organic mat-
ter ina soil with nitric acidandthentreated it with ammonia in the same way.
The first portions of the filtrate showednoammonia inany form; hence he concluded
that organic matter is not essential tothe act of absorption[adsorption]. He further
showed that clay alone is capable of causingabsorption [adsorption] phenomena.
* * * He next tried to trace out the particular compound which caused the
absorption [adsorption]. Having tried various natural silicates, he at last suc-
ceededinproducinga hydratedsilicate of aluminum and soda which exhibited
displacement andabsorptive [adsorptive] properties very similar tothose shownby
the soil (46.1 Si02 , 26.1 A12 03 ,15.8 Na^O, 12.0 H2 0). * * * Eichhorn[13] thought
of tryingnatural hydratedsilicates or zeolites, andfoundthat they exhibitedthe
same power as Way's artificial preparation.
Cushman(11) says inregardtoWay (14):
The more clayey the soil, the more water it seemedcapable of absorbing. But
this was not all; besides water, this clay substance exhibiteda greater facility for
absorbing[adsorbing] the bases containedincertainsalts which were dissolvedin
the water. Alsothis actionwas showntobe selective, certainbases andsubstances
beingheldsothat they couldnot be washedout again. Let us hear what Way himself
hadtosay on the subject: "Coloringmatters are actually precipitatedunchanged
or inthe state of insoluble pigments [technically knownas lakes] by mere mixture
with white clay. Neither tothe actionof capillarity or tothat of oxidationare we
i;oattribute the property of soils toretainthe mineral bases andanimal andvegetable
ingredients of manure." Way found, moreover, that exposure toa high heat destroyed
this peculiar absorptive [adsorptive] power of the clay substance.
GELATINOUS SILICA.
Later investigators failedtoconfirm Way inthinkingthat silica,
organic matter, etc., take nopart inadsorbingsalts, dyes, etc. He
himself (15) foundgelatinous silica invery considerable proportion
(40 per cent) in a "chalk" used for agricultural purposes. Van
Bemmelen(2) foundthat a silica gel of the formula Si02 . 4H2 O retains
aluminum chloride (A1C13 ) so tenaciously that repeatedwashings
10 COLLOID MATTER OF CLAY.
with water fail toshow eventraces inthe wash water, yet that a solu-
tion of potassium chloride (KC1) promptly displaces considerable
amounts, beingitself adsorbed. VanBemmelenconsideredthe ad-
sorptive powers of silicates insoils as for the most part tobe regarded
as such substitutions. He says (16):
Soils contain colloids colloidal silicates, ferric oxide, silicic acid, humus sub-
stances all of which canshow the above effects. The absorption[adsorption] effects
obtainedontreatingsoils with solutions are principally tobe attributedtothe col-
loidal silicates. . .
CameronandBell (19) say:
Evidence is wantingfor the existence of * * * silica coatings onthe minerals
of the soil. It is possible that such a coatingof silica may take place tosome extent.
* * * Microscopic examinations fail to disclose it, such coatings as exist being
mainly of ferruginous materials, generally removable quite easily by mechanical
means andpermeable towater. * * * The mainargument against the formation
of siliceous coatings onthe minerals is, however, the fact that they are continuously
soluble whentreatedwith fresh amounts of water, or whenthe hydrolizedproducts
are removedfrom the solution.
From a study of the evidence collectedinClarke's data of geochem-
istry (44) it appears that gelatinous silica is most likely toappear in
the products of recent rock decay, andleast likely inoldsoils.
FERRIC AND ALUMINUM HYDROXIDES!
Colloidal ferric oxide is more likely tobe foundinthe red-burning
clays thanin the lighter-burning ones. In 1868 Warington (17 )
foundthat hydratedferric oxide, which is commonly present insoils
andclays poor incolor, andhydratedaluminum oxide, which is less
frequently present, 0 are capable of absorbing(adsorbing) potash and
ammonia, andthat the absorptive (adsorptive) power of the ferric
hydrate is twoor three times that of aluminum hydrate. He further
says that humus, andespecially hydratedsilicates, have also been
showntopossess absorptive (adsorptive) powers.
ORGANIC COLLOIDS.
Peats are soils which consist almost entirely of organic matter, and
thus exhibit separately the characteristics that are tobe attributed
tothe organic matter incommonclays andsoils. Schreiner andReed
(6) state that "the amounts of organic matter inordinary soils is
* * * 2.06 per cent for the soil and0.83 per cent for the subsoil."
Such matters are called"humus" or "humic acid" whenthey may
be extractedby 5 per cent ammonia after previous treatment with
1 per cent hydrochloric acid(7 ). Any humus inthe kaolinexamined
by Schloesing would accordingly have beenfoundin his colloidal
residue e.
a CameronandBell (18) outof several thousandexaminations have but once observedaluminum hydrate
A1(OH)3 ina'soil. The sample was from southernCalifornia.
SOTJKCES OF THE COLLOIDS. 11
A. A. Julien(84) describes humic acidandmany similar substances,
inpart, as follows: "Humic acidpossesses a strictly colloidnature/'
It reddens litmus paper. . It dissolves in8,337 parts of water at 6 ,
though insoluble inwater free of nitrogenor air. After dryingat 120
it dissolves in13,7 84 parts of water at 15 . After perfect dryingat
high temperatures it becomes insoluble. "It has alsothe colloidal
property of glueingtogether vegetable earths, such as the siliceous
sands of the Landes near Bordeaux, intoa layer impervious towater."
Ammonium humate, C60H48 (NH4 ) 6 027 , dissolves in22 parts of water.
Calcium humate dissolves in3,125 parts of water; magnesium humate,
pretty easily; ferric, humate, in5,000 parts of water at 19 . Humic
acids are unstable, andtherefore tendtodisappear from olddeposits,
though traces are foundinsome minerals. The humic acids are sol-
vents for silica. The humic acids have decomposedthe upper layers
of the "Champlain" clays of New York andthe New Jersey Cretace-
ous clays, white fire clays, and pipe clays of the "Coal Meas-
ures." The actionconsistedmainly inthe removal of calcium and
iron, which were redepositedtoform a hardpanat the lower limit of
the action. This hardpanmay consist of a layer of limonite. Hard-
panmay oftenbe foundas a thinimpervious layer insands where
clays are practically absent. Gibbsite, the aluminum hydrate, is
occasionally associated as attached crusts with limonite, and is
therefore of the same origin. Amorphous silica may occur as (a)
animal skeletons, (Z > ) deposits from thermal waters, (c) a gelatinous
deposit formeddirectly by the decomposition of rocks by organic
acids, '(d) a deposit from solutioninorganic acids.
Flint, hornstone, andamorphous chert, therefore, seem tome topresent the colloid
form of silica necessarily depositedfrom a solvent of a colloidnature, such as humic
acidandprobably the azohumic acids have beenfoundtopossess. Granular ch'ert,
jasper, etc., * * * appear tobe the crystalline forms of silica, probably inpart
depositedfrom solutioninthermal waters.
H. Borntrager (85) finds inpeat:
Analy ses of peat.
'
Water. .........................................................................
Ash .............................................................................
Humus acids. ..................................................................
1.
29.50
3.05
54.95
12.50
100.0
2.
20.0
3.0
47 .0
30.0
100.0
Charles A. Davis (5) states that:
Some types of peat, notably the brownones, are saidtobecome nearly impervious
towater after they are once thoroughly driedout, because the organic acids which they
containare colloidal or gluelike inform, andwhenthey dry they become insoluble.
* * * With fineness of texture goes greater plasticity. * * * The plastic black
peats are higher inash, are more difficult toburn, andare harder whendry, reaching
nearly the consistency of soft coal.
12 COLLOID MATTER OF CLAY.
ARTIFICIALLY ADDED COLLOIDS.
Consideringalluvial clays, E. Q. Acheson (8) made a few experi-
ments with those substances he thought likely tobe foundm the
washings of vegetation. Additionof gallotannic acidor catechuwas
foundby him togive kaolinmany of the properties of the best highly
colloidal ball clays. Anexcessive amount of water was not required
totemper it; plasticity, tensile strength, andhardness were increased.
Inthe discussionof his paper it was brought out that W. D. Gates had
obtainedsimilar results by the use of silicate of soda, and(according
toCharles Weelans) that gums, glues, andgelatine have longbeen
usedinthe pottery industry for obtainingsuch results. All of these
materials are typical colloids.
SUMMARY.
The colloidmatters inclay are therefore noncrystalline, hydrated,
gelatinous, aluminum silicates, organic colloids, gelatinous silicic acid,
andhydratedferric oxide. Rarely there may alsobe present alu-
minum hydrate.
AGING AND DRYING OF CLAYS.
AIR DRYING.
Grout (9) found0.08 per cent agar-agar (a colloidobtainedfrom
seaweedandresemblinggelatine closely) toincrease plasticity from
36 to57 per cent with twodifferent clays; that 0.2 per cent agar-agar
causes a further but not proportionate increase; that gelatine has
only one-tenth the effect of agar-agar; that 3 per cent of freshly pre-
cipitatedalumina is requiredtogive the same effect as 0.08 per cent
agar-agar. But onair dryingandthenreworkingineach case the
plasticity was found to have dropped to its original figure. He
found that air-dried silicic acid cuts down plasticity as much as
angular quartz sand. He preparedanartificial hydratedsilicate of
alumina by mixingsodium silicate andalum solutions, andfoundthat
after dryingit failedtosofteninwater. Therefore, tohim, it seemed
that none of these or other colloids couldbe responsible for the be-
havior of natural clays; for he apparently thought that clay canbe
driedandwettedrepeatedly without affectingits plasticity injuri-
ously, without affectingthe activity of the colloids.
Inthis suppositionhe was not inaccordwith practical experience.
The clay used by potters has in most cases never been deprived
of its natural moisture. After once beingdriedout at as low a tem-
perature as 60 , it is foundtohave lost noticeably inplasticity. In
consequence many potteries make a practice of usingtheir dry scrap
for the preparationof castingslip, which requires a less plastic mix-
ture thantheir other processes.
Insoakingor blungingtheir clays potters know that the tougher
the clay the more difficult it is to blunge it tomake it take
AGING AND DRYING OF CLAYS. 13
upwater andbecome uniformly suspendedinthe water. Paul Rob-
land (40) compared caoutchouc to the completely impervious,
imdried, highly plastic clays ; which donot take upor allow todiffuse
the slightest amounts of water, which are "completely impenetrable
towater." One of these, the black Striegauclay, whenmoderately
dried, would allow solutions of crystalloids, such as potassium
dichromate, copper sulphate, sodium chlorides, barium chlorides, etc.,
todiffuse through it. It thus actedwhenit hadbeendriedas a semi-
permeable colloidmembrane.
Another reasonfor Mr. Grout's failure toduplicate the actionof
natural colloids is probably tobe foundinthe fact that colloidand
ultimate fine-granular matters are much more intimately mixedin
natural clays than they couldbe inthe mere superficial coatingof
large lumpy flocules inMr. Grout's experiments. With experiments
of longer duration Mr. Grout would probably have observed the
returnof plasticity tohis treatedclay, unless other circumstances
intervened. He wouldhave acceleratedthat returnhadhe ground
Ins material inwater ina ball mill for a sufficient period.
DRYING UNDER PRESSURE.
AccordingtoW. B. Hardy (10) the gel, or solidform, of either
agar-agar or gelatine, whensubjectedtopressure, loses water and
becomes more concentrated. The resulting solid still retains the
oldstructure, which is not destroyedby drying, andthe system tends
to reform itself on the old lines by refilling the original capillary
spaces. Inthis resumptionit shows considerable hysteresis, or lag.
The structure of colloids .has beenshownby the microscopic work of
Butschli andof Nagelli tobe cellular or spongelike. Hardy's experi-
ment is much like squeezingwater out of a sponge. After the sponge
has beendried, it will not immediately take upthe water again, but
requires time tosoak it upthrough its capillary passages, like oil ina
wick. Cushman(38) has recordedthat:
Silicic acidwhich has beenair-driedcanhave water pressedout of it by subjecting
it tovery high pressures; the same phenomenonis knowninthe case of clays inthe
manufacture of hydraulic pressedbrick.
WEATHERING OF FIRE CLAYS.
Fire clays intheir natural beds have beenconsolidatedunder great
pressure and their water content reduced to but little over that
chemically combined. Most emphatically the colloids of fire clay do
not take upwater promptly. Onstandingmonths or years with
water they will soak it up. Ongrindingina wet pan, anoperation
that may be comparedwith kneadingandsqueezinga dry sponge,
they will take upwater intotheir coarser pores. Inits natural bed,
fire clay exists at a very uniform temperature, but whenit comes to
the surface, either ina natural outcropor inthe clayworker's "pile"
14 COLLOID MATTER OF CLAY.
.of weatheringclay, it is subjectedtoalternations of heat andcold,
consequently its minute pores expandandcontract. If the pile is
kept moistenedthe water will penetrate as the pores expand, andas
the pores contract a portionwill be forcedfarther in. Insome plants
it is considerednecessary tosteam the clay, as diffusionof water is
more rapidat high temperatures. Inglass-pot factories it is con-
siderednecessary toage or store the dampbody for a year, inorder
tolet the water have time to penetrate the clay uniformly. The
finishedpots are thenallowedmonths or years toget thoroughly dry.
Evidently plasticity is not the creature of a few hours' laboratory
work.
AGING. OF FELDSPATHIC BODIES.
Cushman (37 ) considers Grout's reasoning invalid, "as both
plasticity andbindingpower canbe showntobe due toa softening
or decomposingactionof water onthe surface of the fine particles,
which is invariably increasedby the actionof wet grinding, pugging,
andpuddling." He points out that " colloids are formedmuch more
slowly innature under temperature andpressure conditions we can
not imitate."
The "decomposingactionof water onthe surface of fine particles,"
mentionedby Cushrnan, is not of importance inthe case of highly
compressed clays low in feldspathic materials, such as fire clays.
But with a body containingground, feldspar the agingmust continue
until, first, the decomposition of feldspar by water into colloidal
silicates, colloidal silicic acid (?), andfree alkali (37 ) has ceasedor
become greatly retarded; anduntil, second, this free alkali has been
neutralizedeither by acids originally present inthe clay or more likely
by the products of bacterial activity (41) inthe agingclay. Roh-
land(43) has advancedwhat is practically this idea, but he applies
it toa toowide range of clays. He refers the matter wholly tothe
quantity of OH ions present,, plasticity varyingsomewhat inversely
with the quantity of these, andsays that as rise of temperature
increases the quantity of OH ions it decreases plasticity. Inoppo-
sitiontothis view it may be notedthat the oldpottery slipkilngave
much more plastic bodies thandoes the moderncold-workingfilter
press, andthat the steamingof fire clays decidedly increases their
plasticity.
FORMS OF COLLOIDS.
SOLS AND GELS.
Colloids exist intwo characteristic forms: (1) as a homogeneous
suspensionina liquid, calleda "sol;" and(2) as a continuous jelly
with pore walls (andpores) filledwith a liquid, calleda "gel." Solids
are includedunder (2) as a limitingcase. The sol or gel is namedby
a prefixaccordingtothe liquidwith which it is associated, as hydrosol,
FORMS OF COLLOIDS. ' 15
alcosol, hydrogel, etc. This nomenclature was proposedby Graham
(86) in1861, and, as it has beenadoptedby practically all writers on
colloids, shouldbe usedinpreference toCushman's terms "pectoid"
(for gel) and"colloid" (for sol).
COAGULATION AND SETTING.
Colloids are commonly spoken of as reversible andirreversible,
accordingtowhether they will pass from sol togel andback tosol,
or whether, havingpassedintothe gel form, they cannot be recon-
vertedtothe sol.
The process of passingfrom sol togel is best called" coagulation,"
though sometimes "pectinization" is used; that of passingfrom gel
to sol is calledpeptinization. Whengranular matter also is pres-
ent, the terms flocculationanddeflocculationare preferable.
Weber (20) speaks of "pectisation" as anirreversible process that
may perpetuate "any physical state (sol or gel) of a colloid." As
this wordsoclosely resembles "pectinize," he has not beenfollowed
inits use. A more serviceable phrase for the same idea is "setting,"
proposedby Hardy (10). Some colloidal solutions (sols) set spon-
taneously onstanding, some by boiling, a large number of the inor-
ganic colloids by freezing, the majority of inorganic colloids onadd-
ingtotheir solutions minute quantities of electrolytes. If resoluble,
sols donot "set" but merely "coagulate" without setting.
Sols whenset form amorphous precipitates which are exactly alike,
whatever the concentration of the sol acted upon. Insetting, a
chemical change is usually produced in the molecule. Therefore,
more thana physical change of conditions is requiredtoreverse it.
EXAMPLES OF SET GELS.
As examples of set gels, may be mentionedfiredclay, wares; gela-
tine treatedwith alum or formaldehyde, as inthe Leuchter process
of reducingor enlarging'models (22).
India rub b er. According to Weber, india rubber (polyprene, of
empirical formula C10H16 ) is a gel practically freed of solvent
(therefore a solid); while ebonite (polyprene disulphide, C10H16S2 )
is the set modification of the same gel producedby the actionof
sulphur invulcanization. Inebonite, polyprene disulphide andthe
excess of sulphur (15 to7 0 per cent) form a new system, probably a
solid solution. (This discussion does not include the case of solid
solutions.) As a chemical process, time, temperature, and mass
alone affect the compositionof the vulcanizationproduct (set gel);
but the physical properties largely dependonthe physical state of
the india-rubber colloid (gel) employed. Ordinary rubber goods
consist of a mixture of ebonite andindia-rubber. Therefore they are
entirely coagulatedandpartly set.
16 COLLOID MATTER OF CLAY.
Charcoal. Charcoal is another example of set gels. It results
from a very complete decompositionof organic gels by heat, andits
structure depends ontheirs. Liquids are probably not ab sorb ed into
the substance of its pore walls, but dissolvedsubstances (solutes) or
suspendedsubstances (sols) are readily attachedtothe surfaces of its
pore walls (adsorption). All of the external andinternal surfaces
are wettedby the liquid.
Silica. VanBemmelen(21) showedthat the silica hydrogel when
concentrated by evaporation undergoes an irreversible inversion
whenthe water content is from 3 to1.5 molecules H2 0 to1 molecule
Si02 andthe vapor pressure between10 and4.5 millimeters. The
positionof this point depends onthe mode of preparation, the age
of the gel, the velocity of the dehydration, etc. The gel at this point
becomes dull, opalescent, andfluorescent, thenwhite like porcelain,
andfinally opaque white, like chalk without any gloss. After the
inversion, dehydrationtakes place more rapidly thanbefore, andthe
dimness disappears just as it has appeared, remainingbright until
the final dehydration. As this modifiedgel cannot resume the con-
ditionof the original gel, it might seem tobe set. But as it fails to
perpetuate the physical state of the original gel, andhas all the ordi-
nary properties of a gel, we must consider it a gel. Therefore, the
original silica gel might be calledthe a gel, andthe modifiedor inter-
mediate gel, the ft gel.
Inchemical analysis silica is separatedfrom solutionby forming
the set gel by dehydrationat 100 + . The failure of the ft gel togo
over completely to the set gel is a frequent cause of inaccuracy.
Hillebrand(23) has shownthat while the bulk of the silica is removed
from solution by evaporating the hydrochloric acid solution to
approximate dryness, takingupinhydrochloric acid, andfiltering,
yet about 1 per cent more is recoveredonrepeatingthe operation.
''Blastingfor 20 to 30 minutes is necessary to expel all moisture
from the silica, andit is thennot hygroscopic."
A few analysts, inrapidprocesses, separate silica from solutionin
a form which is probably the ft gel. The process is as follows: One
gram of blast-furnace slagis put intoa Royal Meissendish, 25 cubic
centimeters of 1:1 hydrochloric acidis added, andthe whole is covered
with a watch glass andboiledviolently till all the free liquidappears
tobe gone, but nothingis dry. Next 10 cubic centimeters of 1:1
acidis added, the mixture boiledfor 1 minute, and 25 cubic centi-
meters of hot water added. It is again boiled and can then be
filtered very rapidly. The process is far from accurate, andit is
questionable if its employment is ever justifiable. A peculiarity of
the process is that Royal Berlinware cannot be used, as the silica
sticks badly toit, a difficulty not foundwith Royal Meissenware.
FORMS OF COLLOIDS. 17
The practicability of this process is relatedpossibly tothe fact noted
by Hillebrand, that "The presence of much calcium chloride seems
tofacilitate dehydrationof the silica."
FORMATION OF SOLS.
AccordingtoWhitney (27 ), "Whenever any substance which is by
nature insoluble ina liquidis producedina fine state of divisionin
that liquid, it will remainincolloidal state (sol) until coagulatedor
precipitatedby external means." Thus "Bredig[28] has shownthat
a great many metals may be producedinthe hydrosol state by simply
forminganelectric arc under water betweenterminals of the metal
desired. The heat of the arc volatilizes the metal, andthe vapors
condense inthe water, yielding deeply coloredsuspensions or col-
loidal solutions." Many aniline dyes donot truly dissolve inwater,
but enter intocolloidal suspension. Inthe cases of some dyes it is
difficult to determine whether the properties are those of a large
molecule of a crystalloidor of a small colloidparticle. It is sometimes
one or the other accordingtothe concentrationof the liquid. There is
probably nodividingline (32, 34). Sols may also be producedby
chemical reactionwithinthe liquid; for example, by the actionof
hydrogensulphide onarsenious oxide.
ELECTROSTATIC CHARGES IN SOLS.
From a review by Whitney. andOber (24), the following para-
graphs are taken:
A clearer idea of the value of what follows will be gainedif one recognizes at this
point the probable necessity of attributingelectrostatic charges toparticles of any
kindwhensuspendedina liquid, andof assumingthat these charges, while they may
be positive or negative for different kinds of suspendedmatter, must still be of the same
signfor all particles of the same substance. It is knownthat twodifferent substances
incontact assume equal andopposite electrostatic charges at their contact surfaces,
andthe work of Quincke, Coehn, andothers have brought tolight the regularities of
this phenomenon.
Suspendedparticles of finely dividedsulphur, silica [probably alsonongelatinous
clay], etc., inwater exhibit negative charges exactly as larger masses of the same
substance incontact with water do, andwhenthe suspensionis placedbetweentwo
electrodes connectedwith a source of electromotive force, the particles all migrate in
the directionof the negative current. Conversely, too, water incapillary tubes made
of such materials as charge themselves negatively incontact with it moves with the
positive electricity through the capillary under the influence of the electric current.
Similarly, particles suspendedinturpentine assume inmost cases the opposite charge
as comparedwith the water, andunder influence of the electric current move inthe
opposite direction.
Coehn[25] was ledtoconclude that a substance havinga Jiigher dielectric constant
thanthe liquidinwhich it is suspendedassumes the positive charge, while if of lower
dielectric constant its charge is negative. It is probable that this does not alone deter-
mine the nature of the charge, which, at least inmany cases, must dependalsoon '
83865 Bull. 388 09 2
18 COLLOID MATTER OF CLAY.
electrolytic solution-pressure andthe partitioncoefficient for the ions of dissolved
electrolyte betweenthe suspendedmaterial andthe liquid[26].
We seemedforcedthentorecognize electrostatic charges onsuspendedparticles, and
it seems just as necessary toaccept the conclusionthat, as a result of these charges, sus-
pendedparticles whose masses are small enough are equally distributedthroughout
the liquidandpreventedfrom ever coalescingor settlingbecause of the mutual repul-
sionof these charges. This mutual repulsionmight alsocause measurable osmose and
correspondingosmotic pressure, properties which colloids have toa small degree.
IONIC REACTIONS.
AccordingtoMayer, Schaeffer, andTerroine (29) ; inall of a series
of tests the additionof traces of alkali toanultramicroscopic sus-
pensionhadthe effect of increasingthe size of the colloidal granules
if the suspensionwas positive andof diminishingthem if the suspen-
sionwas negative; andthe additionof acids producedthe inverse
effect.
AccordingtoWhitney andOber, "Spring[30] believes the statical
charge, which it is assumedthe ions of electrolytes carry, neutralizes
the statical charges of opposite signoncolloidal particles. * * *
For example, he states that certaincolloids are negative andtherefore
require for their immediate precipitation or coagulation a certain
concentrationof a positive ion." PictonandLinder (42) see insuch
precipitations " a remarkable mimicry of ionic dissociation." Others
consider it true ionic dissociation.
A. Lottermoser (31) considers that
' The hydrosol conditionis only possible if one of the reactingions (I/+Ag/, Fex// +
30H', Si03 //+2H/) remains uptoa certainminimum amount inexcess; that onexceed-
ingthis limit the gel formationbegins; andthat with the completedreaction, therefore
(if equivalent amounts of the reactingions are brought together), the gel formation
becomes complete. * * * The hydrosol conditionis boundupwith the presence
of certainions inthe colloid, which are addednaturally tothe colloidas electrolyte
or remaininthe same.
Dialysis decreases stability andleads toprecipitation. Increase of
the same electrolyte increases stability uptoa maximum, thenlets
it fall tozero.
NATURE OF GEL FORMATION.
Some of the simpler colloids, such as those of the nobler metals,
probably donot form gels at all; their decompositionis always the
irreversible one toset gels. Substances that form gels have a tendency
toform crystals, andespecially complexforms, under favorable con-
ditions. With the reactionof gel formation, sufficient freedom or
directive force is apparently not giventhe particles toorient them-
selves intocrystal ranks. The precipitationseems totake place when
the particles get within a certainmaximum range of'each other.
This probably gives a certainregularity of structure winch micro-
scopic workers describe as cellular and an. immense area of surface.
FOEMS OF COLLOIDS. 19
The precipitatingion, whenthe cause is the actionof anelectrolyte,
a,lsotends by its presence tobreak upthe symmetry of arrangement
required for crystals. In the precipitate, positive and negative
valencies 'satisfy each other where near enough, but possibly' many
unsatisfiedvalencies are present. Some whoare not ready toaccept
the conceptionof wholly unsatisfiedvalencies are yet ready toaccept
the idea of residual valencies. The more complexthe chemical ions
.andthe more viscous the medium the more unlikely it is that when
concentratedby itself or precipitatedwith a substance of opposite
electrical sign the ions of a substance will ever be able toarrange
themselves oncrystal lines. Heat, givinggreater mobility, tends to
assist these complexsols toarrange themselves insuch manner as to
precipitate or coagulate; while the simpler ones, havingat all times
sufficient mobility, require merely the oppositely chargedelectrolyte.
Heat may alsoassist by decompositions tosimpler molecules andby
the increase of static charges. This leads tothe conceptionof per-
manent colloids, which, inshort, are substances that never findcon-
ditions favorable for coagulation. Such probably have only small
electrostatic charges inproportiontotheir mass; so that but little
effect upon their properties results from the neutralizationof that
charge b y anoppositely chargedion. The formationof gels is not
noticeable insuch cases. - -
STABILITY OF CLAY SOLS AND GELS.
J. M. VanBemmelen(2) went intothe questionof the settlingof
a clay suspension. As soonas the loosely boundsalts are washed
out of a cla}^ it becomes difficult tocause it tosettle, andit cannot
be filtered, but runs through the filter paper. On addinga small
amount of acidor a salt or analkali (inshort, any electrolyte), the
milk-white liquid coagulates and settles in a short time. It also
cannow be filtered. Washing againwith water, another point is
reachedwhenthe particles become infinitely fine andpass through
the filter.
Aclolph Mayer (3) has determinedthe limitingamounts of electro-
lytes which will permit a fine clay (free from soluble salts by treat-
ment with hydrochloric acid) still tobe kept insuspensioninwater
(100 grams clay, 500 cubic centimeters water). The limits are: Am-
monia, 2.5 per cent; sulphuric, hydrochloric, and nitric acids and
the alkali salts of these acids, 0.025 per cent.
VanBemmelen assumes that the finely dividedsubstance forms
larger molecular aggregates inwhich the addedsubstance takes part.
The solutiontodothis must have a definite concentration, otherwise
toomany molecular aggregates are decomposedby the water and
returntothe finer molecular condition.
Although 2.5 per cent of ammonia causedprecipitationinMayer's
experiments, a less amount favors the deflocculation, or breaking
20 COLLOID MATTER OF CLAY.
upof the lumps. Thus it is the practice inthe laboratory of the
Bureauof Soils of the Agricultural Department (4) toadd10 drops of
strongammonia toa 5-gram sample of clay in7 5 cubic centimeters
of distilledwater inorder toassist inseparatingthe clay intoits finest
particles preliminary to mechanical analysis. With alkaline soils
ammonia hinders the defiocculation, andshouldtherefore be omitted
indealingwith such.
Inorganic sols (34) are frequently coagulatedby freezingor evap-
orating; this is oftenreally due tothe traces of electrolytes always
present in the liquid, which become concentrateduntil they reach
the minimum necessary for flocculation.
PROTECTION COLLOIDS.
Whena very stable sol inthe presence of a less stable sol of the
same signis acteduponby anelectrolyte that will not precipitate
the former, but wouldprecipitate the latter if alone, the influence of
the more stable sol is oftensufficient to" protect" the less stable sol
from coagulation. Noncolloidal substances canexercise protection;
for example, ether protects noble metal hydrosols. Gelatine is a
common "protection colloid" for many substances of small-sized
ions. The colloids of clay may carry intosuspensionsolidparticles
that are wholly noncolloidal by ordinary ideas.
PROPERTIES OF COLLOIDS.
VISCOSITY.
VISCOSITY OF CLAY SLIPS.
Bleininger (49) has made aninvestigationof the viscosity of clay
slips with different percentages of clay andwater. The first addi-
tions of clay (uptoabout 3 per cent) decreasedthe viscosity of the
water. This is to be attributed, as just shown, tocomplete defloc-
culation of the clay by dilution, and also to the solution of the
electrolytes found with the clay; since, as expressed by Charles
Henry (50), the kinetic theory of gases apprises us that the viscosity
decreases whenthe diameter of the particles inceases, andthe inverse.
Bleininger therefore introducedparticles larger thanthe water mole-
cules intosolution, andthereby decreasedthe viscosity. When, how-
ever, the additions hadbecome sogreat that nofurther matter went
intosolutionandthe effect of the clay gel showeditself, thenthe
viscosity increasedwith each additionof clay.
Previous toBleininger's work a negative viscosity for clay slips had
but rarely beenobserved, and, indeed, Dr. MaxSimonis (51) hadpro-
posedthis definition: "Clays are rocks which, pulverizedandbrought
intosuspensionwith equal or greater amounts of water, measurably
PROPEETIES OP COLLOIDS. 21
increase.the cohesionof the water. Nonplastics lack this property."
As Simonis (52, 53) hadpreviously notedthat alkalies cancut down
the viscosity of clay slips, it is evident that he overlookedthe possi-
bility of salts naturally occurringinclay havingthe same effect at
sufficient dilution.
PLASTICITY.
Many plastic bodies consist of a more or less granular material,
coated and held by a viscous substance. Instances are: Putty,
which is a mixture of any white granular material (typically whiting)
with linseedor a similar oil, the latter hardeningonexposure toair;
cake frosting, a mixture of granular sugar with the white of eggs,
becominghard on exposure to air; plaster of Paris, a mixture of
gypsum crystals andanamorphous paste of uncrystallizedplaster,
hardeninguponcompletion of the crystallization; wipingsolder, a
mixture of leadcrystals ina fusedeutectic mixture of leadandtin,
hardeningoncooling; mortars, mixtures of sandwith lime or other
cementingpastes, hardeningonreactionwith the air, or by internal
reactions; waxes, mixtures of oils of high meltingpoints with oils of
lower meltingpoints, hardeningoncooling; and, finally, clays, mix-
tures of granular, nonplastic materials with moist organic andinor-
ganic gels, hardening on evaporation of the water. The term
"nonplastics" for granular materials requires qualification, since
plastic bodies wouldlose plasticity if the granular constituent were
removedandwouldbecome sticky. Plasticity depends ona proper
ratioof granular material andviscous suspensionmedium.
P. Rohland(43) considers that the plasticity of clays depends onthe
amount of hydroxyl ions present inthe water. Whenthis is large,
the negatively chargedclay particles will gointocolloidal suspension.
Whenthe hydroxyl concentrationis depressed, as by additions of
acidor depressionof temperature, the clay will assume the gel con-
ditionandbecome plastic. For decreasingplasticity may be used
all bases, organic andinorganic, all salts of strongbases with weak
acids, which hydrolytically split off OH ions inlarge amounts. To
this classification belong potash, soda, salts of phosphoric acid,
salts of silicic'acid. "Neutral salts with very few exceptions appear
tobehave indifferently." As indifferent salts he mentions sodium
chloride, sodium sulphate, potassium nitrate, magnesium chloride,
and others. "The causes of the abnormal behavior of several are
not yet exactly known."
This conceptionis attractive by virtue of its simplicity andcom-
prehensiveness. It seeks, however, torefer the plasticity of clays to
their vehicle, a water solutionof soluble salts, rather thantotheir
own composition. It seems more logical, though perhaps more
22 COLLOID MATTER OF CLAY.
difficult indetails, torefer plasticity tothe gel structure of the clays
themselves. It must be allowedthat the conditionof the water will
have effects of the nature assignedby Rohland; but as clay is plastic
whenwettedwith, for example, aniline (paint remover), linseedoil
(kaolin putty)', alcohol, glycerin (plastic medical dressing), etc.,
hydroxyl canby nomeans play the principal part. This is substan-
tiatedby the views of Coehn(25). (See p. 17 .)
ACTION OF ELECTROLYTES.
Plastic clays have very little, if any, of their colloidmatter in the
hydrosol condition. They holdintheir natural deposits sufficient
bases, especially lime, to keep them as coagulated gels. Anyone
has but tolook at the clear water comingfrom a pottery filter press
torealize how completely absent is the sol form of the clay colloids.
It is not until a sol has beencoagulatedandthus become a gel that
it has .any plasticity or markedadhesive and cohesive properties.
Thus Hans Kuzel (45) has observed that the pure gels of colloid
metals form exceptionally homogeneous plastic masses when the
mechanically combinedwater is removedby appropriate expression
or other suitable means. (He adds nonplastics.) The sols of such
metals are fluid, therefore wholly unplastic.
It is possible that much of the colloidmatter inclays has never
beeninthe sol form, but is a gelatinous residue left from rock decom-
position, together with crystal rock fragments (46).
AccordingtoHardy (lOa), a sol is coagulatedwhenits static charge
of electricity is neutralized. This is usually done by electrolytes.
With a negative sol, such as a clay that has beenbrought intocolloidal
suspension, the positive ionof the electrolyte is of most influence in
effecting precipitation, the acidiontakinglittle part. The power
seems tovary but little indifferent positive ions of the same valence;
but with certainsols divalent ions have about 60 times the precipi-
tatingeffect of monovalent ions, andtrivalent ions 600 times that of
monovalent ions (27 , 24, 33). The effects are not sogreat onclays.
EXCHANGE OF BASES.
Eugene C. Sullivan (39) has carefully studied the interaction
betweenminerals andwater solutions. Pie concludes that "sofar'
as the evidence goes, then, the action of silicates, clay, andother
constituents of the earth's crust onsolutions of such salts as donot
dissolve inwater with alkaline reaction, consists in an equivalent
exchange of bases." He does not consider pure water, acids, or
alkalies inthis generalization.
If sodium carbonate be added to a clay which has just enough
calcium (the most common"soluble salt" inclay is calcium sulphate)
PROPERTIES OP COLLOIDS. . 23
tokeepthe colloidmatter ingel form, it will (the calcium beingbut
loosely combined) react accordingtothe followingequation:
Ca + Na2 C03 -> CaC03 + Naz
with gel the addition insoluble with the sol.
F. F.orster (87 ) is tobe creditedwith first perceivingthe nature of
tliis actionof sodium carbonate onthe clay gel. The calcium car-
bonate formedbeinginsoluble nolonger has influence onthe colloid.
The sodium, inamount equal tothe calcium, has metal ions of lower
valence than the calcium which originally stabilized the gel. As
many times more sodium atoms thancalcium atoms are requiredto
precipitate the same amount of gel, it is evident that the clay gel will
be brokenup, or the clay will be deflocculatedby the soda, andits
plastichYy will fall off inproportiontothe completeness of the reaction.
When, however, enough sodium ions have beenadded, they may be
expectedtoprecipitate the gel anew.
Such is the caste, as studiedby Mellor, Green, andBaugh (47 ).
These investigators took measurements of the time requiredfor 200
cubic centimeters of anearthenware body sliptorunfrom a modifi-
cationof Mariotte's bottle. Reducedtoa basis a of time for water
equals 10 seconds, their results were:
Additionof sodium carbo-
nate (grams) ............... 0 0.1 0.2 0.3 0.4 0.5 1.0 1.5 2.5 3.5 4.5
Time required(seconds) ..... 10 .8.7 7 .4 6.5 6.1 6.1 6.1 6.1 7 .8 13.9 (& )
Similar results were obtainedby them for potassium carbonate,
sodium bicarbonate, sodium potassium carbonate, sodium sulphide,
potassium hydroxide, gallic acid, ammonium gallate, andtannin. It
cannot be assertedthat with each of these compounds the actionis
the same as with sodium carbonate, for the earthenware body is of
too complex a nature, andthe actionmust be studiedonsimpler
substances for full conformation, but probably the explanationholds
for most of these cases. The insolubility of the compoundformed
may^not be socomplete as that of calcium carbonate in-every case;
it is less so, for instance, with calcium hydroxide formedby actionof
potassium hydroxide.' AccordingtoSimonis's results, sodium hydrox-
ide andrubidium hydroxide behave similarly topotassium hydroxide.
Whenthe addedsalt does not form aninsoluble product with the
salt inthe clay, there is probably part replacement in accordance
with the mass-action law. Thus on addition of sodium sulphate
there was a fallingoff inviscosity, andsufficient sodium ionconcen-
trations were not reachedtoreprecipitate the gel. Such was alsothe
case with sodium sulphite andsodium chloride. It is therefore classi-
fiedhere with hydrochloric acid. Certainsalts, however, were added
a Mellor, Green, andBaugh usedwater at various temperatures, which took insome cases 10 seconds and
ia others more, toflow from the viscosimeter. These results have beenreducedtoa commonbasis of 10
seconds.
& Toostiff toflow through apparatus.
24 COLLOID MATTEE OP CLAY.
insufficient amounts toreprecipitate the gels, viz, potassium acid
sulphate, potassium sulphate, potassium nitrate.
It is difficult toclassify the actionof hydrochloric acidandmer-
curic sulphate. The latter decomposes toinsoluble sulphate andfree
acid.
Divalent ions insome cases reinforcedthe salt inthe cl&y , inothers
the reverse, according to slight variations in precipitating power,
such as have been shown by Schulze (33). Magnesium sulphate
decreased viscosity. Substances increasing viscosity were calcium
sulphate, copper sulphate, calcium chloride, and, accordingtoSimonis,
calcium hydroxide.
Trivalent ions reinforcedthe fiocculation, eventhough associated
with monovalent ions. The case studiedwas potassium aluminum
sulphate (K2 S04 .A12 (S04 ) 3 .24 H2 0).
ORGANIC COLLOIDS.
Insome cases the action is probably not on' the inorganic gel
of the clay, but onthe organic matter. Strongammonia increased
the viscosity in these experiments. Ammonia is known to be a
solvent for humic acids. It is very likely that it actedonthe some-
what insoluble or set humic acids andhumates, formingammonium
humates, which, not having sufficient water for solution, assumed
the gelatinous form andincreasedthe viscosity. Similar actionmay
be attributedtoammonium chloride, aniline, methylamine, andethyl-
amine. This possible explanationneeds verification, andcannot be
consideredas of weight until such studies have beenmade. All of
the other basic ions studiedwere of simple nature. The effect of the
complexity of the NH4 groupmay be of influence. Smaller additions
thanthose tabulatedmay produce deflocculation.
Alcohol additions didnot affect the viscosity. As water additions
wouldhave decreasedthe viscosity, soalcohol sub stitutions for water
wouldhave increasedthe viscosity. The actionof alcohol is there-
fore similar tothat of ammonia, a complexgroup, with solvent effect
onorganic matter.
Humic acidandgrape sugar, beingthemselves colloids, increased
the colloidcontent andthe viscosity. Sodium biborate is possibly
alsotobe classedas increasingviscosity, or onBinn's assumptionof
the basic nature of boron (48). might be considered as having a
trivalent basic ion. 0
MELLOR, GREEN, AND BAUGH'S EXPERIMENTS.
Inthe table of Mellor, Green, andBaugh's results below the times
requiredfor equal Volumes of slips with various additions toflow
through the same orifice are given (reducedtoa commonbasis b of
time for water equals 10 seconds):
Work by the writer in1909 shows that boraxbelongs inthe first or secondof the groups of the table.
6 See footnote, p. 23.
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PROPERTIES OF COLLOIDS. 27
LAWS OF COAGULATION.
A promisingtheoretical treatment of coagulationis that of Hardy
(lOa), whosays: "The concentrationof acids necessary tocoagulate
electronegative colloidparticles, andof alkalis necessary tocoagulate
electropositive particles, is determinedby the laws which governor-
dinary chemical equilibrium," that is, equicoagulate solutions of acids
agree intheir electric conductivity withinthe limits of experimental
6> rror.
Specific conductivity = C = vd (u + v).
a is the fractionof the total number of molecules, v, which ?,re
dissociatedat any one moment, andu + v is the sum of the velocity
of the twoions.
Inthe case of the actionof salts onthese hydrosols, the relationis
riot sosimple. K does not vary directly with a (u + v), but contains
a, factor which is approximately squaredor cubedby a change from
a, monovalent toa divalent or trivalent ion. The relationcanthere-
fore be best expressedas J$ L = va(u + v) A.x , where x is positive and
increases rapidly with anincrease inthe valency of the ionwhose
electric charge is of the opposite signtothat onthe particles.
Actionis onthe liquidor onthe particles or onboth at various
times.
Unfortunately little experimental work has been done along the
line indicatedby Hardy.
ABSORPTION.
LACK OF DEFINITE RELATION OF ABSORPTION TO TEMPERATURE.
It has beenpointedout inthe case of silica that a portionof the
liquidmedium is most tenaciously held by the gel. (See p. 16.)
This is a universal andwell-knownproperty of colloids. Inthe case
of hydrogels it may be saidtocorrespondina rough way towater of
crystallization; but just as colloids have nodefinite form, neither do
they retaina definite amount of water nor give it upat a definite
temperature onheating. Cushman (38) has shownin the case of
several hydrogels the proportionof water that they will absorb after
beingheatedtoincreasingly high temperatures. Similar curves were
obtainedfor silicic acidgel, ferric oxide gel, andtwoclays. The tem-
peratures at which they lost the absorptive power completely are 840
and950 for the twoclays, 1,020 for the ferric oxide gel, and1,200
for the silica gel. As the water regainedwas from over a sulphuric
acid solution of 18 millimeters vapor pressure, it is, according to
Cushman, not tobe consideredhygroscopic, but as due toabsorption.
AccordingtoVanBemmelen (54), hydrogels are not definite hy-
drates, as the vapor tensionandhence the water content change con-
tinuously with temperature, while a true hydrate gives off a definite
28 COLLOID MATTER OF CLAY.
number of molecules of water at definite temperatures. The water
of hydrogels may be replacedby other liquids, such as alcohol, glyc-
erine, etc. The aqueous tensionof colloids alsoundergoes irreversible
Changes ondryingout, heating, etc.
RELATION OF ABSOEPTION TO PLASTICITY.
The amount of water requiredby clays togive them a plastic con-
sistency (which may be considered, as closely relatedtoamount ab-
sorbed) is sometimes takenas a measure of plasticity, but Grimsley
(9) notes that Ries inhis work onthe Michiganclays foundexamples
where 19 per cent of water.was requiredfor a clay of low plasticity,
and17 or 18 per cent for another of high plasticity.
Grout (9) foundthat a shale which hadincreasedlargely inplas-
ticity onweatheringcheckedwithin0.02 per cent of the combined
water originally present. Therefore, plasticity cannot be measured
directly either by the combinedor the absorbedwater.
DISTRIBUTION OF ABSORBED WATER AMONG CONSTITUENTS.
The amount of water absorbedfrom the atmosphere by the various
constituents of clay is remarkable.
For quartz, Patten'andGallagher (55) report at 25 C.
Ab sorption b y quartz at 25 C.
Vapor pressure.
Millimeters.
0.09
8.00
14.00
18.30
23. 50 (water)
Moisture absorbed.
Per cent.
0.07
.10
.11
.12'
.01
For feldspars, Day andAlien(56) findthat the water of constitu-
tion (about 0.60 per cent) frequently reported for feldspars is in
most cases really hygroscopic, andis the larger inamount the finer
the samples are ground.
VonDobeneck (57 ) reports the water absorbedby humus at 20
C. as follows:
Ab sorption b y humus at 20 C.
Humidity.
Per cent.
30
SO
7 0.
90
100
Moisture absorbed.
Per cent.
4.05
.7 .7 6
10.58
15.67
18.02
PROPERTIES OF COLLOIDS. 29
Briggs andMcLane (58) subjectedsoils ina centrifugal machine to
forces 3,000 times that of the earth's gravitation. The water re-
tainedvariedfrom 3.6 per cent with coarse sandy soils to46.5 per
cent inthe case of a heavy clay subsoil. Each per cent of clay or
organic matter correspondedto0.62 per cent of moisture; each per
cent of silt to0.13 per cent of moisture.
Referringtothe work of Schloesing (see p. 8), it will be noted
that he foundthe finest constituent of a very pure clay tohave a
gelatinous nature, with a decidedreluctance togivingupwater.
It will be seenfrom these figures that the large moisture content
of air-driedclays is not toany noticeable degree due tothe granular
kaolinfeldspar andquartz, but tothe organic matter andtothe min-
eral colloidal constituent of the clay.
VOLUMES OF CLAY GEL IN VARIOUS SALT SOLUTIONS.
Schloesinghas notedthe great bulk assumedby the clay gel in
water. PattenandGallagher (55) have studiedthe effect of various
salt solutions onthe bulk of 50 grams of Susquehanna clay shakenup
with 150 cubic centimeters of solution andallowedtosettle for 7
days, as giveninthe followingtable:
Effect ofl5Q cub ic centimeters of various solutions on SO grams of clay .
Solute.
Flocculation:
Deflocculation:
Volume of solutionin
soil.
Y solution.
Cub ic centi-
meters.
60.5
7 3.0
SO. 4
91.4
97 .7
104. 6
108.7
110.4
111. 3
118. 1
120.9
126.1
126.7
128.1
N , t.
JQ solution.
Cub ic centi-
meters.
69.4
89.4
o7 0.1
126. 4
a 69. 8
105.6
123.2
117 .7
117 .6
125. 8
101. 2
113. 8
128.7
131.9
a- Flocculation.
The deflocculationhas not proceededfar enough toresult insol
formationinmost of these cases. It is probable that sol formation
wouldnot be reachedat any concentrationwith potassium nitrate,
sodium nitrate, potassium sulphate, ammonium sulphate, sulphuric
acid, andsodium sulphate.
30 COLLOID MATTEBOF CLAY.
The result is closely parallel tothat of Mellorj Green, andBaugh
onthe viscosity of clay slips. Divalent lime, andcomplexammo-
nium ions caused a decrease inbulk andanincrease of viscosit}^
Ammonium seems topresent anomalies, for which it is possible, but
not profitable, to frame explanations. F. Hofmeister (59) has
shownthat with the same positive ion, different negative ions give-
different amounts of swellingwith plates of glue.
It has beenpointedout by Weber (20) that the water associated
with a gel is dissolvedinthe gel a distinctionfrom ordinary solutions
with a considerable difference. Van Bernmelen (60) states that
it is homogeneously distributedthroughout the substance of the gel,
not concentratedonthe surfaces like hygroscopic water onglass.
DISTRIBUTION OF SALTS IN GELS.
The physical distributionof the salts associatedwith a gel is a
subject of much interest. A small portionof one of the ions is inti-
mately associated, probably by a sort of chemical combination, and
is necessary for the stability of the gel state. This has already been
discussed(p. 18). The amount requiredfor this stability varies with
different elements, andis greatest for the monovalent ions, least for
those of highest valence.
A colloidof opposite sign'may perform the same functionas a salt
ionof opposite signincoagulatinga sol or stabilizinga gel. Accord-
ingtoTeague andBuxton(36, 62), whose work does not seem tobe
publishedinthe language of. their owncountry, some dyes are true
crystalloids, soluble inwater; others are true colloids, suspensions in
water; andthere are all intermediate gradations. Inother words,
there is nodividingline betweencrystalloids andcolloids; but it is
convenient toclassify separately as colloids those substances whose
ions are solarge as togive preeminence tothose phenomena that we
call colloidal. But all dyes canbe treatedas inone group. Teague
andBuxton(62), with especial reference todyes, lay clownthis rule:
"Slightly colloidal substances (sols of opposite sign) precipitate each
other over a wide range of concentrations, but incompletely; highly
colloidal substances, over a narrow range of concentrations, but com-
pletely." Intheir earlier article (36), they say that inthe case of a
highly colloidal color andone slightly colloidal for example, congo
redandmethylene blue the slightest excess of congoreddissolves the
precipitate, but the weakly colloidal methylene blue dissolves nothing
unless inconsiderable excess. Intheir later article (62), they say
that highly colloidal substances canprobably take the more colloidal
member of. a mutual colloidgel away from the weaker member. It
thus appears that inthe matter of replacements, colloidcomplexity
has aneffect similar toincrease of valency with simple crystalloid
ions.
PROPERTIES OF COLLOIDS. 31
Des Bancels (64) states that (1) mixtures of twocolloids of opposite
signs cause a precipitationwhich is complete at a definite proportion;
but addition of an electrolyte capable of precipitatingone of the
two colloids prevents their mutual precipitation; (2-) if tomixtures
containinga constant quantity of negative colloidA andincreasing
proportions of anelectrolyte which does not precipitate this colloid
one adds a constant quantity of colloidB, it is noticedthat for weak
quantities of electrolyte the precipitate is a mixture of A andB, for
increasingamounts of electrolyte the precipitate consists of Balone,
while for the strongest amounts of electrolyte the precipitate con-
tains a mixture of A andB; (3) the precipitate resultingfrom the
mixture of'twocolloids of opposedsigns cangenerally be dissociated
by the additionof anelectrolyte capable of precipitatingone of the
couple.
ADSORPTION.'
STATEMENT OF THEORY.
After a sol has beencoagulatedb y a certainamount of anopposite
ion, the questionis proper, What becomes of the excess of the coagu-
latingionor of other ions of the same signthat may subsequently
be brought intothe liquid? The replacements possible inthe latter
case have already beendiscussed(p. 22). As tothe former case, there
are twoviews: One, that the excess ions are collectedonthe surfaces
of the gel, adsorbed, as is consideredthe case with gases heldby
charcoal; the other, that the excess ions are distributedbetween.the
outside liquidandthe gel, as if the gel were the secondof twoimmis-
cible liquids; that is, that the ions were held insolidsolutionin
the gel.
Walker andAppleyard (61) have disprovedthe latter theory as
applied to dyeing, and their proof is equally applicable in other
cases. The adsorptiontheory not havingbeendisproved, probably
is correct.
The excess of the opposite ionthat has not takenpart incoagu-
latingthe gel andthat is not adsorbedis probably insimple solutionin
the liquidmedium, whether that medium be absorbedby the gel or
free.
CELLULAR STRUCTURE OF GELS.
For the adsorptiontheory it is necessary toconsider that the gel
has a surface proportional to its mass. On page 18 the circum-
stances that may leadtoa cellular structure have beenmentioned.
W. B. Hardy (10) discusses such a state inthe case of gelatine; Van
Bemmelen(63) notes the similarity of such structures andemulsions;
Lottermoser (65) describes a cell-like structure, which he calls an
"emulsion colloid" but which Weber (20) has described as a gel
32 COLLOID MATTER OF CLAY.
swelledupto, near, or above the maximum solubility of water inthe
gel. Butschli and also Nagelli have described the microscopic
appearance of the cellular structure of colloids.
The theory of a cellular structure havingbeenaccepted, its mathe-
matical expressionmay be considered. Bodeker (66) in 1859 con-
sideredadsorptionas proportional tothe square root of the initial
concentration. Wolff (67 ) inthe same year pointedout that the
final, not the initial, concentrationshouldbe considered.
PARTITION BETWEEN IMMISCIBLE LIQUIDS.
Nernst, in1891, formulateda "partitionlaw" for the distribution
of a solute between two immiscible liquids. Distribution is con-
sidereddependent onthe relative solutionpressure intwosolvents.
where Ca is the concentrationinsolvent a, Cb is the concentrationin
solvent & , and/? is a constant, amountingpractically tothe ratioof
the solubilities inthe twoliquids.
If, however, the molecular weight inthe solvent 6 is n times as
great as ina, the equationtakes the form
PARTITION BETWEEN A LIQUID AND A GEL.
Inapplyingthis toadsorptionthe most commonform is
where X = the weight of the adsorbedsubstance, m = the weight of
the adsorbent, Cb = the concentrationof the solution, and/? andp are
constants.
SIL K AND PICRIC ACID.
For picric acid" andsilk, Walker andAppleyard(61) obtained
P= . = 35.5,
2.7 / '
AT
which is of the above form; s = concentration of dye onsilk, and
w = concentrationof dye inwater.
Takinglogarithms
logs = log35.5 + logw.
Differentiating,
ds _ 1 dw
~o~"~9 7 ~ w
o ^.l 6 C /
PROPERTIES OP COLLOIDS.
33
that is, if the concentrationinwater increases by 1 per cent of its
value, the concentrationinthe silk will increase by per cent of its
' . J 2.7
own value. It appears that the molecule is 2.7 times greater in
water thaninthe fiber (if solidsolutionwere tobe assumed), which
is most improbable, especially as picric acid (C0H2 (N02 ) 3 .OH) has
high electrolytic dissociation in water. Therefore, according to
Walker andAppleyard, the phenomenoncannot be explainedby
solidsolution; although the mathematical expressionhas a similar
form, which is tobe ascribedtoadsorption.
GELATINE AND TANNIN.
The colloidnature andhomogeneity of silk beingpossibly some-
what questionable, the equation to represent the results of Wood
(68) onthe adsorptionof tanninby gelatine has beenworkedout.
The calculations are as follows:
Adsorption of tannin b y 1 gram of air- dry gelatine (=0.7 4 gram anhy drous}.
Volume
of solu-
tion
(cubic,
centi-
meters).
100
200
300
400
500
600
7 00
800
Tannin
(grams).
1
2
3
4
5
6
7
8
Tannin
adsorbed
(grams).
0.91
1.50
1.90
2.17
2.28
2.36
2.36
2.36
A.
Tannin
adsorbed
per gram
anhy-
drous
gelatine
(grams).
1.226
2.028
2.567
2.932
3.080
3.189
3.189
3.189
iLogA.
0.090
.307 .
1 .410
.467
.489
.504
.504
.504
Tannin
left in
solution
0.09
.50
1.10
1.83
2.7 2
3.64
4.64
5.64
.
Tannin
per gram
water
(grams).
0.0009
.0025
. 003667
.00457 5
.00544
. 006067
. 00663
. 007 05
LogB.
4.955
3.398
3.565
3.661
3.7 36
3.7 83
3.822
3.849
The foregoingcalculations were made with a slide rule.
Infigure 1, logs A are plottedas ordinates andlogs Bas abscissas.
As the first five points lie closely onthe same straight line, they
represent data that may be expressedby anexponential equation.
Assume A B7 1 = K. Takinglogarithms, logA + n logB= logK = K1.
Selectingtwoconvenient points onthe straight line of figure 1,
0.5000 +3.7 49 w = E>
or
0.0611 + 4.900 n = Kl
0.5000-2.251 n= K>
0.0611 -3.100 n = Kl
_____ ' %,.
These may be solvedsimultaneously for n andK1. From K1, K is
obtained.
83865 Bull, 388 09 3
34 COLLOID MATTER OF CLAY.
Employing a slide rule, five-place logarithms, and seven-place
logarithms, there are obtained, respectively:
, and ^m = 46.3, = 46.09810.
The five-place logarithms secure the equation with sufficient
accuracy only tothree significant figures inthe constant.

-4-6.098
A
3.0 3.2 3.6 3.8 3.4
LOG.B
Tannin in solution
FIGURE 1. Adsorptionof tanninby gelatine.
The same form of equationapplies to tanninandgelatine as to
picric acidandsilk, but reaches a limit after which it fails toapply.
That there is a superior limit toadsorptionmay have animportant
significance.
HAGERSTOWN LOAM AND GENTIAN VIOLET.
CameronandPatten(69) have determinedthe adsorptionof gentian
violet ((CH3 ) 2 N.C6 H3 :SC1N:C6 H3 NH2 ) by Hagerstown loam. The
dye has a solubility of 6.8 per cent at 25 .
PROPERTIES OF COLLOIDS. 35
Their results, as recalculatedby the writer, are giveninthe follow-
ingtable:
Adsorption of gentian violet b y Hagerstown loam.
<
cij oo
Dye
addedper
liter
(grams).
1.33
2.66
3.33
6.67
10.00
13.33
20.00
26.67
A.
Dye adsorbed
per
gram of soil
(grams).
0. 001 999 6
. 003 999 8
. 004 999 6
. 009 982 5
. 014 95
. 019 817
. 020 45
. 020 25
Log. A.
3". 301
3.602
3.699
3.999
2.17 5
2.297
2.310
2.306
B.
Dye remaining
insolutionper
gram of water
(grams).
0.00000023
. 000 001 40
. 000 002 50
. 000 012 0
. 000 032 5
. 000 125 0
. 006 525
. 013 500
Log. B.
7 .362
6.146
6.398
5.080
5.512
1.097
3.815
2.130
=.8375
4.0
L O G .B
3.0 T .O
FIGURE 2. Adsorptionof gentianviolet by Hagerstownloam.
Studying these data inthe manner just described (fig. 2), it is
foundthat the first sixof these points are accurately representedby
the equation
A A
TJ0.39495 = 0.83723Or -DO-3849965 = 0.8375014,
36 COLLOID MATTEE OP CLAY.
Seven-place logarithms appear necessary toobtaina constant accu-
rate inthe fourth significant figure.
Insimilar manner tothe precedingcase, there is a superior limit
toadsorption, beyondwhich the last twopoints lie.
QUAETZ FLOUR AND GENTIAN VIOLET.
CameronandPattenhave alsostudiedadsorptionof gentianviolet
by quartz flour. The writer has recast their results, as giveninthe
followingtable:
Adsorption of gentian violet b y quartz flour.
0.04 .............................................
Equationapplies:
.10.............................................
.5..............................................
.67 ........:....................................
1.33. ............................................
2.00. ............................................
2.C6. .............................................
3.33. ............................................
Equationfails:
4.66. ............................................
6.67 . ............................................
16.67 . ............................................
A.
Dye ad-
sorbedper
gram of
(grams).
0. 000 06
. 000 14
. 000 7 43
. 001 984
. 001 901
. 002 66
. 002 89
. 002 95
. 002 97
. 002 93
. 002 90
A'.
A
1- A
.0035.
0. 000 061
. 000 1457
. 000 945
. 000 457 2
. 004 16
.011 06
.016 6
. 018 7 7
. 019 54
. 018 03
. 016 86
3.7 86
1.164
3.97 5
3.660
3.619
2.045
2.220
2.27 4
5.291
2.256
2.227
B.
Dye un-
adsorbed
per liter
(grams).
Trace.
0. 0001
.0040
.0108
.066
.224
.7 40
1.37 0
2.668
4.7 10
147 * ;
Log. B.
3
nnn
3.602
"5.034
2.820
T ^f;n
T SfiQ
0.137
0
497
0.67 3
1.169
a Evidently erroneous.
The form of equationusedinthe three precedingcases failedto
represent the data. Incastingabout for a more accurate numerical
A
expression, the expedient was evolved of dividingA by 1
U.UUoo*
It will be notedthat 0.0035 is of the same order of magnitude as the
maximum observedadsorptionper gram, 0.00295. The latter figure,
however, failedtowork, andthe value employedwas the result of
repeated trials to get a value that would give a straight line on
'___A
the logarithmic diagram. Then if A' = A , the equation
0.0035
A'
o0. 531404 = 0.01948113 represents the data accurately from the most
dilute solutionuptopractically the maximum of adsorption.
PROPEKTIES OF COLLOIDS.
37
Infigure 3 the logarithmic curves for the equations are givenfor
comparison. Thus A Bn= K (the theoretical curve, which shouldbo
a straight.line if the equationis correct); A' Bn= K, where
A
A'= A~
0.00297
0.00297 being the maximum observed adsorption; andA' Bn= K,
A
where A' =
1-
A , 0.0035 beinga value foundby trial.
0.0035
The superiority of the thirdcurve is easily seen.
FIGURE 3. Adsorptionof gentianviolet by quartz flour.
KLINGEN3ERG CLAY AND BARIUM CHLORIDE.
H. Hirsch has studiedthe adsorptionof barium chloride by various
clays. For Klingenbergclay his results, as recalculated, are givenin
the table following.
38 COLLOID MATTER OF CLAY.
Adsorption of b arium chloride b y 1 00 grams of Klingerib erg clay in 1 liter water.
Barium
chloride
added
(grams).
0.1
.2
.3
.4
. 5
.0
.7
.8
.9
1.0
1.5
2.0
2.5
3.0
4.0
5.0
10.0
15. 0 '
20.0
25.0
A.
Barium
chloride per
per gram of
clay
(grams).
0. 000 90
.001 92
. 002 92
. 003 52
. 004 24
. 004 89
. 005 51
. 006 03
. 006 54
. 007 01
. 008 08
. 009 30
.010 09
. 010 87
.011 64
. 012 31
. 014 12
. 015 27
. 015 35
.015 51
A'.
A
A
1 0.017 8
0.001 013
. 002 15
.003 492
. 004 38
. 005 57 3
. 006 7 5
. 007 98
. 009 13
. 010 33
. Oil 55
. 014 84
. 019 48
.023 3
.028 0
. 033 7 7
.040 0
. 068 2
. 107 4
.111 5
.121 1
Log. A'.
3.000
3. 333
3.543
3.642
3.7 46
3.829
3.902
3.961
2.015
2.063
2. 17 1
2.290
2.368
2". 447
2.529
2.602
2.833
1.031
1.048
1.084
B.
Barium chlo-
ride remain-
inginsolu-
tionper gram
of water
(grams).
0. 000 004
. 000 008
. 000 008
. 000 048
. 000 07 6
. 000 111
. 000 149
.000 197
. 000 246
. 000 299
. 000 692
. 001 07 0
.001 491
. 001 913
. 002 836
. 003 7 69
. 008 588
. 013 47 3
. 018 465
. 023 449
Log. B.
6.602
6.903
a. 6903
5. 681
5.881
4.045
4. 17 3
4.295
4.391
4.47 6
4.840
3.030
3.17 4
3. 282
3. 453
3.57 7
3.935
2.130
2. 267
2.37 0
"Erroneous.
These are plottedin figure 4. The equation representing the
A' A
data is , = 0.7 646805, where A' =
1-
0.017 8
SILVER IODIDE AND SILVER NITRATE.
A. Lottermoser andA. Rothe (7 1) have determinedthe adsorption
of silver nitrate by fresh precipitatedsilver iodide. The concentra-
tions of the solutions employedwere determinedby means of elec-
trical conductivities. The followingis their table:
Adsorption of silver nitrate b y silver iodide.
Co
Silver
nitrate per
cubic centi-
meter of
original solu-
tion
(millimoles).
0. 00045
. 0007 5
.00107
.00163
. 00232
. 00502
. 00988
. 01519
B.
Silver
nitrate per
cubic centi-
meter of final
solution
(millimoles).
0. 00019
. 00045
. 0007 3
. 00123
.00188
. 00450
. 00928
. 01456
LogB.
-3. 7 212
-3. 3468
-3. 1367
-2. 9101
-2. 7 258
-2. 3468
-2. 0324
-1.8308
A.
Silver
nitrate ad-
sorbedper
gram of silver
iodide
(millimoles).
0. 0023
.0026
.0029
.0034
.0038
.0045
.0051
.0054
LogA.
.-2.6383
-2. 5850
-2. 537 6
-2. 4685
-2. 4202
-2. 3468
-2. 2924
-2. 267 6
A as
com-
puted
from
the
equa-
tion.
0. 0024
.0028
.0031
.0035
.0038
.0046
.0051
.0057
PROPERTIES OP COLLOIDS.
39
A millimole is one one-thousandth part of the molecular weight of
a substance expressedingrams. Inthe case of silver nitrate a milli-
mole is 0.17 0 gram.
A
The equationis -p0. 19a6 =
A'
gO.5173
.7647-
0.0/78
4.0 3.0 2.0 1,0
LOG.B
FIGURE 4. Adsorptionof barium chloride by Klingenbergclay.
SILVER IODIDE AND POTASSIUM IODIDE.
Peptization. These investigators further show that the freshly
precipitatedamorphous silver iodide may be peptizedb y treatment
with the soluble iodides of either potassium, cadmium, or barium, as
40
COLLOID MATTER OF CLAY.
shownby the following table for potassium iodide, actingon0.25
gram silver iodide in25 cubic centimeters of water.
Effect of potassium iodide solution on silver iodide.
Concentrationof
potassium iodide
inthe solution
(normality).
0.0005
.001
.002
.004
.01
.02
.03
.05
.07 5
.1
.15
.25
Effect onsilver iodide.
Very weak hydrosol formation.
Beginningof intense hydrosol formation.
Strongincrease of the same.
Further increase. A visible alterationof the silver iodide structure
Stronghydrosol formation.
Do.
Maximum hydrosol formation.
Decreasedhydrosol formation.
Do.
Complete alterationof structure of silver iodide.
Almost nohydrosol formation.
Nohydrosol formation.
The authors say that driedprecipitates or dry preparations of silver
iodide cannot be peptized; That if the hydrosol is once completely
precipitatedit cannot be peptized; that is, the hydrosol phase must
never be completely eliminated, for thenan"alterationof structure"
will occur.
Adsorption. As might be expectedfrom this, on attemptingto
measure the adsorptionof potassium iodide by silver iodide, they
fail toobtaindata that may be representedby the adsorptionequa-
tions. The results follow:
KO = specific conductivity of the solutionbefore adsorption.
K = specific conductivity of the solutionat equilibrium.
Adsorption of potassium iodide b y silver iodide.
Ko .10".
45.1
7 2.2
17 6.0
280.8
448.2
694.8
87 3.2
i.osas
1,27 5.0
1,381.4
0
Potassium
iodide at start
(moles per
liter).
0. 000 299
. 000 481
;001 181
. 001 900
. 003 032
. 004 7 7 2
. 005 997
. 007 231
. 008 894
. 009 637
K .10.
19.7
61.5
164.3
268.8
399.3
646.2
827 .4
- 992. 8
1,245.6
1,359.4
B.
Potassium
iodide at equi-
librium
(moles per
liter).
0. 000 130
.000 410
. 001 102
. 001 819
. 002 7 01
. 004 438
. 005 683
. 006 926
. 008 689
. 009 483
LogB.
-3. 886
-3. 387
-2. 959
-2. 7 40
-2. 569
-2. 353
-2.246
-2. 160
-2. 061
-2.023
A.
Potassium
iodide adsorbed
per gram
silver iodide
(millimoles).
0.0046
.007 8
.0084
. .0087
;0090
.0090
.0085
.007 7
.0055
.0040
LogA.
-2.337
-2. 108
-2.07 6
-2. 061
-2. 046
-2. 046
-2. 07 1
-2. 114
-2.260
-2. 398
Inthe logarithmic diagram (fig. 5) the second, third, fourth, and
fifth points are exactly ona line, and, therefore, may be represented
by anexponential equation, but the fifth point is at a maximum,
higher initial concentrations resultingindecreasedadsorption.
The authors suggest that this phenomenonmay be due tostruc-
ture alterationor tocomplexsalt formation, but findnoconnection
PROPERTIES OF COLLOIDS.
41
betweenit andhydrosol formation. The present writer has made
calculations to ascertainif decreased dissociation due toincreased
concentrationmight account for the decreasedadsorption. Nosuch
relationshipwas indicated.
TENNESSEE BALL CLAY AND MALACHITE GREEN.
Ininvestigationof the adsorptionof malachite greenby Tennessee
ball clay No. 3, of the Tennessee Ball andSagger Clay Company,
Whitlock, Tenn., andthe Potters' Supply Company, East Liverpool,
Ohio, the logarithmic diagram (fig. 6) shows a similar maximum, but
none of the points lie onthe same straight line, evenwhena correc-
FIGURE 5. Adsorptionof pota sium iodide by silver iodide.
tion factor is introducedsimilar to that usedinthe discussionof
Hirsch's results onthe adsorptionof barium chloride by Klingenberg
clay.
SUMMARY.
Inthis discussionof equations are includedonly those cases which
have beenstudiedfrom very small concentrations uptothe highest
possible adsorption. We have then the exact equationA B~n= K,
applyingto
Silk andpicric acid,
Gelatine andtannin,
Hagerstownloam andgentianviolet,
Silver iodide andsilver nitrate;
42 COLLOID MATTER OF CLAY.
the correctedequationA'B~n= K, where A' =
1-
A
-, applying
to-
constant
Quartz flour andgentianviolet,
Klingenbergclay andbarium chloride;
4.5
LOG. B
3.0 3.5
FIGURE 6. Adsorptionof malachite greenby Tennessee Ball andSagger Clay Company's Tennessee Wall
clay No. 3.
andthe cases showingmaxima andnot permittingthe use of such
equations, as follows:
Silver iodide andpotassium iodide,
Tennessee ball clay No. 3 andmalachite green.
It does not yet seem possible toformulate anequationthat shall
apply toall cases of adsorption.
DETERMINATION OF PLASTICITY.
DEPENDENCE ON COLLOIDS.
If the plasticity of clays is mainly due toa proper ratioof granular
materials andactive (that is, not "set") colloidgels, any means of
establishingthe relative or absolute amount of colloids in a clay
shouldsupply a measure of its plasticity.
DETERMINATION OF PLASTICITY.
43
Of course, the shape andsize of the granular materials (whether
of crystal nature or "set" gels) will be of some effect, as will also
the special nature of the active colloids present. Any methods
appliedtotestingother colloids shouldbe of value intestingclays.
For instance, glues andclays are testedby the tensile-strength test
for tensile strength or bindingpower. While this test is of value,
it does not tell how workable a clay is. Sugars andoils are tested
by measurements of viscosity. Simonis (51, 52, 53, 7 2, 7 3), Mellor
(47 ), andBleininger (49) have appliedthis test toclay slips. The
twoformer have shownby this means how plasticity may be altered
by additions to clay slips, especially inregardtotheir suitability
for the castingprocess. Bleininger has showninthe case of three
well-knownclays that the more plastic has the greater viscosity.
ADSORPTION TESTS OF CLAYS.
Hirsch (7 0) inhis paper onthe behavior of clay insalt solutions
saw the possibilities of adsorption. He. said: "We hopedat first to
be able toclassify the clays accordingtotheir plasticities with the
helpof this process [adsorptionof barium chloride]. The lean, very
sandy brick clays fall completely out of the series, andpartially
show a greater adsorptionthanthe fat, highly plastic clays." The
present writer, havingthe informationthat colloids adsorb dyes, but
without any details, alsosought toapply this principle tothe meas-
urement of plasticity.
ADSORPTION TESTS WITH BRILLIANT GREEN.
OnMay 21, 1908, at a meeting of the Pittsburgsection of the
AmericanChemical Society, aninformal discussionwas heldregard-
ingthe results thenattained. The followingtable was shown. The
comparisons were made colorimetrically with improvisedapparatus
of the crudest sort:
Dy e remaining unadsorb ed on treating various clay s (50 grams each) with b rilliant green
(in 1 ,000 cub ic centimeters water}.a
Harris, North Carolina china clay ....
0.10
0.002
0.20
0.002
.002
.007
0.30
0.004
.031
0.50
0.001
.007 3
0.60
O.OCG
.021
.111
1.00
0.001
.017
.07 3
.111
.17 2
,292
2.00
0. 0133
.004
.110
3.00
0.045
All experiments submittedherewith were made with tapwater from OhioRiver, filteredthrough
gravel andledinby a longironpipe.
Inthe columnfor 1.00 gram dye-these clays fall approximately
inthe order of their plasticities. There are, however, various anoma-
44 COLLOID MATTER OF CLAY.
lies, the most strikingof which, is the apparent difference of WH2 and
BBchina clays, which are practically almost duplicates inplasticity.
Inthe discussion, Dr. Joseph H. James suggested.that malachite
greenwouldbe founda more stable dye, less likely tobe affectedby
adventitious circumstances, andsubsequently the use of that dye
was adoptedwith decidedadvantage.
A further series of tests was, however, made with brilliant green.
Ineach case the water, the crushedair-dry clay, andthe dry dye
were put ina small test blunger, blungedfor 30 minutes, andthen
allowed to settle until apparently clear. The dye remaining in
solutionwas determinedcolorimetrically.
Dy e remaining unadsorb ed on treating various clay s (50 grams each, in 1 ,000 cub ic
centimeters water) with b rilliant green dy e.
"Lone Star," Texas "kaolin".. . ...................................
No. 10 run-of-mine Tennessee ball clay, Johnson-Porter Clay Co. ...
No. 12 English ball clay, G. Knowles & Sons. . .....................
No. 1 sagger clay, P. L. Ryan. . ....................................
No. 8 sagger clay, Edgar Bros. Co. .................................
Al English china clay, Hammill & Gillespic. .......................
1.00
0. 0006
. 000338
.006
. 00814
.0095
.011
.017
.018
.020
.022
.028
.0287
.0424
.056
.0562
.0588
.07 3
.084
..094
.098
.111
.126
.17 2
.1886
.292
.314
.314
.37 5
.500
2.00
0.013
.087 8
.0253
.111
.064
.061
.1456
.063
.102
.110
3.00
0. 000097
.045
.0901
4.00
0. 087 8
.1818
a With 7 .00 grams, the result was 0.000827 ; with 10.00 grams, 0.00267 ; with 13.00 grams, 0.01054; with
18.00 grams, 0.1205.
These clays fall neither inthe order of plasticity nor of merit in
the columnwith 1.00 gram dye; 2.00 grams dye give a somewhat
better arrangement, Texas, Pike's No. 20, RyanNo. 1, M. & M. ball,
Knowles's, No. 12 ball, Tennessee No. 3, special sagger, Florida, No. 10
run-of-mine, andTennessee No. 9, fallinginascendingsequence.
If, however, these clays are groupedsothat only clays of a common
originare in the same column, the arrangement is more logical in
each group.
DETERMINATION OF PLASTICITY. 45
Dy e unadsorb ed (1 gram added), arranged b y origin of day s treated.
English ball clays.
Eimor &
Am end
ful ler's
earth.
Pike'5! No.
20.
Knowles's
No. 12.
M ooi." e &
Hunger.
0.0006
.0095
.017
.022
Tennessee ball and
sagger clays.
Tenness e e
No. 3.
No. 10,-run
of mine.
Tennessee
No. 9.
Special
sagger.
P. S. Co.
wad.
J-P. C. Co.
wad.
M-S. C. Co.
wad.
0.008
.011
.020
.028
.098
.126
.314
Atlantic coast
sagger clays.
RyanNo. 1
Edgar No.
8.
Edgar No.
10.
SuchBB..
0.018
.029
.042
.059
Atlantic coast
china clays.
Bryson.....
Penland....
Bluemont. .
0.006
.056
.17 2
.189
English china
clays.
HN. ......
Poole No.
1.
WH2 .......
BE.......
Al.. .......
M GR.....
No. 15......
0.084
.094
.111
.292
.314
.37 5
.500
It wouldappear from.this that the colloidal matter inany one of
these groups, for example, Atlantic coast china clays, has aneffect
on brilliant green different from that of the colloidal matter in
some of the other groups, for example, English china clays. Brilliant
greenmay thenbe of use only tocompare clays of a commonorigin,
or tocheck the uniformity of a particular clay from time totime.
COMPARISON OF BRILLIANT GREEN WITH MALACHITE GREEN.
Schultz andJulius (7 4) give the followingformulae:
Malachite green(oxalate), (C23 H24 N2 ) 2 (C2 H2 04 ) 3 , of which the molec-
ular weight is 890.6, or per one color base ion, 445.3.
Brilliant greencrystals, C27 H34 N2 04 S; molecular weight, 482.4.
The structural formulae may be representedas showninfigure 7 .
The brilliant greenhas the more complexcolor base, havingfour
C2H5 groups against anequal number of CH3 groups in malachite
green. AccordingtoPelet-Jolivet andWild(7 5), malachite greenis
wholly noncolloidal, while from the paper of Hober andChassin(7 6),
brilliant green seems also to be noncolloidal. The former authors
findthat dye solutions, under the influence of electrolytes, goover
tothe colloidcondition, andthink that contact with ;anadsorbent
favors such a transformation.
QUALITY OF WATER USED.
The tapwater usedinthis work containedconsiderable amounts
of calcium sulphate andcalcium carbonate, andlesser amounts of
magnesium sulphate, magnesium carbonate, and sodium chloride.
It wouldconsequently have a considerable precipitatingeffect onthe
oxalic acidions of the malachite green. This was foundtobe the
case, but if the water were of constant composition, it shouldnot
affect the order of the clays inthe classification, as equal volumes were
46 COLLOID MATTER OF CLAY.
usedin all comparisons. However, it was found that acetic acid
wouldprevent precipitation, andit was employedina considerable
number of tests with malachite green. It was thenfound, although
a preliminary test hadgiventhe opposite result, that the weak con^
centration of acetic acidpresent acting on the iron stirrer of the
blunger was effectingsome decolorizationof the dye. These results
were accordingly discardedandthe use of the blunger was abandoned
entirely.
The results with acetic acidfailedtogive a more accurate classi-
fication than did the simple aqueous solution. Consequently the
use of acetic acidwas abandoned.
(CH3 ) 2
Gj.Hj.04.
C iHj.04-
FIGURE 7 . Structural formulas of malachite greenandbrilliant green.
MALACHITE-GREEN ADSORPTION AND PHYSICAL PROPERTIES OF CLAYS.
METHODS OF TESTING.
The following procedure was eventually adopted. Into a 500
cubic centimeter bottle with ground-glass stopper greased with
vaseline, 20 grams clay andthe dye were placed, then 400 cubic
centimeters water was added. The closedbottle was thenfastened
inthe frame of a small ball mill (60 revolutions per minute) sothat
at every revolutionit was upended. This gave a. vigorous andcom-
plete agitation, which lasted for an hour. Although the clay
appearedtosettle clear inhalf anhour, the results were toolarge and
erratic unless the settlingcontinued over night. 0 On the following
a Poole's No. 1 china clay (50 grams clay, 1,000 cubic centimeters water, 3 grams dye) gave:
Grams dye
inexcess.
July 30, after standingsome time.............................................................. 1. 840
July 31, after standingover night.............................................................. 1.7 97
July 31, after rotatingagain(seemedclear)..................................................... 2.012
August 1, after standingover another night.................................................... 1.7 50
U. S. G EO L O G ICAL SURVEY
APPARATUS FO R MAKING CO L O R CO MPARISO NS TO DETERMINE ADSO RPTIO N O F DYESTUFF.
DETERMINATION OP PLASTICITY. 47
day a convenient amount of the clear liquidwas takenout by a
pipette andput intoone of a pair of "carbon" comparison tubes
such as used in steel analysis, and compared by dilution with a
standard solution of 3 grams per liter, using a camera while
matching. (See PI. I.)
RESULTS OF TESTS.
The powers of various clays toadsorb malachite green, together
with other physical properties, are giveninthe following table, in
which the clays, as elsewhere inthis bulletin, are designatedby their
trade names:
A
d
s
o
r
p
t
i
o
n

o
f

m
a
l
a
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t
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p
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s
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c
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l

p
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r
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s

o
f

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s

c
l
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y
s
.
0
0
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e
s
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n
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n

o
f

c
l
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.
-
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N
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3

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9

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>
50 COLLOID MATTER OF CLAY.
MALACHITE-GREEN ADSORPTION.
The results with 3.0-gram dye per 50.0 grams clay in1,000 cubic
centimeters water are usedas a basis for comparison. From these,
columnC has beenpreparedby means of figure 8. a The principle is
this: If there is a certainamount of colloids in, say, 10 grams of No.
3 ball clay, there is twice as much in20 grams, three times as much
in30 grams, etc. Let us call the amount of colloids.in50 grams 100,
in20 grams 40, etc. Treatingeach of these amounts of No. 3 ball
clay with 3 grams of malachite green, we obtainthe curve shownin
figure 8. Now suppose we take 50 grams of any other clay, say,
Moore & Hunger's ball clay, andtreat it with the same .amount of
20 30
Grams P .5.C o.No.3,T ennesse? ballclay
50
100
80
Relative colloid value
FIGURE 8. Adsorptionof malachite greenby Potters' Supply Company's Tennessee ball clay No. 3.
dye, the amount of dye adsorbedproves tobe 2.87 7 9 grams; 2.87 7 9
grams comes onthe curve at 43.35 grams Tennessee ball No. 3, or at
90.7 relative colloids; that is, it is assumed that clays adsorbing
equal amounts of dye containequal amounts of colloids, andthese
are expressedinterms of the amount present inTennessee ball No. 3.
PHYSICAL PROPERTIES O F CLAYS.
ColumnA, Jackson-Purdy surface factor, contains numbers which
it is convenient toassume are proportional tothe total area of all the
a Work performedin1909 with pure water andlonger periods of shakingshow that the twobranches
of the curve showninfigure 8 approximate straight lines, meetingat anangle.
DETERMINATION OF PLASTICITY. 51
particles ina unit weight of clay, and are thus- a measure of the
fineness of the material. The methodwas originally proposedby
W. Jackson(7 7 ) andmade more general by Ross C. Purdy (7 8). The
assumptionis far from correct, as the colloids andsoluble salts are
not granular andthe average size assumedfor the smallest grains is
incorrect, but it is a convenient approximation.
ColumnB, cast air shrinkage, contains values obtainedby casting
a clay slipintoa plaster of Paris mold10 centimeters indiameter,
usingapproximately 50 grams of clay, andgivinga test piece about
.0.5 centimeter thick. A number of precautions are necessary for
accurately comparable work, andit is regrettedthat some of these
figures, three years old, do not have the precision of later work
(7 9, 82).
The columnof fire shrinkage at cone 8 is put inmerely because of
its general interest.
The surface factor, air shrinkage, and relative colloids were in
some cases determinedonone andthe same sample; inothers, on
separate lots; andinstill others they are averages of material exam-
ined over considerable periods. ' However, such error as is intro-
ducedinthis manner is properly tobe chargedagainst the clay.
The maximum errors possible are probably 20 per cent inthe case
of the surface factor, 1 per cent for air shrinkage, and5.0 per cent for
relative colloids. The average errors, however, will not exceed5 per
cent for surface factor, 0.3 per cent for air shrinkage, and2.5 per cent
for relative colloids.
IncolumnD has beenput the surface concentrationof colloids,
obtainedby dividingthe relative colloids by the surface factor. It
is an attempt to express numerically the density of the layer of
colloidmaterial that is consideredas envelopingthe granular mate-
rial. Theoretically, not the surface factor but only that portion
correspondingtothe granular material shouldbe used; but a method
for obtainingthis informationhas not yet beenworkedout. The
values inthis columnshouldclosely parallel the bondingpower of
these clays.
It is assumed that the various clay colloids will differ in their
ability toabsorb water, and, consequently, intheir shrinkage. In
columnE it is attemptedtomeasure this effect by calculatingthe
specific air shrinkage, for which purpose the linear air shrinkage is
dividedby the relative colloids.
The lubricatinglayer,- permittingmotiontothe granular particles,
is made upof colloids holdingwater; andincolumnF this is esti-
matedas deformability, directly proportional tothe surface concen-
trationof colloids andtotheir specific air shrinkage, hence totheir
product.
52 COLLOID MATTER OF CLAY.
, Texas "kaolin."
Mandle-Sant special sagger.
Prall No. 1 sagger.
Prall No. 1 retort.
Knowles No. 12 ball.
Potters' Supply Tennessee ball No. 3.
Pike's No. 20 ball.
EyanNo. 1 sagger.
, Paul groundfire clay.
. Mandle-Sant Tennessee No. 3.
. Atlanta M. & C. Co.
. Kentucky C. & I. Co. No. 1 sagger.
. DiamondFireclay Co.
. Johnson-Porter No. 9 Tennessee.
. Moore & 'Munger ball.
. Excelsior B. C. Co. sagger.
. Potters' Supply Co. Tennessee No. 4.
. Edgar No. 8 sagger.
. Edgar Florida.
. Such BBsagger.
. Edgar No. 1 10 sagger.
. Mandle-Sant No. 11 Tennessee.
. Johnson-Porter wad.
, Potters' Supply Co. wad.
, Johnson-Porter UX sagger.
, Harris Penlandkaolin.
, Harris Bryspnkaolin.
Priem Z ettlitz kaolin.
. Mandle-Sant wad.
Hall Georgia kaolin.
Mandle-Sant Tennessee No. 9.
Johnson-Porter No. 1 ball.
Adolph WE2 kaolin.
Hammill & Gillespie kaolin.
. DuncanWhite Mountainclay.
Poole No. 1 kaolin.
PooleBBkaolin.
Moore & Munger HN kaolin.
Sant Bluemont kaolin.
Peach kaolin.
Moore & Munger MGR kaolin.
Knowles No. 15 kaolin.
.I74O
Deformability
.20 .40
E. Specific air shrinkage of colloids
FIGURE 9. Surface concentrationandspecific air shrinkage of clay colloids as relatedtodeformability.
DETERMINATION OF PLASTICITY. 53
The relations of columns D, E, andF are showngraphically in
figure 9. It will be seenthat ball andsagger clays fall inone group,
havingcolloids of low specific air shrinkage. The china clays fall in
another distinct group, havinglow surface concentrationof colloids.
The wad clays apparently form a distinct group with somewhat
greater surface concentrationof colloids thanthe china clays. The
Texas andFlorida " kaolins " a are distinct from all other clays and
from each other. The twofire clays testedare closely associated
with the ball andsagger clays. With finer grindingthe resemblance
wouldappear stronger.
Finally incolumnG anexpressionis givenfor plasticity. Both
Z schokke (80) andGrout (9) have experimentally determinedplastic-
ity as the product of a deformationby the force producingit. Simi-
larly it is here takenas the product of the deformability by the force
resistingdeformation, assumingthat this resistance is exertedby the
colloids, which are the cementingmaterials supplyingthe cohesion
of the clay. This is the product of columns C andF, but F is the
C B
product of columns D andE, andthese represent -r and prespec-
... , , n CxB
tit very; whence G = -r .
Since ordinarily the shrinkage (B) andthe surface factor (A) are
T O
both highest with high colloidal matter (C), it is evident that -r- will
approximate a constant, andthat plasticity is mainly due tothe rela-
T D
tive colloids (C). The fraction- r seems totake care very satisfac-
torily of the variations inthe nature of the colloidmatter andof the
size of grain.
It will be notedthat increasedfineness of grainis consideredas
cuttingdownthe plasticity. It has beenthe writer's repeatedobser-
vationthat increasedfineness of grainof the granular material ina
clay or body is a source of weakness andtrouble; that, havinggreater
surface, more colloidmatter is requiredtocement the fine granular
matter together andsoshrinkage andliability tocrack are increased.
a Work performedin1909 shows that the surface factor of Florida clay is really 185, sothat the data
basedonthis determinationare inerror, andthe clay really falls nearer the other china clays onthe
deformability diagram.
54 COLLOID MATTER OF CLAY.
PLASTICITY.
AS DETERMINED BY MALACHITE-GREEN ADSORPTION TESTS.
In the following table the clays are arranged as classified by
columnG:
Plasticity of various clay s.
Texas " kaolin"........................................................... 10. 34
Ball andsagger clays:
Maudle-Sant special sagger.............................................? 9. 09
Prall No. 1 light sagger................................... r ............ 7 . 27
Ball clays
Knowles No. 12 ball.............................................. 6. 53
Pike's No. 20 ball................................................ 6. 28
Mandle-Sant No. 3 Tennessee...................................... 5. 96
Johnson-Porter No. 9 Tennessee................................... 5. 7 6
Kentucky ConstructionandImprovement Co., No. 1 sagger........ 5. 69
Edgar Plastic KaolinCo., Florida..................................? 5. 66
Prall, No. 1 retort................................................ 4. 90
Moore & Hunger, ball.............................................. 4. 88
Ryan, No. 1 sagger................................................... 4. 7 9
Atlanta MiningandClay Co., Georgia................................. 4. 7 3
Potters' Supply Co., No. 3 Tennessee................................... 4.62
Potters' Supply Co., No. 4 Tennessee................................... 4. 52
Excelsior Ball Clay Co., sagger........................................ 4. 20
Such, BBmixture .................................................. 3. 66
Edgar Bros. Co., No. 8 sagger......................................... 3. 51
Johnson-Porter, No. 10 Tennessee...................................... 3. 45
Edgar Bros. Co., No. 10 sagger......................................... 2. 63
Paul Clay Co., groundfire clay........................................ 2. 595
Wadclays:
Johnson-Porter, X wad..................................:............? 1. 867
Johnson-Porter, TJX sagger............................................ 1. 824
Potters' Supply Co., wad............................................. 1. 7 7 5
Mandle-Sant Clay Co., wad...........................................? 1.530
Mandle-Sant Clay Co., No. 9 Tennessee...................................... 1. 47 3
Johnson-Porter, No. 1 ball................................................. 1.37 8
China clays:
Hall Clay Co., Georgia sagger (kaolin) .................................. 1. 335
Priem, Z ettlitz, kaolin................................................ 1. 335
Harris, Penlandchina clay........................................... 1.117
Adolph, WH2 china clay............................................... 1.104
Harris, Brysonchina clay.............................................. 1. 097
Poole, No. 1 china clay. ............... i............................... 1. 097
Sant, Bluemont china clay............................................ . 916
Duncan, White Mountainclay........................................ . 903
Poole, BBchina clay................................................ .87 3
Hammill & Gillespie, Al china clay.................................... . 868
Moore & Munger, H N china clay...................................... . 67 5
Moore & Munger, M G R china clay................................... . 647
Knowles, No. 15 china clay........................................... . 618
Peach KaolinCo., china clay.......................................... . 556
DiamondClay Co., groundfire clay........................................ . 000
DETERMINATION OF PLASTICITY. 55
PLASTICITY AS FOUND IN PRACTICE.
Various anomalies have tobe explained. Experimental errors in
elutriation, clue toincomplete deflocculationof the clays, have prob-
ably made too high the values markedwith a ?. Inthese cases
the dyedclay was elutriated. It was foundout later that dyeing
increases the size of the floccules andhence decreases the surface
factor. The twoNo. 3 Tennessee ball clays occur onadjacent prop-
erties. It is believedthat the shrinkage measurements or the sur-
face factors of one or both are inerror, the former havingbeenmade
three years agofor one of the clays andthe latter presentingdifficul-
ties in deflocculation. The Mandle-Sant No. 9 Tennessee ball is
much more plastic thanits positioninthe table indicates. Neither
UX nor Johnson-Porter No. 1 ball is a strong clay, and they are
correctly placed. Amongthe china clays there is the possibility of
the additionof some whitening agent, or of wetting by salt water
intransit across the ocean, that wouldinterfere with the colloidtest.
The lowest English clay onthe list, Knowles No. 15, has a very good
reputationas a " safe" clay. The DiamondClay Company's fire clay
with finer grindingwill have a measureable shrinkage, andis capable
of beingclassedwith the sagger clays if soground. But as supplied,
i.ts shrinkage-is less thanthe possible error of measurement, andit is
correctly placedas tothe plasticity inthe coarse groundcondition.
Very few people will agree exactly intheir conceptionof plasticity.
Each considers a body most plastic whenit best suits his work. A
jiggermananda presser inthe same clay shopwill not agree as to
the amount of moisture requiredinthe body used. Whena brick-
maker calls a clay plastic he means that it will work well inhis
machine; but a potter means by the same phrase that it is fat enough
to mix with considerable inactive material ("flint," spar, etc.) to
make a workable body. An electric porcelain plant will have a
tube, wet-press, or plastic body anda dry-press or insulator body.
The writer hopes to show by later investigations that a certain
"degree" or measure of plasticity is best suited to each class of
manufacture.
The errors of measurement are in most cases small, andon the
whole the table accurately represents those properties of clays that
may be collectively describedas plasticity. -
o Invaluingclays, plasticity is but one of the factors tobe consid-
ered; refractory properties, color, cleanness, etc., all gotogether in
the selectionof the clays tobe usedfor the manufacture of wall and
floor tiles, sanitary ware, terra cotta, pottery, etc. The measure-
ment of the relative colloids, surface factor, andcast air shrinkage
of various clays will give, however, anaccurate andcomplete idea
of their workingproperties or plasticity.
56 COLLOID MATTER OF CLAY.
MISCELLANEOUS APPLICATIONS OF MALACHITE-GREEN
TEST.
EFFICIENCY OF GRINDING.
The Texas "kaolin" andthe fire clays .mentionedinthe preceding
pages were testedas suppliedtothe trade. They were alsotested
as tothe effect of fine grinding.
Test of 50.0 grams Tex as "kaolin," 5.00 grams malachite green, and 1 ,000 cub ic centi-
meter's of water.
Grams dye unaclsorbed.
As supplied.................................................... 0. 0456
Ground1 hour inball mill with dye............................ . 0314
Ground2 hours inball mill with dye........................... . 0315
Test of 50.0 grams Paul Clay Company 's ground sagger (fire clay ) ivith malachite green
and 1 ,000 cub ic centimeters of water.
1.00 gram 3.00 grams
dye. dye.
As supplied............................................ grams dye unadsorbed.. 0.023 25 0.57 8
Ground1 hour ...........................................................do.... .001 515 ............
Ground2 hours ..........................................................do................ . 2513
Test of 50.0 grams Diamond Clay Company 's ground fire- clay with malachite green and
1 ,000 cub ic centimeters of water.
1.00 gram 3.00 grams
dye. dye.
As supplied............................................grams dye unadsorbed.. 0.018 95 1.058
Ground1 hour............................................................do.... .000 309 ............
Ground2 hours...........................................................do................ .065
Ineach of these cases finer grindingcausedincreasedadsorption
of dye, but the extent of the effect is markedly different inthe three
cases andseems tocorrespondtothe development of the so-called
"latent" plasticity of fire clay. This has already been ascribed
(p. 13) toa reabsorptionof water anda swellingtothe original bulk
of the clay, possessedages agobefore the clay hadbeensubjectedto
pressure inits place of deposit.
The dye test thensupplies a measure of the efficiency of grinding
inincreasingthe plasticity of a fire clay.
It was noticed that brilliant green, insteadof retainingits usual
bluish-greentint, became a much purer greenwith Pike's No. 20 ball,
Eimer & Amend's fuller's earth, andSant's Tennessee ball No. 3;
noexplanationis offered. Malachite greendevelopeda purer blue
with Eimer & Amend's fuller's earth.
APPLICATIONS OF MALACHITE GREEN TEST. 57
FULLER'S EARTH.
Fuller's earth has beenshownby W. L. Dubois (35) tobe utterly
unreliable as a means of estimatingcolorirnetrically the amount of
caramel invinegar, whenequal amounts of fuller's earth are used
with equal amounts of vinegar. With pure vinegars any givenlot
of fuller's earth wouldhave noeffect onsome vinegar, andwould
remove upto60 or 7 0 per cent of the color from other vinegars. The
results appearedextremely erratic. While this problem is separate
from the present investigation, it is closely parallel; inboth cases a
colloidal earth is usedtoremove a coloringmatter from solution. In
the light of this experience it is thought that the followingarrange-
ments would lead to comparable results: As, in this work, the
additionof acetic acidincreased the apparent intensity of the dye
upto33 per cent over that inaqueous solution, it wouldappear that
vinegars shouldbe brought toa uniform acidity before applyingthe
fuller's-earth test; that is, either water or pure acetic acidshouldbe
addedtobringthe acetic acidtoa standardconcentration. Dubois
"usedvarious fuller's earths of unknowncolloidal strength toprecipi-
tate caramel of unknown strength. The proper procedure would
seem tobe todetermine what proportionof a particular fuller's earth
will remove caramel most completely from a particular vinegar when
brought tothe standardacetic-acidconcentration. Thenstandardize
this fuller's earth against a pure dye solution, such as the malachite
greenoxalate usedinthis work. Inusingother lots of fuller's earth
such quantities should be taken as will have equal decolorizing
actiononthe standarddye.
By this procedure the writer feels confident that the fuller's-earth
test for caramel wouldbe much improved.
PARIS WHITES.
The malachite greentest has beenappliedtoa number of " English
cliffstone Paris whites" with the followingresults:
Test of English cliffstone Paris whites with 3 grams of malachite green dy e.
Dye
unadsorbed.
0. 0218
.0224
.0251
.0280
Relative
market
150
120
115
100
Surface
factor.
182
168
168
165
Remarks.
Claimedtobe finest sold.
It appears that there is a close relationshipbetweenmarket price
andfineness anddye precipitated. It is alsotobe remarkedthat
carbonate of lime inthis form removes the dye very completely from
solution, andtoa much greater extent thancorresponds tothe very
slight plasticity it possesses. Way (15) observed the presence of
58 COLLOID MATTER OF CLAY. 4
gelatinous silica inthe chalk formations; sothat it will be necessary
tofindout whether pure dalcium carbonate has the same actionas
this English cliffstone Paris white.
FUTURE WORK.
There is still considerable work tobe done inconnectionwith this
test for colloids.
While malachite greenseems excellent for the purpose, other dyes
may be equal or better. Messrs. H. A. Metz & Co. have kindly sup-
plieda very comprehensive set of dyes for studyingthis point. The
dye selectedshouldbe testedto see whether suppliedinuniform
quality from various sources.
'The possible disturbingeffect of various soluble salts andminerals
shouldbe determined.
The rate of deteriorationof standardsolutions shouldbe studied.
These studies have beenconfinedtohigh-grade clays, anda wider
range of materials shouldbe studied. Samples of the various bodies
usedinthe ceramic industries have beencollected, andit is intended
toascertainwhether definite numerical limits canbe givenfor the
plasticity requiredby each.
It is also intended to study the process of aging clays, as this
method will permit measurement of the progressive increases in
plasticity.
It is intendedtoformulate a fieldtest for plasticity that will deter-
mine whether the clay is worth more accurate investigation.
Seger (81) has notedinseveral places that there seems tobe a close
relationshipbetweenthe amount of soluble salts ina clay andits
plasticity. Purdy andMoore consider it "anexceedingly probable
assumptionthat it is the influence of the adsorbedsalts that gives to
a day its plasticity" (83). It is probable that inthe malachite green
test the color base is exchangedwith the bases that stabilize the gel
andwith the bases of the soluble salts present, andthat the oxalates
of lime, etc., are precipitated. It is possible that a dye havingits
color base unitedwith hydrochloric acidmay supply an excellent
means of studyingthe soluble salts inclay. Hirsch's work with alumi-
num chloride indicates the feasibility of such a procedure (7 0).
As anaccurate surface factor is essential toa careful study of a clay,
the best means of defiocculationof the clay particles before elutriation
shouldbe studied. It is not believedthat ammonia, or longboiling,
or violent shakingis the proper means; but that the formationof the
clay hydrosol canbe better effectedby the additionof a more suitable
chemical reagent or solvent. This is beingstudied.
KEFERENCES. 59
SUMMARY. t
. Clay is definedas a mixture of granular matter anda colloidgel.
The sources of the colloidmatter are organic, resemblingpeat, and
inorganic, principally colloidal silicates andsilica andless commonly
alumina andferric oxide.
Adsorption, the property colloids have of takingother substances
out of solutionor suspension, may inmost cases be representedby
exact equations.
The adsorptionof a dye by clays supplies anapproximate measure
of plasticity.
The plasticity, takenas the product of the deformability by the
CxB
force resisting deformation, reduces tothe expression - , where
A.
C is the measure of colloids present, Bis the cast air shrinkage, andA
is the Jackson-Purdy surface factor.
The dye test supplies a measure of the efficiency of grindingin
increasingthe plasticity of a fire clay. Questions that call for further
study are the possible findingof a better dye thanmalachite green,
the* disturbinginfluence of minerals andsalts inclays, andthe formu-
lationof a fieldtest for plasticity.
REFERENCES.
1. Schloesing, Th., The constitutionof the clays: Compt. Rend., vol. 7 9, 187 4,
pp. 37 6-380, 47 3-47 7 .
2. VanBemmelen, J. M., Compounds of several soliddioxide hydrates with acids,
salta, andalkalies: Jour, prakt, Chemie, 2dser., vol. 23, 1881, pp. 324-349, 37 9-395.
3. Mayer, Adolph, Forschungenauf dem Gebiete de'r Agricultur Physik, vol. 3, pt. 2.
4. U. S. Dept. Agr., Bur. Soils, Bull. 24, 1904, p. 9.
5. Davis, Charles A., Peat: Eighth Ann. Kept. Geol. Survey Michigan, 1906, pp.
320, 325.
6. Schreiner andReed, Certainorganic constituents of soils inrelationtosoil fer-
tility: U. S. Dept. Agr., Bur. Soils, Bull. 47 , 1907 , p. 10.
7 . Methods of analysis; humus insoil: XL S. Dept. Agr., Bur. Chem.,Bull.
107 , 1907 , p. 19.
8. Acheson, E. G., Egyptianizedclay: Trans. Am. Ceram. Soc., vol. 6, 1904, p. 31.
9. Grout, F. F., West Virginia Geol. Survey, vol. 3, 1906, p. 47 -.
10. Hardy, W. B., Onthe mechanism of gelationinreversible colloidal systems:
Proc. Roy. Soc., vol. 66, 1899, pp. 95-109.
lOa. Idem, p. 112.
11. Cushman, AllertonS., The colloidtheory of plasticity: Trans. Am. Ceram. Soc.,
vol. 6, pp. 65-7 8.
12. Wiley, Harvey W., Principles andpractice of agricultural analysis, vol. 1, p. 120.
13.. Eichorn, , Landw. Centralbl., vol. 11, p. 169.
14. Way, J. T., Jour. Royal Agr. Soc., vol. 11, 1850.
15. Way, J. T., Ondeposits of soluble or gelatinous silica inthe lower beds of the
chalk formation: Jour. Chem. Soc., vol. 6, 1854, pp. 102-106.
16. VanBemmelen, J. M., The absorptive power of soils: Jahresber., 1888, pt. 2,
p. 27 37 .
60 o COLLOID MATTER OF CLAY.
17 . Warington, Robert, jr., Onthe part takenby oxide of ironandalumina inthe
absorptive actionof soils: Jour. Chem. Soc., 2dser., vol. 6, 1868, pp. 1-19.
18. Cameron, F. K., andBell, James M., The mineral constituents of the soil solu-
tion: U. S. Dept. Agr., Bur. Soils, Bull. 30, 1905, p. 22.
19. Idem, p. 23.
20. Weber, Carl Otto, The chemistry of india rubber, London, Charles Griffin& Co.
(Limited), 1902, p. 7 9.
21. VanBemmelen, J: M., The absorptionof water inthe colloids, especially inthe
gel of silicic acid: Z eitschr. anorg. Chemie, vol. 13, 1896, pp. 232-357 .
22. The Leuchter process of reducingor enlargingmodels: The Brass World,
vol. 3, 1907 , p. 37 1.
23. Hillebrand, William Francis, Some principles andmethods of rock analysis:
Bull. U. S. Geol. Survey No. 17 6, 1900, pp. 52-53.
24. Whitney, W. R., andOber, J. E., The precipitationof colloids by electrolytes:
Jour. Am. Chem. Soc., vol. 23, 1901, p. 844.
25. Coehn, , [Electric charges]: Wied. Ann., vol. 64, 1898, p. 217 .
26. Bredig, , [Similarity of actionof colloidal platinum andorganic ferments]:
Chem. Z eitung, vol. 24, 1900, p. 895.
27 . Whitney, W. R., Colloids: Trans. Am. Electrochem. Soc., vol. 7 , 1905, pp. 225-
233.
28. Bredig, G., Z eitschr. angew. Ghemie, 1898, p. 951.
29. Mayer, Schaeffer, andTerroine, Influence de la reactiondumilieusur la gran-
deur des granules colloidaux: Compt. Rend., vol. 145, 1907 , pp. 918-920.
30. Spring, -^ , Recueil trav. chim. Pays-Bas, vol. 19, 1900, p. 204.
31. Lottermoser, A., The formationprocess of hydrosols andhydrogels: Z eitschr.
phys. Chemie, vol. 60, 1907 , p. 451. l!
32. PictonandLinder, Solutionandpseudosolution: Jour. Chem. Soc., vol. 61,
1892, p. 17 1.
33. Schulze, , Jour, prakt. Chemie, vol. 25, 1882, pp. 431-452.
34. Proctor, H. R., Colloidal chemistry: Chem. News, vol. 98, 1908, pp. 152, 167 ,
17 5.
35. Dubois, W. L., The fuller's earth test for caramel invinegar: Jour. Am. Chem.
Soc., vol. 29, 1907 , p. 7 5. Also, U. S. Dept. Agr., Bur. Chem., Bull. 105,1907 , p. 23.
, 36. Teague, Oscar, andBuxton, B. H., The precipitationof aniline dyes: Z eitschr.
phys. Chemie, vol. 60,1907 , p. 469.
37 . Cushman, AllertonS., Rock decompositionandclay formationinthe laboratory:
Trans. Am. Ceram. Soc., vol. 8, 1906, p. 180.
38. Cushman, AllertonS., Onthe cause of the cementingvalue of rock powders
andthe plasticity of clays: Jour. Am. Chem. Soc., vol. 25, 1903, pp. 451-468.
39. Sullivan, Eugene C., The interactionbetween minerals andwater solutions:
Bull. TJ. S. Geol. Survey No. 312, 1907 .
40. Rohland, Paul, The semipermeability of clays: Sprechsaal, vol. 39,1906, p. 129.
41. Stover, EdwardC., Bacteria inclay mixtures: Trans. Am. Ceram. Soc., vol. 5,
1903, pp. 358-361.
42. PictonandLinder, Solutionandpseudosolution: Jour. Chem. Soc., vol. 7 1,
1897 , pp. 568-57 3.
43. Rohland, P., The means for alteringthe amount of plasticity of clays: Sprech-
saal, vol. 39, 1906, pp. 137 1-137 2.
44. Clarke, F. W., Data of geochemistry: Bull. U. S. Geol. Survey No. 330, 1908.
45. Kuzel, Hans, Process of manufacturingincandescent metal filaments: German
patent 194348, July 25, 1905.
46. Clarke, F. W., Data of geochemistry: Bull. U. S. Geol. Survey No. 330, 1908,
p. 423.
EEFEEENOES. 61
47 . Mellor, J. W., Green, S. A., andBaugh, T., Studies on clay slip, I: Trans.
English Ceram. Soc., vol. 6, pp. 161-17 0.
48. Binns, Charles F., The functionof boron inthe glaze formula: Trans. Am.
Ceram. Soc., vol. 10, pp. 158-17 4.
49. Bleininger, A. V., The viscosity of clay slips: Trans. Am. Ceram.. Soc., vol. 10,
pp. 389-395.
50. Henry, Charles, Spectophotome'trie, viscosime'trie, et signes electriques des
solutions: Compt. Rend., vol. 145, 1907 , p. 1415.
51. Simonis, Max, Physical definitionof clay andnonplastics: Sprechsaal, vol. 38,
1905, pp. 1625-1626.
52. Simonis, Max, The tenacity of clay slips: Sprechsaal, vol. 38, 1905, p. 597 .
53. Simonis, Max, Z ettlitz clay andalkali: Sprechsaal, vol. 38, 1905, p. 881.
54. VanBemmelen, J. M., The nature of colloids andtheir water content: Chem.
Centralbl., 1888, p. 1255.
55. PattenandGallagher, Absorption of vapors andgases by soils: U. S. Dept.
Agr., Bur. Soils, Bull. 51, 1908. ~
56. Day andAlien, Isomorphism and thermal properties of the feldspars: Am.
Jour. Sci., 4th ser., vol. 19,1905, p. 127 .
57 . VonDobeneck, , Porsch. Geb. Agr.-Phys., vol. 15, 1892, p. 201.
58. Briggs andMcLane, The moisture equivalent of soils: U. S. Dept. Agr., Bur.
Soils, Bull. 45, 1907 .
59. Hofmeister, F., The functionof dissolvedsubstances inprocesses of swelling:
Z eitschr. phys. Chemie, vol. 7 , 1891, p. 432. Arch. exp. Path. u. Pharm., vol. 28,
1891, pp. 210-238.
60. VanBemmelen, J. M., Z eitschr. anorg. Chemie, vol. 23, 1900, pp. 321-37 2.
61. Walker, James, andAppleyard, James R., Absorptionof dilute acids by silk:
Jour. Chem. Soc,, vol. 69, 1896, p. 1334.
62. Teague, Oscar, andBuxton, B. H., The Mutual coagulationof colloids: Z eitschr.
phys. Chemie, vol. 62, 1908, pp. 287 -307 .
63. Van Bemmelen, J. M., The formation of gels andtheir structure: Z eitschr.
anorg. Chemie, vol. 18, 1898, pp. 14-36.
64. Des Bancels, J. Larguier, Colloidreactions andthe mechanism of mordenting:
Rev. g6n. mat. color., vol.'12, pp. 193-201.
65. Lottermoser, A., The preparationof colloidal elements: Z eitschr. angew. Chemie,
vol. 21, 1908, pp. 632-639.
66. Bodeker, , Jour. Landwirtschaft, vol. 3, 1859, p. 48.
67 . Wolff, , Landw. Z eitungNordundMitteldeutschland, Nos. 32 and33,1859.
68. Wood, J. T., The compounds of gelatinandtannin: Jour. Soc. Chem. Ind.,
vol. 27 , 1908, pp. 384-387 .
69. Cameron, F. K., andPatten, H. E., The distributionof solute betweenwater
andsoil.
7 0. Hirsch, H., Behavior of clay insalt solutions: Tonindustrie-Z eitung, vol. 28,
1904, p. 491.
7 1. Lottermoser, A., and Rothe, A., Adsorption of silver nitrate andpotassium
iodide by amorphous silver iodide: Z eitschr. phys. Chemie, vol. 62,1908, pp. 359-383.
7 2. Simonis, Max, The settling'of castingbodies andits prevention: Sprechsaal,
vol. 39, No. 5, 1906, p. 169.
7 3. Simonis, Max, Further contributions onthe relations of clays andnonplastics
towardelectrolytes: Sprechsaal, vol. 39, 1906, pp. 1167 , 1184.
7 4. Schultz andJulius: Organic colouringmatters. 3ded.
7 5. Pelet-Jolivet, L., andWild, A., Dyestuffs insolution: Z eitschr. Chemie u. Ind.
der Kolloide, vol. 3, 1908, pp. 17 4-17 7 .
7 6. Hober, R., andChassin, S., Dyes as colloids: Z eitschr. Chemie u. Ind. der
Kolloide, vol. 3, 1908, pp. 7 6-80,
62 COLLOID MATTER OF CLAY.
7 7 . Jackson, W., Trans. English Ceram. Soc., vol. 3, p. 16. AlsoCeramic calcula-
tions.
7 8. Purdy, Ross C., The calculationof the comparative fineness of groundmaterials
by means of a surface factor: Trans. Am. Ceram. Soc., vol. 7 , 1905, p. 441.
7 9. Ashley, HarrisonEverett, The testingof the raw materials of a whiteware pot-
tery: Trans. Am. Ceram. Soc., vol. 9, 1907 .
80. Z schokke, B., Investigations onthe plasticity of clays: Bull. Soc. d'Encour-
agement, vol. 103, 1902, pp. 619-658. Baumaterialienkunde, 1902, Nos. 24, 25-26;
1903, Nos. 1-2, 3-4, 5-6. Tonindustrie-Z eitung, vol. 29, 1905, p. 1657 .
81. Seger, HermannAugust, Collected writings, translated by members of the
AmericanCeramic Society, p. 357 .
82. Ashley, Harrison Everett, Pottery plaster: Trans. Am. Ceram. Soc., vol. 10,
1908, pp. 7 6-90.
83. Purdy, Ross C., andMoore, J. K., Pyrophysical andchemical behavior of clay:
Trans. Am. Ceram. Soc., vol. 9, 1907 , p. 222.
84. Julien, A. A., Onthe geological actionof the humus acids: Proc. Am. Assoc.
Adv. Sci., 187 9, pp. 311-410.
85. Borntrager, H., Z eitschr. anal. Chemie, vol. 39,1900, p. 694, vol. 40,1901, p. 639.
86. Graham, Thomas, Liquiddiffusionappliedtoanalysis: Philos. Trans. Royal
Soc., 1861, pp. 183-224.
87 . Forster, F., Die chernische Industrie, vol. 28, No. 24.
INDEX.
A. Page.
Absorption, discussionof.................... 27 -31
relationof, toplasticity.................. 28
totemperature...................... 27 -28
Acheson, E. G.,011 addedcolloids............ 12
Adsorption, destructionof, by heat.......... 9
discussionof............................. 31-42
estimationof colloids by................. 43-54
investigationof.......................... 7
apparatus for, plate showing......... .40
theory of................................ 31
Ageing, eflect of............................ 14
Alcohol, effect of, onclay.................... 24
AlienandDay, onabsorptionby feldspar... 28
Aluminum hydroxide, adsorptionby........ 10
Appleyard, J. K., and Walker, J., onad-
sorption......................... 31
onpartitionof solutes.................... 32-33
Ashley, II. E., work of....................... G
B.
Barium chloride, adsorptionof, by Klingen-
bergclay........................ 37 -38
chart showing........................... 39
Baugh, T., Mellor, J. W., and Green, S. A.,
onclay slips..................... 23-26
Bell, J. M., and Cameron, F. K., onsilica
coatings......................... 10
Bibliography................................ 59-62
Binns, C. F., onactionof boron............. 24
Bleininger, A. V., onviscosity of clays....... 20,43
preface by............................... 5-6
Blunging, difficulties in...................... 12-13
Borntrilger, H., onpeats .................... 11
Bredig, G., onformationof soils............. 17
Briggs andMcLanc, onabsorptionby soils.. 29
Brilliant green, adsorptiontests of........... 43-45
comparisonof, with malachite green..... 45
Butschli, onstructure of gels................ 32
Buxton, B. H., andTeague, 0., ondyes..... 30
C.
Cameron, F. K., andBell, J. M., onsilica
coatings......................... 10
Cameron, F. K., andPatten, H. E., onad-
sorption................................... 34-37
Charcoal, absorptionandadsorptionin...... 16
nature of................................. 16
Chassin, S., andHober, R., onbrilliant green. 45
Olarke, F. W.,onoriginofsilica gel.......... 10
Clays, absorptionby. See Absorption. Page,
adsorptiontests of....................... 43-53
aginganddryingof........'.............. 12-14
constituents of,"absorptive powers of.... 28-29
definitionof............................ 7 -8,59
effect of sodium carbonate on............ 22-23
further study of......................... 58,59
plasticity of. See Plasticity.
properties of.. '. .......................... 48-53
chart showing....................... 52
viscosity of.............................. 20-21
Clay gels, stability of......................... 19-20
volume of............................... 29-30
Clay sols, stability of........................ 19-20
Coagulation, laws of......................... 27
nature of................................ 15
Coehn, , onelectrostatic charges....... 17 -18
Colloids, additionof, toclay, eflect of........ 12
coatingby................................ 7 -8
definitionof............................. 7 ,12
forms of.................;............... 14-20
mixtures of........................'...... 31
properties of............................. 20-42
sources of.............................. 9-12,59
Colloids, organic, nature of.................. 10-11
' viscosity of................ '.............. 24
Color comparisons, apparatus for, plate show-
ing.............................. 46
Cushman, A. S., onplasticity............... 14
ontemperature effects................... 27
onwater inclay......................... 13
onWay's experiments................... 9
D.
Davis, C. A., onpeats....................... 11
Day andAlien, onabsorptionby feldspar... 28
Definitions, statement of.................... 7 -8
Deflocculation, extent of, insalt solutions.... 29-30
nature of................................ 15
Des Bancels, J. L., oncolloidmixtures...... 31
Drying, effects of............................ 12-14
Dubois, W. L., onfuller's earth andvinegar. 57
E.
Ebonite, nature of........................* ... . 15
Eichhorn, , onadsorptionof zeolites... 9
Electrolytes, actionof....................... 22-27
F.
Feldspar, absorptionpowers of.............. 28
agingof................................. 14
Ferric hydroxide, adsorptionby............. 10
63
64
INDEX.
Page.
Fire clays, grindingof, effect of.............. 56
weatheringof............................. 13
Forster, F., onnature of adsorption......... 23
Fuller's earth, effect of, onvinegar........... 57
G.
-, andPatten, H. E., onab- Gallagher,
sorptionby quartz.............. 28
Gates, W. D., onaddedcolloids............. 12
Gelatine, adsorptionof tanninby............ 33-34
adsorptionof tanninby, chart showing.. 34
Gels, cellular structure of.................... 31-32
formationof............................. 18-19
nature of................................. 14
partitionof solute betweenliquids and.. 32-42
salts in, distributionof.................. 30
solutionof water by.. ................... 30
Gentianviolet, adsorptionof, by Hagerstown
loam............................ 34-36
adsorptionof, by Hagerstownloam, chart
showing......................... 35
by quartz flour...................... 36-37
chart showing................... 37
Geological Survey, investigations by......... 5-6
Graham, Thomas, nomenclature by......... 15
Green, S. A., Baugh, T., andMellor, J. W., on
clay slips........................ 23-26
Green. See Malachite green; Brilliant green.
Grimsley, G. P., onabsorptionandplastic-
ity.............................. 28
Grinding, effect of, onplasticity............. 56,59
Grout, F. F., ondryingclays................ 12,28
onplasticity............................. 53
H.
Hagerstownloam, adsorptionof gentianvio-
let by........................... 34-36
adsorption of gentian violet by, chart
showing......................... '35
Hardy, W. B., onactionof electrolytes...... 22
oncoagulation........................... 2.7
ondryingunder pressure................ 13
onsetting............................... 15
onstructure of gelatine.................. 31
Henry, Charles, onviscosity................. 20
Hillebrand, W. F., ondehydrationof silica.. 17
Hirsch, H., onadsorption................ 37 -38,43
Hober, E.., andChassin, S., onbrilliant green. 45
Hofmeister, F., onswellingof glue........... 30
Hurnic acid, nature of....................... 9-10
Humus, absorptionby...................... 28
adsorptionby........................... 10
I.
India rubber, nature of. 15
J.
Jackson, W., onclay particles............... 50-51
James, J. H., onadsorptiontests............ 44
Julien, A. A., onhumic acid................. 11
Julius andSchultz, onformulseofgreens..... 45
K.
Kaolin, fractionationof.
nature of...........
Page.
Klingenbergclay, adsorptionof barium chlo-
ride by .......................... 37 -38
adsorptionof barium chloride by, chart
showing......................... 39
Kuzel, Hans, onplasticity. .................. 22
L.
Linder andPicton, onionic reactions. ......: 18
Liquids, partitionof solute betweengels and. 32-42
Liquids, immiscible, partitionbetween. ..... 32
Lottermoser, A., onionic reactions. ......... 18
onstructure of gels ...................... 31
Lottermoser, A., andRothe, A., onadsorp-
tion............................. 38-41
M.
McLane andBriggs, onabsorptionby soils. . 29
Malachite green, adsorptionof, by Tennessee
ball clay. ..................... 41-42, 50
adsorption of, by Tennessee ball clay,
charts showing.................. 42, 50
tests of .............................. 40-50
applications of. ............... 54, 56-58
Mayer, Adolph, onsettlingof clay. .......... 19
Mayer, Schaeffer, andTerroine, onionic re-
actions. ......................... 18
Mellor, J. W., Green, S. A., andBaugh, T.,
onclay slips. . ................... 23-26
Moore, J. K., andPurely, R. C., onplasticity. '58
N.
Nagelli,
Nernst,
, onstructure of gels. . ......... 32
, onpartitionbetweenimmis-
cible liquids ..;.................. 32
O .
Ober, J. E., andWhitney, W. R., onelectro-
static charges. ................... 17 -18
onionic reactions. ....................... 18
P.
Paris whites, malachite green, tests of....... 57 -58
Patten, H. E., andCameron, F. K., onad-
sorption......................... 34-37
Patten, H. E., andGallaghcr, , onab-
sorptionby quartz............... 28
Peats, adsorptionby........................ 10-11
analyses of............................... 11
Pectinization, use of term.................... 15
Pectisation, use of term...................... 15
Pcctoid, use of term......................... 15
Pelet-Jolivet, L., andWild, A., onmalachite
green............................ 45
Peptinization, use of term................... 15
Picric acid, partitionof dye betweensilk and. 32-33
PictonandLinder, onionic reactions........ 18
Plasticity, causes of.......................... 21-22
determinationof...................... 42-55,59
by malachite green.................. 54
loss of, by drying........................ 12-14
nature of................................ 8
relationof, toabsorption................. 28
tocolloids........................... 42-43
INDEX.
65
Page.
Potassium iodide, adsorption of, by silver
iodide........................... 39-41
adsorption of, by silver iodide", chart
showing......................... 41
Pressure, dryingunder, effect of............. 13
Proctor, R. H., oninorganic sols............. 20
Protectioncolloids, nature of................ 20
Purdy, R. C., onclay particles............... 50-51
Purdy, R. C., andMoore, J. K., onplasticity. 58
Quartz, absorptionby....................... 28
Quartz flour, adsorptionof gentianviolet by.. 36-37
adsorption of gentian violet by, chart
showing......................... 37
R.
References, list of............................ 59-62
Ries, H., onplasticity andabsorption....... 28
Rohland, Paul, onOH ions.................. 14,21
onpermeability of clays................. 13
onplasticity of clays..................... 21-22
Rotho, A., andLottermoser, A., onadsorp-
tion............................. 38-41
Salt solutions, volume of clay gels in......... 29-30
Salts, distributionof, ingels................. 30-31
Schaffer, Mayor, andTerroine, onionic re-
actions .......................... 18
Schioesing, Th., isolationof colloids by...... 8-9
onabsorptionby clay.................... 29
Schultz andJulius, onformula? of greens..... 45
Seger, H. A., onplasticity.........'.......... 58
Set gels, examples of......................... 15-17
Setting, nature of............................ 15
Silica, dehydrationof........................ 16-17
Silica, gelatinous, adsorptionby............. 9-10
Silicates, hydrated, adsorptionby........... 9
Silk, partitionof dye betweenpicric acidand. 32-33
Silver iodide, adsorptionof potassium iodide
by............................... 39-41
adsorptionof potassium iodide by, chart
showing......................... 41
adsorptionof silver nitrate by........... 38-39
Simonis, Max, onviscosity of clays........ 20-21,43
Sodium carbonate, actionof, onclay......... 22-24
Sols, formationof............................ 17 -18
nature of................................ 14
Stover, E. C., onagingof clay............... 14
Structural materials, investigationof........ 5
Sullivan, E. C., oninteractionof minerals and
solutions..................
T.
Page.
22.
Tannin, adsorptionof, by gelatine........... 33-34'
, adsorptionof, by gelatine, chart showing. 34
Teague, 0., andBuxton, B. H., ondyes..... 30
Temperature, effect of, onabsorption........ 27 -28
Tennessee ball clay, adsorptionof malachite
greenby......................... 41-42
adsorptionof malachite greenby, charts
showing......................... 42,50
Terrome, Mayor, andSchaffer, onionic re- .
actions.......................... 18'.
VanBemmelen, J. M., onsettlingof clay.... 19
onsilica gel.............................. 9-10'
onsolutioningels....................... 30
onstructure of gels...................... 31
ontemperature effects................... 27 -28-
Vinegar, effect of fuller's earth on............ 57
Viscosity, discussionof...................... 20-27
VonDobeneck, , onabsorptionby humus. 28
Walker, J., andAppleyard, J. R., onadsorp-
tion............................. 31
onpartitionof solutes................... 32-33
Warington, Robert, jr., onferric, andalumi-
num hydroxide.................. 10
Water, quality of, intests................ 43,45-40.
Way, J. T., experiments of, onseat of adsorp-'
tive powers..................... 9
Weathering, effect of, onfire clays........... 13-14
Weber, C. 0., onpectisation................. 15
onsolutioningels....................... 30
onstructure of gels................. T.... 31-32
Weelans, Charles, onadditionof colloids..... 12
Whitney, W. R., onformationof sols....... 17
Whitney, W. R., andOber, J. E., onelectro-
static charges................... 17 -18-
onionic reactions........................ 18
Wild, A., andPelet-Jolivet, L., onmalachite
green............................ 45
Wiley, H. W., onWay's experiments....... 9
Wood, J. T., onadsorptionof tannin........ 33
Z schokke, B., onplasticity. 53.
o
83865 Bull. 388 09-