Bentonite C. W. Davis and H. C. Vacher

Teclmical Paper 438
DEPARTMENT OF COMMERCE
WILLIAM F. WHITING, S&CRE;TARY
BUREAU OF MINES
SCOTT TURNER, DIRBcroll
BENTON IT
reoAonA ~
t
34
KOIT Al:MATOACriA
L---~~~~~~~~~---~
ITS PROPERTIES, MINING, PREPARATION,

AND UTILIZATION
BY
C. W. DAVIS and H. C. VACHER
Thjs report represents work done under a cooperative agreement between

the Bureau of Mines, Department of Cornrneree, and the Mackay
----school of Mines , Univer sity of N e vada
PRICE 10 CENTS
}loldonlybytheSuperintendentof Documents, U . S. Govermnent Printing Office
washinllt<m.
D.
c.
UNITED STATES
GOVERNMENT PRINTING OFFICE
WASHINGTON
1928
CONTENTS
Page
Introduction----------------------------------------------------Acknowledgments____________________________________________
General geology-- r---------- -------------- ~- -- --- ---------------Deposits--Mining and production__________________________________
VVyonling____ __ ____ __ _____ ___ _____ __ _____ ______ ___ ____ ___ ____
California___ _______ __ ___ ________ ___ _________ __ ____ __ ____ _____
South Dakota ____________ "___________________________________
~evada_______________________________ ____ __________________
Mexico __________ --_____________________________________

Idaho_____ ___ ________ _________ ___ ____ ___ ___ ___ ______________
Tennessee, Kentucky, and Alabama_____________________________
Other States __ ________ __ _ ---" __ __ ___ -- ---- - - --------_________
Canada ___ ___ ____ __ ______ __ ___ ___ ______ ___ ___ __ ______ ___ ____ _
Othercountries______ __ ____ _____ __ _____ ___ ________ __ ______ ____
Investigation of properties of bentonite______________________________
Definition__________________________ ___ ______ ________________
General characteristics _______________ --~- -- ___________________
Composition ______________ __ ____________ __----------------___
Experiments on effects of liquids on swelling and disintegration____ _
Action iri water______ ____ ___ ____ __ ____ :__________ _________ ___ _
Control of the swelling of bentonites___ ___ ____ ___ __ ________ ____ _
~ew
D~cusmon_ __ _____ ___ __ ___ ____ _ ___ __ _ ______ __ ______ __ __ _ _
Conclusions___ __ __ __ ___ __ _____ ___ __ _____ _______ ____ ___ ___

Loss of colloidal properties on heating___________________________
Fe20.+Al203:Si02 ratio of decanted materiaL_ ___ ____ ______ ____ __
Experiments in dye absorption________ __________________ _____ __ _
Removal of alumina by sulphuric acid _______ ______ _______ .:._ _____
Temporary osmotic pressure___ __ __ ______ __ ________ __ _____ ______
Effect of NaCl and CaCh solutions on bentonite__ __ __ ___ ___ ____ __
Identification and classification of commercial bentonites____ ______ __ ___
Properties that determine uses of bentonite __ ___ __ ____ __ __ ___ ___- - --Adsorption and absorption of liquids by solids__________ __________
Adsorption of gases by solids---- - --- --- - -- ---- -- ------ --- --- --Use as a colloid______ ________________ ______ _______ ___ _________
Present and proposed uses for bentonite___ ___ __ ____ __ ___ _____ ___ ____ _
Bentonite as filler, binder, or plastic _____ __ __ ___ _______ __ __ ___ __ _
Paper, oilcloth, curtain cloth, linoleum, or cordage _____ ____ ___
Rubber--- -- -- - -- --- - - -- --- - - ---- -- ---- - -- - ---- -- -- - - --- Ceramics___ ___ ____ ___ ___ ___ ____ __ ____ ____ ______ __ ___ ___ __
Portland cement_ _______ __ ______ __ __ ____ ___ __- __ -- ----- -- Road building_ ______ _________ _____ ___ ______ __ __ ___ ____ __ _
Lubricating greases ___ ___ __ ___ ____ _____ - __ ___ _- -- ---------PuttY---- - -- - -- - ----- - ------- - ----- - ---- - -- - --- - - --- - -- - Foundrywork___ ___ _____ _____________ ____ ___ ___ ___ ____ __ _
Phonograph records and electrical insulation_____________ ___ __
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IV
CONTENTS
Present and proposed uses for bentonite-Continued.

Bentonite as filler, binder, or plastic-Continued.
Pencil leads, crayons, and pastel colors_______________________
Plasters________________ ___ ______________________ __ _______
Paste, glue, or size ______ _____________ ---------- ---- - ______
Miscellaneous filler uses ______ - - -______________ _______ __ __ __
Bentonite as adsorbent, emulsifier, or peptizer________ _____ ____ ____
Soaps and detergents__________________________ __ ______ ____
Deinking printed papers______________________ _____________
Refining of oils and fats___________________ ________ _____ ____
Horticultural sprays, animal dips, and insecticides_____________
Fungicides __ :.._____________________________ ___ _____ _______
Use in paints, enamels, and inks___________ ____________ _____
VVood dips______ ______ ________________ ____ _______ ______ __
Roofing preparations and waterproofing_ ____ ___ _____________ _
Coal-mine dusting________________________ __ _______________
Dusting agent for other uses_______ ___ ______________________
Desiccating agent_______________ ______ ____________________
Removal of water from petroleum____ _____ __________________
In manufacture of dynamite_______ __________ ________ _______
Absorbent of miscellaneous substances_____________________ __
Bentonite as chemical reagent____ __ ________ ___ ____ _____________
VVater softener___ ______ ____ ___ ___.______________ __________ _
As an aid to soil fertility___________________________________
In treatment of molasses----- -- ----- --~- ------------ --- ---Bentonite as medicament and cosmetic_____ __ ____________________
As an antiphlogistic____________ ___________________ ________
In drugs____________ __ ___ ____ ______ _________________ _____
In cosmetics___ - -----_____ ______ _____ _________ _________ ___
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ILLUSTRATION
Fig.
1.
Scheme for classifying bentonites__ ______ ____ ________ __ ___ ______
23
BENTONITE: ITS PROPERTIES, MINING, PREPARATION, AND

UTILIZATION 1
By C. W.
DAVIS 2
and H. C.
VACHER
INTRODUCTION
Bentonite is a rock that contains 75 per cent or more of the crystalline claylike minerals montmorillonite or beidellite. 4
The only comprehensive treatise on bentonite,5 although comparatively recent, is already out of date in several respects. The present
investigation, undertaken in an endeavor to add to our information
on bentonite, includes a brief compilation of its geologic and geographic occurrences, a study and discussion of its nature which covers
a definition and methods for its identification and classification, a
study of the properties of different samples of bentonite-like materials, and a study of the known and suggested uses of bentonite.
Investigators have recognized the occurrence of a peculiar claylike
substance which, when wet with water, resembled soft soap and was
called "mineral soap" or "soap clay" for a long time. Early reports show that such material had long ago been used at the Hudson
Bay posts in Canada for washing blankets. 6
The first shipments for commercial purposes were made in 1888 by
William Taylor of Rock Creek, Wyo., after whom the material was
called "taylorite." In 1898 however it was learned that the name
taylorite had already been used as a mineral name for potassium
ammonium sulphate ( 5K2 S04 (NH4 ) 2804 ) , so that this substance was
then designated as bentonite from its occurrence in the Fort Benton
formation of the Rock Creek district. 7
At the time considerable interest in bentonite was aroused, but it

quickly subsided and the price of $25 per ton was soon reduced to $5
Work on this manuscript completed May, 1927.
Associate chemist, Bureau of Mines, in charge of the investigation.
Graduate research fellow under the ;fohn Armstrong Chaloner fellowship (1925-2~)
at the University of Nevada.
~Ross, C. S., and Shannon, E. V., "The minerals of bentonite and related clays and
their physical properties" : Jour. Am. Ceram. Soc., vol 9, 1926, pp. 77-79.
6 Spence, H. S., Bentonite: Canada Dept. Mines, Rept. 626, 1924, 35 pp.
6 See footnote 5.
Knight, W. C., "Mineral soap" : Eng. and Min. Jour., vol. 63, 1897, p 600; Vol. 66,
1898, p. 491.
1
BENTONITE
per ton. Within the last few years the interest in bentonite has revived, resulting in investigations that have developed industrial
processes and products in which bentonite apparently has an important part. The price to-day at Western points for the finely
pulverized material approaches the iirst quoted price.
In September, 1926, the R. T. Vanderbilt Co., New York, reported
that dried bentonite ground to minus 100-mesh was offered f. o. b.
cars in bags (bags extra) at Chicago and other shipping points for
prices ranging between $40 and $50 per ton and that crude bentonite
with 12 to 30 per cent o:f moisture content was offered f. o. b. cars.
at point of origin for $4.50 to $10 per ton.
0: the many uses suggested only a few have been tested, a.nd
investigators have not worked out the properties of bent onite that
determine its usefulnBss or made tests to determine what type of
material is best suited to the different uses.
ACKNOWLEDGMENTS
The authors acknowledge the kindness of Master Minerals Co.,

General Clay Co., Filtrol Co. of Los Angeles, Trojan Mining Co.
of South Dakota, Wyoming Bentonite Co., and Owyhee Chemical
Co., Wyoming, and the courtesy of Wilbur A. Nelson, State geologist, Tennessee, in furnishing samples of bentonite used in this
investigation. Appreciation is expressed to members of the faculty
of the University of Nevada and to the members of the Bureau
of Mines and United States Geological Survey, who have aided us
by valuable suggestions. Other assistance is acknowledged in
footnotes.
GENERAL GEOLOGY
Bentonite deposits occur in beds from a few inches to many
feet thi.ck, mainly in the Tertiary but t o some extent in the Paleozoic
and Mesozoic rocks in many parts of the United Stat_es and Canada,
and deposits have been reported from Mexico, China, and France.
Hewett, Wherry, Nelson, Ross, and Shannon 8 have shown that
most bentonite deposits are the result of devitrification and partial
decomposition of glassy volcanic ash. Their evidence includes the
existence of thin sections of bentonite with the chara~teristic structures of volcanic ash; the presence of feldspar; the absence of an
appreciable quantity of quartz (usually contained in all or dinary
clay sediments); the chemical composition (whi.c h is just what
8
Hewett, D. F., "The origin of bentonite and the geologic range of related materials
in Bighorn Basin, Wyoming" : Jour. WasiL A cad. Sci., vol. 7, 1917, pp. 196-198 ; Wherry,
E. T ., "Clay derived frcm. volcanic dust in the Pierre of Sout h Dakota" : J our. Wash.
Acad. Sci., vol. 7, l!H 7, pp. 576--583; Nelson, W. A., " Volcanic ash bed in the Ordovician
of Tennessee, Kentucky, and Alabama " : Bull. Geol. Soc. Am., vol. 33, 1922, pp. 605--616.
See aliio footnote 4, p. 1.
GENERAL GEOLOGY
would be expected to result from the partial alteration and leaching of volcanic glass by water where part o the alkalies have been
removed and water added); field relationships, such as the presence
o alkaline salts near by (which probably resulted from decomposition); and the extension of individual beds, often very thin and of
fairly uniform thickness, over great distances (such as would result
from the settling of ash from a volcanic eruption).
Wherry 9 points out that these deposits may well have been formed
during expulsion from a volcano and subsequent distribution by
air currents in contact with corrosive gases which attacked the
surface of the particles and rendered them open to relatively rapid
disintegration when the ash fell in moist climates or into shallow
bodies of water. Such conditions may have existed in Cretaceous
and Tertiary times in the districts where we now find bentonite.
Wherry postulates further that the action of water first caused the
ash to distintegrate into hydrous silica and alumina with colloidal
properties and the bases to dissolve. P art of the soluble salts were
adsorbed and the rest leached out. This state was supposed to have
been followed by the incipient growth of crystals from a large
number of nuclei with the formation of the metacolloidal condition
(in which the whole mass is made up of minute crystal grains in
contact with one another). Bentonite is then supposed to consist of
colloidal matter, minute crystalline matter, and included impurities.
Although most bentonites are believed to have been formed from
volcanic ash Ross and Shannon 10 pointed out that some deposits
have been formed in situ by the devitrification not only of glassy
igneous ash or tuff but occasionally of lava flows and. even of
hypabyssal intrusives. Prof. Virgil R. D. Kirkham, o Moscow,
Idaho, considers that much Idaho bentonite is the r esult of the
alteration of acidic lava not necessarily o glassy texture; To substantiate his belief Professor Kirkham submitted specimens, one
containing fresh lava and bentonite and others showing a slightly
altered acid lava with part bentonite.
Melhase 11 describes an unusual occurrence of bentonite near
Daggett, Calif., as follows :
The inclosing rocks are rhyolites of Tertiary age in which the bent onite occurs
~asses of' 10 to 200 tons, separ ated fr om one another
by distances of sever al hundred f eet. H ere, the bent onite masses exhibit no
evidence of stratification nor of t r ansportation and ar e clearly t he result of
local alteration of t he country rocks in situ.
m " pockets " or irregular
Bentonite outcrops are unique and striking. As little vegetation

will grow on them, they are barren, and because of the peculiar
Alexander , J"., " Ben tonite" : Colloid Symposium Mon ograph, vol. 2 . 1925, pp. 99- 105.
See f ootnote 4, p . 1.
n Melhase, J"ohn, "Mining ben tonite in Califor n ia": E n g. and Min . J"our., vol. 1 21,
1926, p. 838.
9
'
BENTONITE
physical properties of bentonite these weathered outcrops often present a crinkled corallike appearance. This latter effect has been
studied by Twenhofel,12 who concludes that the surface cracks are
caused by the lag in absorption of water bybentonite. The internal
portion of bentonite is dry, but finally absorbs water and swells
greatly, producing cracks in the surface layer, which has meanwhile
become more or less dry. After a rain many bentonite outcrops are
covered with a thick mass of slippery jelly, but in dry weather the
surface may be dry and fluffy or may have a peculiar granular
a;ppearance.
DEPOSITS-MINING AND PRODUCTION 13
WYOMING
The bentonite of Wyoming is usually considered a standard ty"Qe

in studying other so-called bentonites. As already stated, the first
shipments were made from the Rock Creek district in 1888, and from
then until1896 an average of 60 tons of bentonite per year was sold
at a price of $25 per ton f. o. b. cars. In 1902 the production rose
to 1,200 tons, but the price dropped to $5 per ton. In 1919 the price
rose to $7, with a production of about 25 cars per year. One of the
important producers is now the Owyhee Chemical Products Co.,
which has deposits a:t Medicine Bow and a grinding plant at Cheyenne. This plant markets bentonite as crude, coarsely ground, and
pulverized. The main deposit worked by the company is about 5
feet thick, with a light overburden, which is removed by scrapers.
The bentonite bed is then broken up by a plow and loaded into
wagons. The mill process consists of drying, crushing, and reduc~
tion in a hammer mill or an air-float roller mill to obtain the grade
or product desired. .Another important producer in Wyoming, the
Wyoming Bentonite Co., has a mine at Clay Spur, near Newcastle.
A large new deposit of bentonite has recently been reported 14 in
Johnson County. Wyo., 35 miles from the Salt Creek oil fields and
85 miles from the refineries at Casper. It outcrops in many places
and has been penetrated to a depth of 10 feet.
CALIFORNIA
The largest known California bentonite deposits occur in the arid

desert regions along the Amargosa River in Inyo County. The material of these deposits is known as shoshonite and amargosite, and
"'Twenhofel, W. H., Researches in Sedimentation in 1924: Rept. Nat. Res. Council,
1925, p. 75.
"'Ladoo, R. B., Nonmetallic Minerals: New York, 1925, p. 93. See also footnotes 4, 5,
and 11, pp. 1 and 3.
"Timmerman, H. C., " Bentonite discovery reported in Wyoming " : Eng. and Min
Jour.-Press, vol. 122, 1926, p. 310.
DEPOSITS-MINING AND PRODUCTION
its analysis corresponds to that of montmoril!o~ Although ap-~~

parently a bentonite, it has characteristics considerably different
from the typical Wyoming variety. At Ash Meadows the Standard
Oil Co. mines bentonite from a bed 4 to 12 feet thick, overlain by
50 to 100 feet of sandstone, clay, and marl. As stripping proved impractical drifting methods have been used. The main haulage ways
are timbered, and no difficulty has been experienced in supporting
the roof. The overburden is weli consolidated and firm, but the
bentonite is so saturated with water that it heaves, often completely
blocking the workings. Air-tight doors are provided at the entrances
to prevent unnecessary drying and crumbling of the bentonite. The
freshly mined material is spread on wooden platforms and turned
and pulverized by hand shovels. By this treatment the desiccating
atmosphere removes the free moisture in three or four days, after
which the bentonite is shipped to refineries for further treatment.
At Shoshone the Associated Oil Co. of San Francisco and the Fiitrol
Co. of Los Angeles have worked bentonite deposits whieh adjoin
the Tonopah and Tidewater Railway right of way on the we~t. The
deposits have an area of several hundred acres and are 1 to 10 feet
thick. Filtering clay has been supplied since 1920 and enough is
blocked out to insure an ample supply for many yearsY Tho overburden is so thin that it is removed with horse scrapers. The bentonite is quarried with pick and shovel, dried on wooden platforms,
and shipped to refineries. A third deposit in this district, 4 miles
southeast of Tecopa, is about 6 feet thick and outcrops in a canyon
wall. It is of good quality and easy to mine but contains impurities
that would have to be removed before marketing.
A deposit of bentonite locally known as otaylite, located 4 miles
east of Otay in San Diego County, forms a lenticular bed 4 to 6 feet
thick on the west but thins out and disappears in the easU5 The
bentonite bed consists of numerous thin strata of colors ranging from
white to green, pink, and chocolate. These colored layers are intimately mixed to form a commercial product of uniform light gray.
The composition of the different colored layers is the same and resembles that of montmorillonite. The deposit covers several thousand acres and has an overburden about 100 feet thick that thins
out toward the outcrops. The southern half of this deposit is owned
by the General Petroleum Corporation and the northern half chiefly
by the Stauffer Chemical Co. Although the strata are well drained
so that no water is encountered in the mining operations, which consist of stripping or drifting, depending on the thickness of the overburden, the bentonite is always quite moist and contains about 30
' 5
See footnote 13, p. 4.
4713-28--2
BENTONITE
per cent of water. The freshly mined product is spread on the open
quarry floor in a layer 6 to 12 inches thick and stirred every day by
horse-drawn harrows. A week's treatment reduces the moisture to
about 7 per cent.
Between Barstow and Daggett, in San Bernardino County, the
bentonite occurs in masses ranging from 10 to 200 tons each. Deposits which outcrop are being mined by underground methods by
the Master Products Co., which ships the air-dried material to Los
Angeles, where it is ground in a Raymond mill and air-floated. The
200-mesh product has sold for about $20 per ton, f. o. b. Los Angeles.
Frank L. Hess, Bureau of Mines, reports the ocurrence of bentonite
near Ransburg, in Kern County, as follows:
Five miles north of Ransburg beds of rhyolitic volcanic ash are partly altered
to a beautiful white bentonite that is estimated to take up about 64 times
its bulk of water. The beds are possibly of Pliocene age and are largely covered by lavas and lake beds. The bentonite is probably not pure enough to be
of much value.
Other deposits of bentonite have been reported in Imperial, Fresno,

and Kern Counties, Calif.
SOUTH DAKOTA
A material closely resembling Wyoming bentonite occurs at Belle

Fourche, S. Dak. The Belle Fourche Bentonite Products Co. owns
154: claims, containing what is estimated at 14,000,000 tons of highgrade bentonite. 1 6
Another deposit, called bentonite, although differing somewhat
from the type mineral, occurs at Ardmore in a number of beds ranging from a few inches to 4 feet in thiclmess, overlain by 2 to 6 feet
of black soil. This soil is stripped off with a steam shovel, the beds
drilled and blasted, and the loosened material transported to the mill
at the railroad by motor trucks. A considerable quantity is used by
the Refinite Co. at Ardmore for the manufacture of water softeners.
NEVADA
The General Clay Co., of Los Angeles, Calif., was mining and shipping about 1,000 tons of bleaching clay per month in 1926 from a deposit in Nye County, Nev. The deposit consists of Tertiary beds
:from a few inches to several feet thick below an overburden 1 to 5 feet
thick. The overburden is stripped off, and the clay is quarried in
open pits. This material is air-dried on platforms, hauled to the
railroad, and shipped to oil refineries where it is used raw.
1 Fellows, R. 0., " Bentcmite in South Dakota" : Eng. and Min. ;Tour.-Press, vol. 122,
11l26, p. 182.
DEPOSITS___:_MINING AND PRODUCTION
A deposit resembling typical Wyoming bentonite has been found

in the Silver Peak mining district of Esmeralda County, Nev. 17 The
material is said to occur as bedded layers in what was formerly
a lake. The surface layer, about 6 feet thick, is mainly volcanic ash
with enough bentonite to make it stick together when moi,stened and
pressed, while below this is a layer of bentonite with some gangue
about 10 feet thick. A layer of fairly pure bentonite about 15 feet
thick is below this.
The ,surface presents the characteristic barren appearance, and
crystals of gypsum and other salts are often in evidence. This
deposit is thought to be 5 miles across.
A partly altered volcanic deposit has been reported about 3 miles
southwest of the Lahontan dam, near Fallon, Churchill County, Nev. 18
Deposits of similar grade occur near Las Vegas, Clark County,
and in the eastern part of the State. Other deposits of bentonite
have been reported from Rhyolite, Beatty, Tolicha, Mina, and the
Amargosa Desert regions.
NEW MEXICO
There are deposits of bentonitic material 3 to 5 feet thick about

35 miles north of Santa Fe, N. Mex., near the Denver & Rio Grande
Railroad. The material di,sintegrates rapidly in water to a soapy
flocculent mass, but does not remain in suspension. Frank L. Hess,
Bureau of Mines, reported another deposit at San Antonio Creek,
Rio Arriba County.
IDAHO
Material closely resembling Wyoming bentonite is found in Cassia

and Owyhee Counties, Idaho.
TENNESSEE, XENTUCXY, AND ALABAMA
An enormous bed of clay classified as bentonite covers an area

about 800 miles long and 450 miles wide in Tennessee, Kentucky, and
Alabama~ with a maximum thickness of 10 feet near High
Bridge, Ky. 19
OTHER STATES
Deposits of bentonite have been reported from Colorado County,

Tex., 20 Amarillo, Tex., from Monroe and Prentiss Counties, Miss., 21
and from various districts of Montana, Arizona, Utah, Arkansas,
Infol"lllation and samples furnished by J". W. Crane, Goldfield, Nev.
' " Information and samplEl by H. D. Winten and C. Wiley, Hazen, Nev.
"'Nel son, W. A., " Volcanic ash bed in the Ordovidan of Tennessee": Bull. Geol. Soc.
A.m., vol. 33, 1922, p. 605.
20 Bailey, T. L., The Geo)ogy and Natural Resources of Colorado County, Tex.: Univ.
Texas Bull. 2333 , 1923, 159 pp.
:n Grim, R. E ., Bentonite in Mississippi: Mi..ssiBsippi Geol. Survey Bul. 22, : .928, 14 ))p.
17
BENTONITE
Washington, Oregon, Kansas, Oklahoma, Louisiana, Minnesota,

Wisconsin. Virginia, Pennsylvania, and Alaska.
CANADA
Bentonite occurrences have been reported at a large number of

localities in Saskatchewan, Alberta, British Columbia, and Manitoba, but no a.ttempt to develop any of the deposits had been made
up to 1924 as there was no important demand for the material.
OTHER COUNTRIES
Bentonite has also been reported from China, France, and Mexico.
INVESTIGATION OF PROPERTIES OF BENTONITE
DEFINITION
After the study of a number of samples of bentonite from widely

separated districts, Ross and Shannon," 2 following the usual method
of rock classification by mineral content, proposed that the name
bent<>nite include all rocks that contain -'W )er cen _or more of the
crystalline claylike minerals ~.J2ri.llonite _gr "!2eidellit!:\ formed by
the alteration of igneous material. They stated that. bentonite is
characterized by a texture inherited :from volcanic tuff or ash; that
the minerals are eharacterized by their micaceous habit, faeile cleavage, and high birefringence; and that common accessory minerals
are feldspar_,_. biotite,-quartz, jJyroxenes, y:ircon, and others typical of
volcanic rocks. They suggest that if the claylike ma.terial contains
between 25 and 75 per cent of sandy impurities the substance be called
an arkosic bentonite and with less than 25 per cent of bentonite
minerals a bentonite arkosey This definition includes the original
type bentonite from .Wyoming and such material as the so-called
"bleaching clays."
GENERAL CHARACTERISTICS
Nearly all deposits of be-n tonite contain gritty or sandy inclusions,

which are considered impurities and must be removed before ma.r keting. Pulverized bentonite is fine grained and commonly light colored, ranging from cream to olive green; but it may be pink, dark
brown., or even black, the color usually but not always becoming
darker on wetting., When fired the color is white, buff, or brown.
"When cut the fresh material usually has a waxy luster which may
become dull or powdery on drying. Some varieties may be cnt. into
thin shavings. The Wyoming type of bentonite has a roughly con23
Ross, C. S., and Shrumon, E. V., "The minerals of bentonite and related clays =d
their physical properties " : Jour. Am. Ceram. Soc., vol. 9, 1926, pp. 7T-i9.
choiclal fracture, but some varieties have a platy, shalelike f racture

or no distinctive fracture.
Certain bentonites have a strong affinity for water, absorbing three
times their weight or as much as 10 or more times their volume of
wa,ter with a consequent increase in volume (which may be 10 or
more times the original volume) and with the formation of a
slippery, plastic, gelatinous mass that resembles soft soap. When
agitated with more water a permanent suspension results, unless
enough soluble electrolytes are present to prevent dispersion, in
which case the soluble sal.ts ma.y be washed out by dialysis and the
resulting residue suspended in water. Typical bentonites do not always retain their original form on swelling, as a cube of one bentonite
dropped in water expanded in the dit;ection of each original cube, face,
forming a symmetrical pile of six cubes, one for the original cube and
one for each original cube face (except the bottom face which was
protected from water).
COlr!POSITION
As previously stated, the most plausible explanation of the formation of bentonite is that of vVherry/ 3 which assumed that volcanic
ash or lava was altered to a hydrous silica and alumina (and in some
cases to hydrated iron oxide). Part of the soluble salts produced by
the action were adsorbed, and the rest leached out. The composition
of the original rock would largely determine the nature of the resulting substance, but replacement of the bases may have taken place
later. Crystallization then probably started at a large T1umber of
nuclei with the formation of a mass of minute micaceous mineral
gmins in contact with each other, the crystal leaves being capable of
.separation into flakes of colloidal thickness.
'
Alexander concludes that much of the substance of bentonites has
not progressed beyond the colloidal stage, as ultramicroscopic study
showed that fully one-half o the particles in certain samples were
of ultramicroscopic size.24 Other investigators considered bentonite
a mixture of colloidal silicates and nne-grained Iraolinite 25 or a typical negative suspenoidal colloid. 20 Ross and Shannon 2 ' state that
solid natural bentonites contain no gel colloids and that few crystal
particles are as small as colloidal size. These investigators found
that bentonite is commonly composed of montmorillonite and less
often of beidellite, minerals resembling micas.
Alexander. :r., "Bentonite" : Colloid Symposium Monograph, vot 2, 1925, pp, 99-105.
~~ See foo i~Jote 23,
20 ~churecht, H. G., and Douda, H. \V., "The properties of some clay like mat<;rials ot
the bentonite type": :rour. Am. Ceram. Soc., vol. 6, 1923, p, 940,
.
""Coward, H. F., "Sedimentation of bentonite" : Jour. Chern. Soc., vol. 125, '1924, p.
1470.
01 ltoss, C. S ., and Shannon, E. V., "The minerals of bentonite and their physical
properties": .Tour. Am. Cerum. Soc,, vaL 9, 1926, pp. 77- 79.
10
BENTONITE
Montmorillonite is designated as (Mg,Ca)O. Al 2 0 3 .5Si02 .nH2 0),

with n equal to about 8. Larsen and Wherry 28 named beidellite
and assigned to it the formula Al 2 0 3 .3Si0 2 .xH2 0, in which x is
frequently eqttal to 4 and the alumina is replaceable by other oxides;
Ross and Shannon concluded that this mineral consists o:f isomorphous series of Al 2 0 3 .3Si02 .nH 2 0 and Fe2 0 3 .3Si0 2.nH 2 0, with n
equal to approximate!~ 4 29 and with the wat{3r replaceable by alkali
or alkaline-earth oxiaes. Varying amounts of other minerals may
be included as impurities. This also explains the differences in
the variou~ published analyses of crude bentonite. The few analyses
given in Table 1 stress these differences and show that partly purified
samples agree much more closely with the theoretical compositions of
their essential minerals than do crude samples. The optical properties of different samples are also affected by the presence of oxides
of iron or potassium. 30
Bentonites, although varying widely in composition, have many
properties in common. Wherry 31 has attributed the colloidal properties of bentonite to a felted texture and a micaceous structure, in
which the crystals have appreciable size in two dimensions but. a
thickness of colloid magnitude and also have the property of splitting
up into still thinner plates. The texture supposedly lets water penetraw the mass quickly, wet the surface, and force its way between
the micaceous leaves of the crystals.
TABLE
Composition of
sample
No.
1
No.
2
No.
3'
!.-Analyses of bentonites
No.
4
No.
5
No.
61
No.
7
No.
8
No.
9'
No.
10;
No.
11'
No.
12 '
No.
13 ..
------1-- - - - - - - - - - - - - - - - - - - - BiOs---------------- 61. 5 55.22 48. 80 60.64 49. 56 50.60 45.52 50. 85 63.9 63.8 67.2 62.4 60.18
Ab0 3 ____________ _ ___ 21.2 21.00 21. 08 23. 26 15.08 17.23 ?:1. 52 28.81 17. 7 17. 9 18. 6 19. 3 26. 53
Fe1o,_______________
.1
3.61
.92 3.92 3.44 ______ 2.80,_____
.5
1.2
.7
.1 ______
TiOs.---- - --- -- - --- --- --- --- ---- . 12
.4Q ______ - --------- - ------ - - - ---- ----- ---- - - -- - -CaO_________________
. 4 4. 94 1. 36
. 59 l. 08 3. 21
. 52----. 9 3. 1
.9
1. 28
. 23
MgO_______________ _ 1.1
3. 04 4. 84 2. 19 7. 84 4. 56 3. 00 --- --- 3. 3 5. 4
1. 9
3. 5
1. 01
~~~o:::::::::::::::: 1: ~ --i~56 :::::: 4: lll::::::l:::::: :::::: :::::: :~ R 1'i ~: & __:_~

H,opp~;;;c::::::::: s:iii -iii:zs -20~92 --i.-83 22:% 24~32 'i9:oo -2o~34 ~: i~ ~: k U~ g: !?ho:w
Loss 1os to 1,000 _________ ----- ------ ______ - -- --- ______
6. 201 i. 30 4. 3.5] 4. 90 ----
-----+-----
Bentonite, near Fallon, Nev. H. C. Vacher, analyst.

Bentonite, Ardmore, S. Dak. (Ladoo, Nonmetallic Minerals, 1925, p. 92.)
'Bentonite, Ardmore, S. Dak., purified. (Ross and Shannon, Jour. Am. Ceram. Soc., vol. 9, 1926, p. 88.)
Bentonite (yellow colloidal), Belle Fourche, S. Dak. (Ladoo, p. 92, work Cited .)
Otaylite (pink), Otay, Calif. (Ross and Shannon, p. 88, work cited.)
1 Montmorillonite, to satisfy (Mg, Ca) OAb0s.5 Si0,.8H,O; ratio MgO to CaO, 2 to 1.
Bentonite, Mine Creek, Ark. (purified). (Ross and Shannon, p. 88, work cited).
Beidellite, to satisfy AhOs. 3 SiO,. 4H,o.
.
' Montmorillonite, from General Petroleum Co., Los Angeles, Cahl. H. C. Vacher, analyst.
; Halloysite, from Filtrol Co., Los Angeles, Calif. H. C. Vacher, analyst.
Bentonite, from Trojan Mining Co., Deadwood, S. Dale H. C. Vacher, analyst.
r Kentucky bentonite. from W. A. Nelson, Tennessee. H . C. Vacher, analyst .
m Type bentonite, near Rock Crook, Laramie Ba&in, Wy-o.
(Ladoo, p. 92, work cited.)
""Larsen, E. S., and Wherry, E. T., "Beidellite, a new mineral name": Jour. Wash.
Acad. Sci., vol. 15, 1925, p. 465 .
.., Ross, C. S., and Shannon, E. V., " Chemical composition and optical properties of
beidellite": Jour. Wash. Acad. Sci., vol. 15, 1925, p. 467.
""For a:nnlyses of other samples or bentonite see footnotes 5, 9, 18, and 29, pp. 1 and 3,
and above.
:n Wherrry, E. T., "Bentonite ns a one-dimensional colloid": Am. Mineral., vol. 10.
1925, p. 120.
11
Different bentonites were studied to obtain a better understanding

of their properties and to derive a scheme for their commercial
identification and classification.
EXPERIMENTS ON EFFECTS OF LIQUIDS ON SWELLING AND
DISINTEGRATION
In Bureau of Mines experiments a large number of samples of

bentonites and clays from many sections of the United States were
used, but to correlate the observed results more clearly tests made
from four samples that seem to re-present respectively four types of
bentonite will be summarized. The analyses of these are given in
T able 1, analyses 9, 10, 11, and 1~. Special work was done on these
and other samples to determine the effect of solutions on their swelling and ~o attempt to solve the difficulties encountered in drilling
through bentonite.
ACTION IN WATER
To determine the action of water, small lumps of each type of

be.ntonite were placed in 100 c. c. of water and care was taken not
to shake the container. Sample 9 broke down rapidly, swelling a
little. On standing overnight a fin~ . mud covered the bottom of the
beaker. Sample 10 acted in the same way, except that no portion
diffused through the solution. Sample 11 did not break down; it
swelled considerably without disintegrating and on standing diffused
and covered the bottom of the beaker. Sample 12 broke clown into
small fragments but did not diffuse.
The relative swelling in water was determined by gradually adding
2.5 grams of air-dried minus 10-mesh bentonite to a test tube
containing water and observing the volume of the swelled sample
after 24 hours. Sample 9 occupied a volume of 4.5 c. c.; sample 10,
2.5 c. c.; sample 11, 15.5 c. c.; and sample 1~, 1.7 c. c. The relative
amount of swelling in water seems a rough method for classifying
bentonites.
CONTROL OF THE SWELLING OF BENTONITES
A study of the swelling of bentonite and its control 32 follows. In

drilling wells for oil, potash, or other minerals water is generally
used. If bentonite is encountered the drilling water causes the
bentonite to swell and form a sticky mass which flows into the hole.
As more water is mixed in, the mass becomes, less viscous and finally
results in a permanent suspension. There is a continuous transition
from the stiffest paste to the most mobile suspension, all dilutions
being capable of holding other minerals in suspension. If oil is
present bentonite promotes the formation of water-in-oil emulsions,
""Davis, C. W., "The swelling of bentonite and its cont.rol": lnd. and Eng. Cbem.,
vol. 19. 1927, p. 1350.
12
BENTONITE
which may be either very viscous or practically solid. as will be

explained later. (See p. 27.) In any case bailing is very difficult
and tedious. The sides of the hole may swell, heave. and cave and
may result in the collapse of casing. Prevention of the swelling
of bentonite encountered in drilling is therefore an important
problem.
Wanen 33 in a few qualitative experiments found that a. bentonite
that swelled greatly when placed in water broke down without appreciable increase in volume or absorption of the solution when
placed in a saturated sodium chloride brine. A solution 50 per cent
saturated with sodium chloride acted similarly, but more of the solution was absorbed by the bentonite. A 25 per cent solution of
methanol in water caused the bentonite to expand considerably and
was absorbed to a notable extent. Warren applied his results in
the field and demonstrated that by dumping 200 polmds of common
, salt in the hole a bed of pure bentonite 6 feet thick encountered
at a depth of 1,895 feet could be drilled wet without difficulty. He
also pointed out that when salt water is encountend in drilling
bentonite should present no difficulty.
To obtain further data of the effect of different solutions on ben. tonite and on claylike materiar that might cause difficulty in wet
drilling about 500 tests were made. The air-dried samples were
stage-crushed through 10-mesh. The apparent volume of 2.5 grams
was measured, and this sample passed slowly thtough a funnel into
a test tube containing about 20 c. c. of the solution being tested.
After 24 hours the height of the swelled sample was marked on the
test tube, the appearance and feel of the material were noted, the
tube was washed clean, and the volume occupied by the swelled
sample measured by observing the quantity of water run from a
burette that filled the tube to the mark.
Preliminary experiments indicated that there were two pertinent
types of apparent increase in volume. The first type is due t 0 the
breaking down o granules into a state of finer division when placed
in a liquid. Material that exhibited none of the properties o bentonite showed this tendency. For example, the apparent volume of
a 2.5-gram sample, which was 2.4 c. c. at minus 10-mesh, when pulverized in a mortar to minus 200-mesh became 4.9 c. c.; and 2.5 grams of
the minus 10-mesh sample when placed in water broke down, giving
an apparent volume, of 5.2 c. c. Although this breaking down was
considerably decreased in saturated solutions of several salts, only
gasoline, kerosene, and lubricating oil of the liquids tried had no
visible effect on the clays and bentonites (except to change their
color). In these liquids the soils retained their original hard gran""Warren, J. A., "E!fect of salt water on bentonite": Min. and Met .. voL 7,
p. 349.
1~26,
13
ular character, and the resultant volumes were the same as the
apparent volume of dried samples of the same fineness.
The second type of expansion is a real swelling. It is very marked
in water for material similar to typical Wyoming bentonite, being
up to about seven times the original apparent volume and about
eighteen times the actual volume of the bentonite dried at 105 C.
(average specific gravity, 2.7 5).
Table 2 gives a few typical results showing the volumes of different bentonites and clays result.ing from the addition of solutions
that might be used commercially to aid in wet drilling.
TABLE
2.-Arrpa.rent
vol1~mes
occupied by bentonites and clays
[Measured in c. c., 2.5 grams in contact with different solutions for 24 hours at 20 0 .]1
No. 1' No. 9 ' I'< o. uINo. 14' 'No. 15 ' l'<o. 16 7 No. 17 s No. 18 o
- - - - - - - - - - 1- - - - - - --------------Dry volume. .. ----------- -- ----- -----
Volume in water---------- -- -- ------ Volume in !'laO! solution:

0.5 per cent . . -- --- -- --- - -------2per cent --- --- --- -- - - -------- 10 per cent _______ __ . -- ~ ----- . ..
Saturatod _____ ... ___ . _. __ ... ---solution:
Volume
in cent
KCl_______________________
0.5 per
2 per cent_ __ __ ___________________
10per c-ent.-- .. ----.-- -------- Saturated __ ___ _________ -- - -- Volume
in cent
MgCb
solution:
0.5 per
_______________________
2per cent. __ . _____ . _____ .. _______
lOper cent. __ ___ _____ --------- ..
Saturated ________ . _____ .. . ____ . __
Volume in Na,so, solution:
0.5 per cent_______________________
2 per cent ....... -- -- -- ------ --- -10 per cent. ___ . ______________ ---Saturated ...... __________________
Volume in K.so, solution:
0.5 per cent ______________ _________
2 per cent_ _________ ____________ __
lOper cent. ___________ __ __ _______
Saturated ..... ___ .. _. - -----. ____
Volume in MgSO, solution:
0. 5 per cent. ... . ____ ------------2 per cent . .. ____ .. --------------10 per cent . .. .. -----------------
Saturated .. -- --- -. ___ __ . . _____ ___
2.0
10.0
8. 0
5. 5
4.4
3. 8
7. 1
4. 8
4. 3
3. 4
6. 2
5. 2
4. 7
4. 6
7.6
6.0
4. 8
4. 8
' 7. 5
5. 6
4.3
3.9
6.9
5. 3
4. 2
3. 7
2.4
2. 0
7. 5
13. 5
7. 2
6. 5
11.2
5.8
5. 2
6. 7
6.5
5. 5
4. 8
3. 2
5. 8
6.6
3. 9
3.7
5. 5
5. 3
5.1
5. 0
12.2
5. 5
5.3
5. 2
3. 7
5. 0
4. 7
3. 5
6. 0
5. 8
4. 9
4.0
-------- ------ -- --------------- -------- ------- -------- -------- --------------- -------- --------------- ----- --- --------------- ---- --- - --------------- -------- ---------- ----- -------- -------8. 0
fj, 6
.5. 3
3.7
2. 3
2. 3
9. 5
15. 0
7.1
6. 3
11. 5
5.4
4.8
6. 5
4. 3
2.3
6. 7
6. 7
6.1
2.9
12.6
5. 1
8. 1
6. 7
4.9
4.5
3. 8
4.4
6. 6
6.0
5. 2
4.6
11.1
4.8
6.0
7. 6
5.8
4.9
6. 2
3. 2
6. 8
6. 5
5.4
4.4
8. 7
6.1
7. 9
6. 8
5.4
4.7
7.1
6. 4
3.2
4.4
4. 9
4.4
6. 9
6.5
6. 5
4. 6
3. 9
4.5
14.8 - ------- -------8. 5 -------- -------5. 7 ----- --- -------4. I
13.0
7.0
5.4
4.7
4. 4
4.4
7. 0
6. 4
5.2
4. 2
6. 6
5. 2
-------- --------------- --------------- --- ----------- - ---------- ----- --------
9. 2
3.8
6. 8
6. 6
5. 8
5. 6
' The results are probably accurate to withil1 0.5 c. c.

'No. !-Bentonite from near Fallon, Nev. (similar to Wyoming-type bentonite).
' l'<o. 9-0taylite from Otay, Calif.
'l'<o. 11-Bentonito from near Belle Fourche, S. Dale. (similar to Wyoming-type bentonite).
' l';o. 14-Shoshonite from Shoshone, Calif.
6 No. 15-" Oil-filtering clay" from Nye County, Nev.
7 No. 16-Bentonite from Medicine Bow, Wyo. (similar to Wyoming-type bentonite) .
'No. 17-Bentonite from north of Santa Fe, N. Mex.
'No. IS-Bentonite from near Randsburg, Calif. (similar to Wyoming-type bentonite).
These tests and others show that the addition of quantities up to

about 2 per cent. o any one of a number of soluble salts marlredly
decreases the swelling produced when bentonites are treated with
water. The additional retarding effect becomes less as the salt solution becomes more saturated.
Combinations of various salts resulted in the increase in volume
that one would expect from consideration of the action of the single
salts; no a.bnormal action was encountered.
4713-2.&--3
14
BENTONITE
Soaked bentonite residues from the more dilute solutions were not
visibly granular and felt smooth when rubbed between the fingers;
but as the salt concentration became greater the residues became
visibly granular, although still soft. When the solutions were saturated all residues were visibly granular and many remained hard,
resembling the original dry-crushed material. The firmness of clay
and bentonite residues (except those from substa.nces not affected by
water) seems to be a function of the nature of the solution and of the
material; and the degree of this hardness follows approximately in
reverse order the apparent volume of the soaked residue, regardless
of the solution used-that is, the smaller the resulting solid the
harder it is. This may be exemplified by the action of different reagents upon a typical bentonite the apparent volume of which was
2.3 c. c. dry and became 16 c. c. when placed in water. This matBrial, as well as all other samples of clay or bentonite tested, pro.
duced a very harsh, firm residue when soaked in gasoline, kerosene,
or lubricating oil, and there was no visible evidence of disintegration
or increase of volume after several days of treatment. A saturated
solution of lithium chloride gave a very hard residue with an apparent volume of 2.6 c. c. The residues became successively softer and
more voluminous in saturated solutions of the following salts: LiCl,
NH4 Cl, (NH 4 ) 2 80 4 , FeCl3 , KCl, Na 2 C0 3 , N aCl, MgSO 4 , MgCl 2 , SrCl2 ,
AlCl 3 , CaCl2 , BaCl2 , Al 2 (S0~) 3 , 95 per cent C2 H.OH, Na 2 S0 4 , and
c~o~
Two factors, temperature and hydrogen-ion concentration, which

are known to have considerable effect on the swelling of gels, were
studied in their relation to the swelling of a bentonite (sample 16)
from Medicine Bow, 'V"yo. The results are given in Table 3.
TABLE
3.-Effect
ot t em peraJt!re ancl nydrogenrion concentration on tlbe sweavn.g

ot bento?Yite
Hydro-
Volume of 2.5 grams at different temperatures,
gen-ion
Solution
c. c.
~~~~~~ 1 - - - - - , c - - - - - . - - - - , - - or pH
1 C.
I 20 C.
45 c.
94" C.
- - - - - - - - - - - - - - -1--- - - - - - - - - - - - H CL. - -- - __ --- . __ .. __ . . ---- ------ - c -- - - -- ----
Do_ .... -- ---- - ____ . ..... .. .. ------.- -----. ___ ___

Do.- ------ - ---------- -.------ ----------------Do ___ __ ______ _____ . ___ . __ __ .. -- -- --- ------ - ____ _
Do .... - ----------- -------------- ------------- -__ . ___ -------- -- ------ -- -- -- _____ _
n,oDo
__ .__________
___ . ______________
. ______ .. __ ____ __ _____ _______ _
Nao H __________ ___ .. ___ . ___ . ___ . ________ ______ _. _. . _
Do.- --- ---- -- ______ . ___ __________ . ___ ___ . ______ .
Do.--- -- -- --- --- -- __ ____ ____ ______ __ . __________ _
.Do . __ ____ __________ _. ___ ______ _--- ---- ---- - -. __ _
Do ____
. .. ------------ ----- ---- ---------------Do
___ ____
. -------- -- ____
-- ---- __ ____ . __ . __ _
Do _______________ .. ---- --------. _______ ------- ..
Do ... ----- -- ---------------- -- -----------------NaCI (N/10) .__ ------- -------------- _______ . ______ ..
NaCI (N) .. --. ---- - __ ------ - ----- -- --- . --- - --- . -----NaCI (saturated ). __ . ____ .. -- -- - .- ---- __ . ____ . __ ___ _.
0.1
1
2
3
11.1
5
6
7
8
9
10
14.3
11
12
13
11.2
14
6
11.2
4. 3
3.8
5. 5
11. 7
13.5
14. 5
14.8
15.0
15. 0
14.8
14.8
14.7
14. 6
14.4
14.2
12. 0
6. 6
11. 5
4,5
3. 8
__ __ ___ , __ ---------12. 3
13.1
---- -- - --- -- -- -- -- ---- -- - - - - ---- --------- ------ ---- - -- --- -- - -- - -- - --- - -----15. 4
15. 6
- -- ---- -------- - --- -- -- - ---- - - ----------- ------ -------- - ---------- - - -- -- -- - ---------- ----------- --- - ---- -- - --- - - - 13. 2
13. 1
---- ---- -- ----- - -- - 12. 0
12, 5
4.8
5.1
3. 6
3, 7
15
INVESTIGATION OF PROPERTillS OF BENTONITE
Increase in temperature apparently promotes swelling, but the

small effects shown in the table may be due to increased rate of
swelling (readings may have been taken before the maximum volume
was reached) rather than to an ultimate difference in volume.
Increased acidity or alkalinity caused a reduction in swelling, but
the retardation was small near the neutral point, where many salt
solutions have a large effect.
To determine the relative effect of different salts in solutions of
equivalent concentrations, experiments using a bentonite from near
Newcastle, Wyo., were performed. The results are given in Table 4.
TABLE
4.-Appa.rent
vol1~me
occupied by a typical b entonite
[2.5-gram samples were left in contact with equivalent quantities of dllierent solutions for 24 hours at
20 C . Dry volume, 2.3 c. c.; volume in water, 16 c. c.]
Concentration, c. c.
R eagent
Concentration, c. c.
Three
Reagent
Three
normal
- - - -- - - - - - - - ----111- - - - - - - - 1 - - - - - - - - LiOL ____ ____ ____ __ ------------- ------5. 8
4. 2
3. 7
4. 2 Na:so,
AloCio. ___________
---- ---- ----_
3.9
NaOL_____________
7.4
4.4
10.0
5.1
4. 1
normal
KCI________________
5.2
NH,Ql____________ _
6.0
MgOJo_ ___ ___ ______

CaOh ---- --- ----SrOh_______________
B aCh --------- -- --FeCI,_____ ___ _____ _
3. 8
4.0
7.3
5.0
6.4
4.8
4. 9
4. 9
4.2
6. 0
6.4
5.9
3.6
3. 8
4. 2
4.1
4.1
4. 2
3. 6
K,so. __________ _
(NH,)oSQ, ________ _
MgS0<------------Feso, _____________ _
Ah(SOla----------r.a,oo, ___________ _
7.0
4.1
6. 2
4. 6
7.3
5.4
4.3
4.1
5. 6
6.3
6.4
6. 2
4.0
4. 2
3. 6
3. 6
4. 0
' A normnl solution contains 1 gram-equivalent of the solute in I liter of solution.
There is a greater chance for error in the results :for the 0.5 normal
solutions than in the others, because the rate of change of volume
with change of concentration and the effect of small amounts of
soluble impurities is greater in the more dilute solutions.
The method gives results accurate to about 0.5 c. c., showing that
equivalent concentrations of different neutral salts cause very nearly
equal retardation in the swelling of bentonite.
The prevention of swelling by the addition salts thus depends largely
on the effect o the salt concentration and on the resulting hydrogenion concentration, the first effect being more important :for most
salts, but the second effect becoming evident for ferric and aluminum
sulphates and chlorides, whose acid hydrolyses aid in cutting down
the swelling. (In saturated solutions and at elevated temperatures
considerable chemical action was noted when these salts were added.)
16
BENTONITE
DISCUSSION
Many substances swell when placed in a suitable liquid. A large

number of investigators have studied this.34
Bartell and Sims 35 have discussed the more important theories to
account for this swelling and list them under the following titles:
(a) The capillary theory, (b) the osmotic theory, (c) the lipoidmembrane theory, (d) the colloid-chemical theory, (e) the repulsion
theory, () the diffusion theory, and (g) the solid-solution theory.
They suggest that all these concepts, including that of the principles
underlying anomalous osmose, are necessary to explain .satisfactorily
all cases. Swelling, whatever its mechanism, is an increase in
volume due to the absorption or adsorption of a liquid.
An understanding of the swelling of crude bentonite is compli. cated by the facts that the material is not a pure substance, that it
has no definite chemical composition, that its composition may
change in the presence of salt solutions, and that it frequently
contains varying amounts of soluble salts.
Factors such as temperature, hydrogen-ion concentration, and the
presence of soluble salts are known to have an important effect on
the swelling of gelatin, proteins, and other substances.
Fulmer 36 has pointed out that the effect of various salts on the
swelling of gels may depend on the temperature in such a way
that the arrangement of salts in order of their suppression of swelling
(their dehydration power) for one temperature would not necessarily
hold for another. As has been shown, however, the swelling of
bentonite is changed little by temperatures between 1 and 94 C., but
certain solutions might change it considerably due to increased ionization of the salts and accelerated chemical reaction.
:-. Wilson, J. A. , "Theories of leather chemistry": Jour. Am. Leather Chem. Assoc.,
vol. 12, 1917, p. 1 08-122 ; The Chemistry of Leather Manufacture: New York, 1923, 350
pp.; Wilson, J . A .. a nd Wilson, W. a., "Colloidal phenomena and the adsorption formula ": Jour. Am. Chem. Soc., >ol. 40, 1918, pp. 886-895; Procter, H. R., "The equilibrium of dilute hydrochloric a cid and gelatin": Jour. Chem. Soc., vol. 105, 1914, pp.
313-3137; Procter, II. R., and Wilson, J. A., "The acid-gelatin equilibrium": Jout. Chem.
Soc., vol. 109. 1916, pp. 307-319; Loeb, J acques, Proteins and the Theory of Colloidal
Behavior: New York, 1922, 292 pp. ; " The stoichiometrical cha racter of the action of
neutral salts upon the swelling of gelatin": Jour. Bioi. Chem., vol. 34, 1918, pp. 77-95;
Proctor, 11. R., and Burton, D., " The swelling of gelatinous tissues " : Jour. Soc. Chern.
Ind., vol. 35, 1916, pp. 404-409 ; Fischer, M. n., " Hydration and ' sol ution' in gel atin ":
Science, vol. 42, 1915, pp. 223-23() ; Soaps and Proteins : New York, 1921, p. 222; 'l'olman, R. C., and Stearn, A. E., "~Ioleculru mechanism of colloidal behavior " : Jour. Am.
Chem. Soc., vol. 40, 1918, pp. 264-272; Lloy<l, D . J., "The swelling of gelatin in hydrochloric acid and sodium hydroxide": Biochem. J our., vol. 14, 1920, p. 147; Katz, J . R.,
" Micella are not necessary for the explanation of uncomplicated s welling" : Z. Physiol.
Chem., vol. 96, 1916, pp. 255-287; Bartell, F. E., and Sims, L. B., "The relation of
a nomalous osmose t o the swelling of colloidal material" : Jour . Am. Chem. Soc., vol. 44,
1922, pp. 289-299 .
.. See footnote 34.
"" Fulmer, E. I ., " The effect of ammonium salt s upon the swelling of colloids and upon
the g rowth of yeast at various t emperatures" : Colloid Symposium Monograph, vol. 2,
1925, p. 206.
17
The addition of acid or alkali decreases the swelling power of bentonite in water, but this effect is very small in the range pH 4 to 9.
The measurable effect of neutral salts on swelling depends somewhat on the concentration. Ostwald 87 states that the order of the
cations of the Hofmeister series varies with the concentration and
also with the nature of the colloid, giving data that clearly show this.
The results given in Table 4 show that each neutral sulphate is less
effective than its corresponding chloride in the dehydration of Wyoming bentonite, but the difference is so small as to be within the
probable limit of error for the tests. Table 4 also shows a slight
difference in the effects of neutral cations on t he swelling of bentonite.
Again the differences are so small as to preclude a sure statement as
to the specificity of the ions, but the order of the chlorides and sulphates, so far as it was determined, was the same. The series for the
chlorides in the order of their greatest dehydrating effect for normal
and three normal solutions is K, NH" Na, Ca, Sr, Ba, and Mg, and for
the sulphates is K , NH4 , Na, and Mg.
CONCLUSIONS
From a consideration of the behavior of the_~l of Wyoming bentonite one would judge it to be ~n_ inorganj_c, hydrophilic colloid.
Material such as the samples of bentonite from Texas and New Mexico, whose apparent expansion in water evidently is due to breaking
down, should cause no trouble in wet drilling except through caving
of the well walls, since the increase in volume is small and the resulting product is not pasty; however, certain bentonites swell markedly
in water and are known to cause the difficulties enumerated. The
tests described show that lubricating oil, kerosene, or gasoline could
be used to replace water in wet drilling through bentonites, to prevent swelling and breaking down; however, water would have to be
excluded to prevent the formation of emulsions. Cheap saltS could
be used to form dilute solutions that would cut down the swelling of
bentonites in water considerably, but they would probably not prevent caving. Apparently, the addition of a large amount of these
salts would prevent detrimental action of the solutions on bentonite.
For some bentonites sodium chloride evidently gives satisfactory
results; other bentonites, however, become soft in a saturated solution
of this salt, indicating breaking down and caving of the walls of
wells being drilled. Bentonites that become soft in saturated sodium
chloride solution may remain firm in a solution of some other common.
salt, so drilling difficulties caused by bentonite may be overcome in
almost all cases.
"Ostwald, W., and Fischer, 111. H., Handbook or Colloid Chemistry: Philadelphia, 1915,
p. 168.
18
BENTONITE
LOSS OF COLLOIDAL PROPERTIES ON HEATING
A small portion of minus 10-mesh material was put into a porcelain

crucible and heated in an electric muftl:e. The temperature was raised
by intervals of 50 C., and the samples allowed to remain 24 hours at
each temperature. After each heating small samples were placed in
test tubes of water and shaken. Below 350 C. all the samples absorbed water. Sample 12 lost its colloidality (was no longer affected
by water) at 410 ; sample 10, at 510 ; sample 9, at 575 ; and sample
11, at 670 C.
Regulated heat treatment differentiates the types of bentonite. in
the same order as swelling in water ; that is, t he less t he swelling in
water, the lower the temperature at which colloidality is destroyed.
Fe. Oa+Al.Oa: Si02 RATIO OF DECANTED MATERIAL
A 5-gram pulverized sample was mixed with 500 c. c. of water and

coagulated with sodium chloride. The flocculated material was then
decanted. Although the properties of different soil colloids follow
2.pproximately the ratio of alumina plus iron oxide to silica,38 the
results in Table 5 indicate that no such relation holds for different
types of bentonites; t he swelling in water showed no dependence on
the oxide ratio.
TABLE
5.-Coffl1}arison ot the ratio of
A.~Oa+Fe.Oa
to
sw. ana to swelling

A'O+FeoO,+SiOo
Sample number
Swelling, ,
crude
Floccu
bentonite Crud~
lated
bentorute material
----------------------------------------------------------1-----------9 . - - - ------.------------------- - -
--------------------------------------1
c. c.
i~::: :::::::::::::~::::::::::::::::::::::::::::::::::::::::::::::::::::::
4. 5
t~
0. 285
. 300
. 288
o. 298
. 311
334
. 336
307
EXPERIMENTS IN DYE ABSORPTION
Using the information given by Moore, Fry, and Middleton,89 who

worked out conditions t hat gave quantitative estimates of t he colloidal
material of soil by absorption of malachite green oxalate (after the
removal of lime by an oxalate salt), the relative absorption of this
dye by sample,s of bentonite was determined. A weighed amount of
bentonite and 25 c. c. of water were placed in a 100-c. c. test tube and
then 5 c. c. of N/10 K 2C 20 4 solution was added. A 0.4 per cent
,. .Anderson, M. S., a nd Mattson, S., Properties of the Colloida l Soil Material : U. S.
Dept. .Agriculture Bull. 1452, 1926, pp. 1-46.
Moore, C. J ., Fry, W. II., a nd Middlet on, H. E ., " Me thods for det ermining the amount
ot colloidal material in soils " : Ind. and E ng. Chem., vol. 1 3, 1921, p. 527.
19
INVESTIGATION OF P ROPERTIES OF BENTONITE
malachite green solution was added until the dye concentration in the
clear solution was approximately the same in the different tubes.
With sample 11 a 0.2-gram sample was used because of its large percentage .of flocculent material, while 0.5-gram samples of the others
were used. The ratio of the dye absorbed to bentonite was: No. 9,
0.306; No. 10, 0.241; No. 11, 0.380 ; No. 12, 0.107.
The results again follow the order of the swelling of bentonite in
water. The greater the swelling the greater the dye absorption.
This gives another method ior differentiation of bentonites.
REMOVAL OF ALUMINA BY SULPHURIC ACID
Five grams
of 20 per cent
of the filtrate
mesh material
of crude 100-mesh bentonite was boiled with 100 c. c.

(by volume) H 2S04 for one hour. The Al2 0 8 content
was determined. A second test was made using 150~
and boiling the mixture for t hree hours.
P er cent of .Al,O, clissoT!Ved

Sample number
First test Second test
9------ ------------------------------ ------------- - --~ 93.2
92.2
10---------------- -------------------- - - -------------- 67.0

11-------------- ------------------ - ------------------- 15.5
12---------------------------------------------------- 17.6
93.8
67.2
81. 3
To .study t he residue fr.om the H 2 S04 treatment 200 grams of crude

(100-mesh) bentonite was boiled for one-hal hour with 600 c. c. of
25 per cent (by weight) H 2 S0 4 , filtered, washed twice, and dried
at room temperature. R esidues 9 and 10 resembled dehydrated silica
gel, filtered easily, retained ver y little :free acid, and when dried
formed a powder. R esidues 11 and 12 filtered with difficulty, forming
a p lastic mass, retained a large amount of free acid, and when dried
formed a hard cake.
Bentonites may be divided into two gr.oups according to the difference in the action of sulphuric acid on their alumina content. The
Wyoming-type bentonite which contains alumina resistant to the
a ction of sulphuric acid will be called " bentonite," while the type
in which the alumina i,s mostly dissolved by sulphuric acid will be
termed "subbentonite."
TEMPORARY OSMOTIC PRESSURE
One gram of crude pulverized bentonite was p laced in a 20-c. c.

collodion sac fitted with a small glass tube, one-eighth inch bore;
the collodion sac was suspended in 1,000 c. c. of distilled water and
the maximum temporary osmotic pressure measured. The height of
the water in the tube was : No. 9, llh inches; No. 10, less t han %
inch ; No. 11, 8 inche.s; No. 12, less than ljz inch. The samples are
again arranged in the .order of their swelling in water-
20
BENTONITE
EFFECT OF NaCl AND CaCl, SOLUTIONS ON BENTONITE
Five grams of bentonites 9 and 11 were dialyzed against distilled

water until the dialyzing water was free from soluble salts. The
samples then showed no temporary osmotic pressure. The dialyzed
bentonites were dried at room temperatures. Sample 9 disintegrated
i n water, giving a larger amount of finely dispersed material than
before dia.lysis, but the swelling properties of sample 11 were reduced considerably and it dispersed less readily in water after t reatment. Two more samples were dialyzed free from soluble salts, then
dialyzed against 0.05 normal CaCl 2 for 5 days (the solution being
changed each day), and then dialyzed against distilled water until
free from CaCl 2 Neither the material containing excess CaCl 2 nor
that from which the excess salt had been r emoved showed appreciable osmotic pressure.
The triply dialyzed samples, dried at room temperature, did not
swell or disintegrate when placed in water; however, they formed
plastic masses wpich if dispersed in water flocculated upon the addition of electrolytes. Two more samples were dialyzed free from sol- 1
uble salts, treated with CaCl2 , dialyzed free from CaCl 2 , and against
N / 10 N aCl until dialyzing water was free from Ca, and then dialyzed 1
free from NaCl. A temporary osmotic pressure began to show as the
N aCl was washed out; increasing at each change of dialyzing water
until a maximum was reached, then decreasing to a small constant
value. When the pressure was near its maximum a sample was
removed and dried. This.. material sh.o.::w.e.<Lp:mperties-si-mila-r -to
t hose of Wyoroing;~pe bentonite.
By treating 5 grams of samples, 9, 10, and 12 with normal N aCl
solutions at five-hour intervals 20 times, then dialyzing with water
until the temporary osmotic pressure was near its maximum, a material was formed that resembled Wyoming-type bentonite very
closely. The change was brought about more easily with samples
9 and 10 t han with 12.
Bentonites having the properties of Wyoming-type bentonite
would probably have sodium (or other alkalies) as exchangeable
bases, and bentonites with alcium (or other alkali earths) as exchangeable bases could be made to resemble t he type material by
treatment with an alkali salt solution (to replace the alkali earth
with an alkali) .
A differentiation between these types of bentonites will be made
by calling those which seem to have exchangeable alkali bases "alkali bentonites" and those which seem to have exchangeable alkaliearth bases "alkali-earth bentonites."
The residues from an acid t reatment were impregnated with norm'll NaCl as above. Samples 11 and 12 gave a temporary osmotic
COMMERCIAL BENTONITES
21
pressure on removal of NaCl, but 1 and 10 (subbentonites) did not.

After the removal of N aCl t he material was dried. Samples 11 and
12 showed bentonitelike properties but samples 9 and 10 still tesembled dehydrated silica.
The authors attempted to determine the amount of Ca replaced by
N a but wer e unsuccessful because of the small amounts of Ca to be
determined in the solutions. In the first three dialyzing solutions
of N aCl, samples 10 and 11 showed respectively 0.009 and 0.007
grams of CaO per gram of crude material.
..,. ., ,.. i
IDENTIFICATION AND CLASSIFICATION OF COMMERCIAL
:BENTONITES
Bentonites similar to the Wyoming-type material (without soluble

salts) can be recognized easily by their marked swelling and dispersion when placed in water, but for the other types no ,simple test
is available.
A scheme has been selected and tried out to identify commercial
bentonites and to separate them according to their properties into
four groups term-ed " alkali bentonites," " alkali subbentonites,"
"alkali-earth bentonites," and " alkali-earth .subbentonites." Definitions of t hese groups follow.
Alkali bentonrite.-A bentonite containing easily replaceable alkali
bases and having original properties which are not permanently
destroyed by the action of sulphuric acid as they can be restored by
treatment with an alkali salt followed by regulate dialysis. This
group includes \Vyoming-type bentonite and others similar to it.
Alkal!i subbentonrite.-A bentonite containing easily replaceable
alkali bases, but having original properties destroyed by acid
treatment.
A lkali-earth be-ntonite.- A bentonite .containing easily replaceable
alkali-earth bases and, either before or a~er acid treatment, capable
of being made to assume t he p roperties of an alkali bentonite by
treatment with an alkali salt followed by regulated dialysis.
A lkald-earth 8'Ubbentonite.-A bentonite containing easily replaceable alkali-earth bases, but after treatment with acid not capable of
being made to assume the properties of an alkali bentonite. Most
oil-refining clays are in this clas,s.
A study of the properties of the bentonites named shows t hat swelling in water, loss of colloidality in heating, absorption of dye, and
temporary osmotic pressure place bentonites in the same groups. The
first of these, although easy to apply, is subject to serious error if
soluble salts are present in samples to be tested; the second and third
require careful manipulation and are also affected by impurities;
the fourth properly can be used to separate bentonites into two
4713-28----4
22
BENTONITE
groups, alkali bentonites and alkali-earth bentonites, and is readily

applicable in the presence of soluble salts.
This classification depends upon the temporary osmotic pressure
produced by bentonites having exchangeable alkali bases and upon
the absence of temporary osmotic pressure produced by bentonitep
with alkali-earth bases.
Test 1.- An emulsi<m containing 1 gram of the sample to be tested
and 20 c. c. of distilled water is placed in a collodion sac of 20 to 25
c. c. capacity, .fitted with a cork stopper through which one end of a
glass tube (about 12 inches long and with a lfs-inch bore) passes.
The collodion sac as prepar ed by Nevy and others is described by
Bigelow and Gemberling.40 The sac is placed in 1 liter of distilled
water, and, if the sample is free f rom appreciable quantities of soluble
salts, the temporary osmotic pressure will cause the water to rise 6
inches or more in t he tube when the sample is an alkali bentonite such
as those of wyoming or South Dakota, or an alkali subbentonite. The
material within the sac will become uniformly dispersed. If there are
soluble salts in the sample the water in the beaker should be replaced
with fresh distilled water every six hours until the bulk of the salts
has been r emoved, at which time the temporary osmotic pressure
and uniform dispersion of the material within the sac will be observed with alkali bentonites and alkali subbentonites. If there is
maximum temporary osmotic pressure without dispersion of the
sample the material is not a bentonite.
Test 2.-The effect of sulphuric acid on bentonites may be used
to differentiate bentonites f rom subbentonites; the former are but
slightly altered while the latter are attacked so that their original
properties can not be restored. In applying test 2 a 1-gram sample
(minus 100-mesh) is boiled with 50 c. c. of 25 per cent (by weight)
sulphuric-acid solution for 3~ minutes, then filtered and washed with
distilled water until freed Jrom soluble sulphates.
Test 3.-A third test is required to determine the effect of test 2
and to differentiate alkali-earth bentonites (or alkali-earth subbentonites) from other rocks. The material is treated with alkali salts
so that temporary osmotic pressure and uniform dispersion will be
given to the alkali-earth bentonites, alkali-ear th subbenton~tes, acidtreated alkali bentonites, and acid-treated alkali-earth bentonites,
but not to acid-treated alkali subbentonites, acid-treated alkali-earth
subbentonites, or rocks other than bentonites. Test 3 is performed
as follows :
A 1-gram sample is pulverized and heated on a water bath with
50 c. c. of normal NaCl and 5 c. c. of N/ 10 Na2 C0 3 solutions for two
"'Bigelow, S. L., and Gemberling, A.., "Collodion membranes" : Jour. A.w. Ch ew. Soc.,
vol. 29, 1907, p. 1578.
PROPERTIES THAT DETERMINE USES OF BENTONITE
23
hours, then decanted and the residue put into a collodion sac and
dialyzed in distilled water. High temporary osmotic pressure and uniform dispersion indicate a bentonite. If a high temporary osmotic
pressure develops and the material is not dispersed through the sac, too
much Na2 C03 has been used or the material is not a bentonite. The
difficulty can be removed by using an alternative method in which
the hydrogen-ion concentration is not altered. This method involves
treating 1 gram of crude material with 150 c. c. of normal NaCl for
six hours, shaking occasionally, decanting, and repeating the treatment 20 times. The residue is then dialyzed to remove excess NaCl,
after which bentonites show a high temporary osmotic pressure and
uniform dispersion of material throughout the sac. Although this
method requires considerable time, it is more reliable than the former
method.
Apply test l to the sample
No tempora.ey oamot1o preaaure

(Alkali earth ben toni tee
aubbentoni tee, or clay~
~J.f..h
temporary osmotic pressure

Un1torm dispersion
Ko dlsE!:rslon
(Alkali benton! tes and subbontonl tesl {clay I
Apply test 2;
then test 3
m:r.,=mpo=ra=ry::-::-os=m'=:ot"lc::-:::pr=-=e-::-:ss=ur=e
(Alkali benton! tes )
Apply test 3
No temporary osmotic pressure

(Alkali subbontonl tos)
llo temporary oamot1o

pressure
(cle,;v)
Hisb temporary osmotic pressure
Uni form cUspersion
No dispersion
(clay)
Apply tst 2; then test 3

(uslll8 original clay as sample)
High to:nporary oamouc pressure
(Alkali ear th bonton1 tes)
:to
temporary osmotic pressure
(Allcali earth sub benton! tes)
FIG. 1.-Scheme for classifying bentonites
By the use of these tests commercial bentonites may be identified

and separated into four groups. Figure 1 explains how such a
classification can be made.
Other rocks are not like bentonite as they may have difficultly
replaceable bases or may contain salts with a low degree of hydration.
PROPERTIES THAT DETERMINE THE USES OF BENTONITE
The commercial importance of bentonite may depend on its physical condition (marked adsorption, absorption, or coalesce,nce and its
effect on emulsions, suspensions, and surface tension) or on its chemical reactivity or on both. Some of these properties have already
been discussed, but certain phases merit further mention.
ADSORPTION AND ABSORPTION OF LIQUIDS BY SOLIDS
A liquid is adsorbed by a solid when a surface of the solid becomes

wet through the mutual attraction between the surface and the liquid,
24
BENTONITE
whereas absorption involves the penetration of the solid by the liquid.

Bentonite may act in different capacities in its relation to adsorption
and absorption.
The direct imbibing of water and various solutions by bentonite
is undoubtedly a combination of adsorption, absorption, and chemical
reaction. These properties grade into each other and overlap, the
most important function depending upon the actual nature o bentonite. I mainly crystalline adsorption would predominate, and i
mainly a lyophilic 41 colloid absorption would be involved. An alkali
bentonite takes up five or more times its weight o water and swells
as much as 13 times its original size, while agitation with enough
water, unless excess electrolytes are present, forms a nearly permanent suspension. These characteristics determine several uses of this
type of bentonite. Bentonites also take up a considerable quantity
of dye.
The refining of oil by bentonite apparently depends largely on the
selective adsorption of coloring matter, both suspended and dissolved,
from the crude oil; but chemical reaction seems to have some part.42
acid-treated subbentonites are largely used for this purpose.
The effect of bentonite on interfacial tension in r elation to the
spreading of liquids on other substances is another example of
adsorption of liquids by solids. It is well known that soap added to
various commercial preparations promotes spreading or wetting, and
it has been stated that bentonite can actually replace the soap substance in soap. This has led to various predictions that bentonite
would promote spreading. The principle upon wh ich spreading of
liquids depends has been known a long time.
Recently a great deal of work has been done in studying the
wetting properties of different liquids and in developing the theory
as applied t<? various uses,' 3 so that a workable numerical expression
was produced. The matter has been developed from thermodynamic
principles and placed on a satisfactory theoretical basis by Harkins
and Feldman, 11 who show that spreading occurs i the adhesion beu From lyophile, a term introduced in 1905 by J. Perlin (Ann. ch!m. phys., vol. 3, 1905,
p. 84) to indicate t hose systems in which there is a marked affinity between the two
phases of a colloidal solution.
"'Rogers, T. II., Grimm, F. V., and Lemmon, N. E., "Adsorption studies on the d ecolori
zation of mineral oils": Ind. and Eng. Chem., vol. 18, 1926, p. 164.
43 Moore, Wiiliam, Spreading and Adherence of Arsenical Spr ays : Minnesota Agr. Expt.
Sta. Tech. Bull. 2, 1921, 50 pp. ; Thornton, W. M., "Experiments on liquid mixtures f or
laying coal dust": Eng. :t.Un. J our. Press, vol. 94, 1911, p. 531 ; Hillyer, W. H., "On tlle
cleansing power of soap": Jour. Am. Chem. Soc., vol. 25, 1903, pp. 511-532 ; Cooper,
W. F., and Nuttall, W. II., " The theory of wetting and the determination of the wetting
power of dipping and spraying fluids containing a soap basis": Jour. Agr. Sci., vol. 7 ,
1915, pp. 219-2<19; Robinson, R. H ., " Spreaders for spl'lly materials and tlle relation of
surface tension of solutions to tlleir spreading qualities": Jour. Agr. R es .. vol. 31, 1925,
pp. 71-81 ; CoglT!ll, W. H., and Anderson, C. 0., Certain Interfacial 'l'ension EquilibriA
Important in F1otatlon : Tech. Paper 262, Bureau of Mines, 1923, p. 48.
.. Harkins, W. D., and Feldman, A .. " Films. The spreading of liquidf' and tlle spreading coefficient" ; Jour. Am. Chem. Soc., vol. 44, 1922, p. 2665.
25
tween two liquids is greater than the cohesion in the liquid which
is in the position for spreading. This has been expressed in terms
of tension by stating that a liquid will spread on a solid (or other
liquid) if the surface tension of the solid (or second liquid) is equal
to or greater than the su:rp. of the surface tension of the liquid and
the tension of the liquid-solid (or liquid-second liquid) interface;
that is, spreading will take place if the tension at the liquid-solid
interface is less than the difference between the surface tensions,
and the greater this difference is the greater the tendency to spread
will be.
This effect can be brought about in two ways-by changing the
nature of the solid surface and by lowering the tension of the liquid
or of the liquid-solid interlace or of both. A liquid that wets a
smooth solid surface may not spread on a rough surface of the
same material; and the presence of adsorbed substances-gases, liquids, or solids-at the solid surface will have an important effect on
its surface tension, since the free surface energy of the solid may be
lowered by the contaminating substance. (The substance already
adsorbed must be replaced.) Changing the surface conditions by
polishing, dissolution, heating, replacement, or other action allows
a certain amount of control of spreading. 'Where it is not feasible
to change the nature of the solid surface the surface tension of the
liquid may be decreased by regulating the temperature or by adding
suitable substances to produce the conditions necessary for wetting.
To promote spreading, bentonite would have to raise the surface
tension of the surface to be wet or lower the tension of either the airliquid interface or of the liquid-solid interface or both. Bentonite
might tend to produce the first result by cleaning the surface or by
its strong affinity :for gases, liquids, and solids and if adsorbed at the
air-liquid or liquid-solid interface might lower the tensions at these
interfaces.
That bentonite has been long used for detergent purposes gives
evidence that the nature of a dirty surface may be changed by bentonite. Oiled surfaces were investigated by smearing two pieces of
glass with lubricating oil and sprinkling one with bentonite and the
other with an equal quantity of pulverized quartz. After the surfaces
had stood over night they were rinsed with water, and after drying
were tested with drops of distilled water. The surface that had been
covered with bentonite permitted the drops to spread much more
than the surface that had been covered with quartz, showing that
bentonite had removed oil, thus changing the nature of the surface.
To determine the effect of bentonite on the surface tension of
water, bentonite was shaken with distilled water. No permanent
froth formed, which indicated that bentonite is not adsorbed at the
water-air interface. Surface tension measurements by the capillary
26
BENTONITE
tube and the drop weight and de Noiiy apparatus methods were the
same for distilled water as for water to which bentonite had been
added. These results indicate that bentonite does not change appreciably the surface tension of pure water. However, bentonite
might have considerable influence on a sol~tion containing absorbable
substances, and bentonites that contain soluble salts would probably
affect the surface tension. There seems no good way to determine
the effect of bentonite on the tension at a solid-liquid interface.
Robinson 45 tried to substitute an oil for the solid, but although he
used various oils as substitutes for leaf and apple surfaces he was not
able to predict the spreading of solutions on these surfaces from his
surface-tension and interfacial-tension measurements. In wetting
oily surfaces Cooper and Nuttall 4 6 successfully evaluated the wetting
power of various stock dips from surface tension results. Experiments performed in the study of emulsions show that bentonite goes
to the oil-water interface and influences the type of emulsion produced, indicating that bentonite has an appreciable effect on the oilwater interfacial tension.
A summary of the effects of bentonite on the factors important to
spreading shows that bentonite may change the nature of a solid surface and may influence the oil-water interfacial tension but has little
or no effect on the surface tension of pure water.
Bentonite, however, may have an important though indirect action

in spreading. Ostwald 47 pointed out that the external phase of an
emulsion placed in contact with a substance capable of being wet
will wet the substance. An emulsifying agent which produces a certain type of emulsion will therefore determine indirectly which part
of the emulsion will be effective in wetting. As explained under the
section on emulsions, bentonite acting in the capacity of an emulsifying agent has this directive influence.
ADSORPTION OF GASES BY SOLIDS
All solids tend to adsorb or condense upon their surface any

gases or vapors with which they are in contact, the adsorption being
specific for the solid and the gases. I no chemical reaction or
solution is involved, the gaseous adsorption may be used as a measure of the surface. This method has been used for determining soil
colloids by their adsorption of ammonia gas, but for bentonite
would be less accurate, due to the reactivity of its bases. As bentonite has an enormous surface, it could probably be used as an adsorbent for various gases, but its properties in this connection have
not been noted in the literature.
" See footnote 43, p. 24 .
.. See footnote 43, p. 24.
"Bancroft, W. D., Applied Colloid Chemistry: l\ew York, 1921, 345 pp.
27
USE AS A COLLOID
In addition to the properties of bentonite usually attributed to

colloids, such as adsorption, swelling, formation of stable suspensions, peptization, and flocculation, its plasticity and action as an
emulsifying agent merit further treatment.
Plasticity has been defined as a condition such that a finite force
is required to give a permanent deformation and one in which any
cracks formed are self-healing.48 To the clay worker the plastic substance must retain its form on drying and burn to a coherent mass.
This latter condition, according to Bancroft, requires a liquid gelatinous film which is strongly adsorbed by solid particles and which
can take up and lose water rapidly. 49 Although many indirect schemes
have been devised to measure the plasticity of clays, such as adsorption of malachite green, drying, shrinkage, length of a clay column
extruded from a die, tensile strength and extensibility of a clay
pencil, angle of bending before fracture, and amount of water necessary to give greatest plasticity,60 no satisfactory method has yet
been devised for its absolute measurement; and although the subject
has been much studied no satisfactory explanation has been given
of the nature of the colloidal gel that remains plastic after moderate
drying and then readsorbs water to form a gel. No known mixture
of colloidal alumina and silica will do this, but Bancroft and Jenks
found that the addition of sma.ll amounts of lithium chloride would
make alumina or kaolin (but not silica) very plastic.u1 Alkali bentonites are extremely plastic and also have the property of readsorption of water after drying, seeming to indicate particles coated with
a gel.
An emulsion consists of drops of one liquid suspended in another,
and for much stability a third 15ubstance known as an emulsifying
agent must be present. Any substance adsorbed at the interface
of two immiscible liquids may act as an emulsifying agent and may
determine the type of emulsion formed. If the emulsifying agent
is peptized by one liquid and not by the other the former will be the
external phase ; and the emulsifying agent supposedly will be more
strongly adsorbed on t he external phase side of the interface, the
tension on that side being lowered and the interface becoming convex
toward it.
When an alkali bentonite was added to a test tube containing
water and oil considerable bentonite was held at the oil-water inter Bancroft , W. D., "The development of colloid chemistry": Jour. Frank. Inst., voL
199, 1925, p. 759.
See footnote 47, p. 26.
,. Bleininger, A.. V., " The properties of clays " : Colloid Symposium Monograph, vol. 2,
1925, pp. 80-97.
"'Bancroft, W. D., and Jenks, L. E., "The plasticity of clay : Jour. Phys . Chern., voL
W , 1925, pp, 1215-1217.
28
BENTONITE
face. This was true of linseed oil, cottonseed oil, pine oil, and a
medium grade of lubricating oil. The above oils when agitated with
water a short time formed a temporary froth, but in the presence of
alkali bentonite produced a rather permanent froth. This is in accord
with Bancroft's 52 theory that the bentonite is adsorbed by the oilcoated air bubbles, causing the film to become viscous and preventing
direct contact and coalescence of the oil films. Vigorous agitation
of oil and water in the absence of bentonite produced emulsions of
oil in water. After settling the liquid consisted of a layer of cleat'
oil at the surface, but the rest was a cloudy emulsion and remained
so for a long time. With alkali bentonite as an emulsifying agent
violent agitation produced an emulsion of water in oil (for the oils
mentioned above), and after settling there was a layer of clear water
at the bottom, the rest being an emulsion. The type of emulsion
produced was determined by the method devised by Briggs.53 A
small amount of the emulsiun was examined under a microscope
while being stirred, and a little water or oil was added. If the oil
was the external phase, the added water did not mix with the portion of emulsion examined, but oil a.dded to an emulsion of this type
resulted in mixing. The light petroleum fraction.s such as kerosene
form an emulsion of water in oil when agitated with water, but the
presence of an alkali bentonite results in an emulsion of oil in water
when agitated.
The action of bentonite as an emulsifying agent is not like that
of water dispersed in kerosene by being shaken with soot, as observed by Schlaepfer. 54 It resembles an ammonium chloride solution
dispersed in oil by shaking with carbon, as performed by Moore 55 ;
but it is probably more closely related to the dispersing of water in oil
by the colloidal ash and asphaltic material of crude oils, shown by
Dow and Reistle 56 to be the result of a gelatinous colloid as an
emulsifying agent. The action of bentonite as an emulsifying agent
. is similar to that of casein, which Seifriz 57 has found stabilizes an
emulsion o water in petroleum products whose specific gravity is
greater than 0.86, and of oil in water if the specific gravity of the
:former is less than about 0.82.
""Bancroft, W. D., "The t heory of emulsification": Jour. Phys. Chern., vol. 17, 1913,
p. 514; vol. 19, 1915, p. 275. Soo also footnote 47, p. 26.
"'Newman, F. R., "Experiments on emulsions" : Jour. Phys. Chern., vol. 18, 1914, p. 34.
04 Schlaepfer, A. V. M., "Water - in-oil emulsions": Jour. Chern. Soc., vol. 113, 1918,
p. 522.
"Moore, W. C., "Emulsification of water and of ammonium chloride solution s by
means of lamp black": Jour. Am. Chern. Soc., vol. 41, 1919, p. 940.
,. Dow, D. B., and R eistle, C. E., jr., P hysical Chemi stry of Oil-Field Emulsions: Repts.
of Investigations, Serial 2692, Bureau of J\fi nes, 1925, 14 pp.
"Seifriz, Wm., Types of hydrocarbon-oil emulsions" : Jour. P hys. Chern., vol. 29.
1925, p. 587.
PRESENT AND PROPOSED USES FOR BENTONITE
29
The action of bentonite as an emulsifying agent may be explained

by Bancroft's theory stated as follows:
An emulsif}'ing agent is a substance which goes into the interface and produces a film having satisfactory physical properties. If the adsorption of the
emulsifying agent lower s the surface tension on the oil side of the interface
more than it does on the water side, the interface will tend to curve so as to
be concave on the water side and we shall have a tendency to emulsify water
in oil.
Alkali bentonite, then, must be more strongly adsorbed or wet by

most oils than by water and should be concentrated at the interface
on the oil side, t hus lowering the tension of the oil more than that
of the water; but in the case of light fractions the reverse is true.
Bentonite, therefore, might be used as an emulsifying agent to remove water from light petroleum fractions by percolating a mixture
of kerosene and water through air-dried bentonite, the water being
taken up by the bentonite and the kerosene coming out free from
water.
Anything that destroys the film of a peptizing agent at the oilwater interface tends to break the emulsion. Since petroleum-water
emulsions are r eversed by alkali bentonites the addition of the right
quantity of bentonite would prevent the formation of a stable emulsion. Another way in which acid-treated bentonites might prevent
stable emulsions is by removing the colloidal matter of the petroleum
which is supposed to act as an emulsifying agent.
Prospectors or others who become interested in the production of

bentonite should make a careful innstigation of the commercial possibilities of the deposit in question before investing heavily. Such
a study should include the possibility of marketing the product, the
specifications demanded, the price obtainable, the cost of mining,
treating, and shipping to market, the size of the deposit, and the
nature of the crude bentonite. One should also realize that most consumers desire a homogeneous product that will remain uniform over
a period of years and t hat deposits containing bentonite which will do
this are not common; that most crude bentonites contain appreciable
quantities of objectional impurities such as sand, gypsum, carbonaceous matter, or soluble salts that must be removed at considerable
expense by washing; and that the purified bentonites from different
deposits and even from different levels or parts of the same deposit
may have very different properties, such as variation in color, colloid
content, and ease of hydration. In general, consumers want a clean,
homogeneous, finely divided substance.
30
BENTONI TE
Although a number of uses have been proposed for bentonite more

work to determine its suitability for these uses is desirable.
BENTONITE AS A FILLER, BINDER, OR PLASTIC
A filler is a finely divided inert substance added to give body or

weight or to produce other desirable physical conditions in another
substance. It may be mixed with the other ingredients to form an
integral part of the body or it may be applied in the form of a wash
or suspension to fill pores or to form a coating. The general characteristics, such as extreme state of fine division, property of remaining in suspension, plasticity, and high absorbent power, that make
purified ground alkali bentonites admirable fillers, binders, or plastics have been discussed in previous sections; their specific uses will
be considered next.
PAPER, OILCLOTH, CURTAIN CLOTH, LINOLEU:M, OR CORDAGE
Paper manufacturers consume most of the clay in the filler industries. They consider absence of grit, white color, and retention 58
the most important properties of a filler for high-grade paper.
These requirements would rule out most crude bentonites, as well as
many that had been purified, since a white bentonite is not common.
Where a light-colored material can be produced, or where the color
is not important, alkali bentonite and subbentonite should market
well for filling paper, as it is very efficient in promoting the retention of china clay. The retention of clay alone is 45 per cent; with
10 per cent of alkali bentonite it is 58 per cent; with 20 per cent of
bentonite, 64 per cent; and with 100 per cent of bentonite, 84 per cent.
Alkali bentonite also gives a superior feel 59 to the paper and overcomes the gumming of the screens used in the pulp industry by
forming an emulsion with the r esinous matter. A Denver paper
company is reported to have used a large quantity of Wyoming bentonite as a filler or loader. 60 Other paper companies have rejected
bentonite because of its cost, although they admitted it h ad certain advantages ; and still others are using alkali bentonite to repl ace part or
all of the china clay formerly used. When suitable bentonite is
favorably situated with respect to the m~rket its sale to the paper
industry may be profitable.
Although there are no standard tests for evaluating clay fillers for
oilcloth, curtain cloth, linoleum, or cordage, specifications usually
"' Weig el , W. M., Georgia a nd Alabama Clays as Fillers: T ecb. P a per 343, Bureau of
Mines, 1925, p. 13.

'" Ladoo, R. B., NonmetaJlic M JneraJs: New York, 1925, p. 93. Sec also footnotes. 5, 9 ,
13, and 2 5, pp. 1, 3, 4, and 9.
"'::ipen ce, H. S., B entonite : Canada D ept. Mines, R cpt. 626, 1924, 35 pp.
31
include freedom from grit, ready slaking to a smooth soapy feeling

cream or slip without lumps, comparatively low oil absorption, and
in some cases a pure white color. Bentonites are not known to have
been used to replace clay in these industries, but their physical properties indicate that they should be of value for this. A laboratory
test showed that less linseed oil is required to produce a certain
consistence with alkali bentonite than with kaolinite.
RUBBER
Considerable finely divided inert material is used as a rubber filler,

and although the only reliable way to determine its value for this
purpose is by compounding and comparing the properties of the
product with those of a standard compound, a few consumers have
stated that the filler should be free from grit, should pass a 200-mesh
screen, should not contain over 4 per cent of moisture, and should
not lose more than 8.5 per cent on ignition. Recent work by Thies 61
indicates that clays having low absorption for dye (malachite green)
are best suited for use in rubber, where an organic accelerator wa~
introduced, as those with high absorption for dye also absorbed
the accelerator. As alkali bentonite absorbs much malachite green 1
usually contains more than 4 per cent of moisture, and loses more
than 8 per cent on ignition, its usefulness as a rubber filler is doubtful; but practical tests should be made with all types of bentonite
to decide the matter.
One investigator has also suggested 62 that alkali bentonite or
subbcntonite might find use in the preparation of rubber emulsions
for sprayed rubber.
CERAl\HCS
The value of bentonite in the ceramic field has been demonstrated.

Manson 68 found that 1 per cent of alkali bentonite gave a much
better suspension of enamels in grinding frit for making a ground
coat than was secured by 2.5 per cent of clay, and Cox 64 determined
t hat alkali bentonite added to certain mineral mixtures produced
a plasticity identical to that of the clays liked best by practical
potters and that kaolin could be made to have the pasticity of highgrade ball clay by the addition of alkali bentonite. Most bentonites
burn to buff or light red and sinter in a Bunsen flame.
"'Thies , IJ. R., "Relation between dye adsorption of clays a nd their behavior in rubber
compounds " : Ind. and Rng. Chern., vol. 17, 1925, p. 1165.
"' Kirschbraun, L., Emulsion of Bentonite and Rubber: United States Patent 1498387,
June 17, 1924 .
.;, Manson, M. E., "'l'he use of bentonite for suspending enamels": Jour. Am. Ceram.
Soc., vol. G, 1923, p. 790.
.. cox, I'. E., "The s tu!ly of plasticity by practical potter's methods": Jour. Am.
ceram. Soc., vol. 7, 1924, p. 151.
32
BENTONITE
Bentonite has also been suggested for use in this field in the preparation of graphite crucible bodies to cause a closer bond between the
particles of graphite and other constituents and as a substitute foi'
part or all of the bonding clay used in electrical porcelain, chemical
porcelain, or abrasive wheels. The high shrinkage would seem,
however, to detract from its value for this work.
PORTLAND CEMENT
Spence's experiments with Portland cement indicate that the

mechanical strength was increased and the time of setting reduced
by;adding up to 1 per cent of bentonite,65 and Collings has patented
the use of bentonite, treated with mineral oil and mixed with concrete, as a filler and waterproofing agent. 66 A large amount of
alkali bentonite ,could not be used because of its shrinkage on drying,
but a small amount in stucco mixes of either Portland or magnesian
cements might make them impervious to water by filling up po~e
space.
ROAD BUILDING
Bentonite was thought to have some value in surfacing highways

because of its binding power and its resistance to the passage of
water. To test this the State Department of Highways constructed
a road in the vicinity of Carrara, Nev., by pulverizing and spreading
a bentonitelike clay over a sand road that had been oiled but not
stirred. The State highway engineer reports that, after a year and
a hal of service, this road has held up very well and is now in good
condition. Bentonite could doubtless be used as a substitute for
clay in the construction o: such roads, but its price might not make
its sale for this purpose attractive.
LUBRICATING GREASES
There are two ways in which bentonite absolutely :free from grit
might have some value in lubricating greases. First, bentonite might
be mixed directly with the grease and its selective adsorption :for
oil and metal with its slippery nature might aid in the retention of
a protecting film at metal surfaces. Se.condly, alkali bentonite
might replace the calcium soap used to prepare emulsions of water
in heavy oils, since such emulsions are stabilized by this bentonite.
An extensive investigation would have to be made before bentonite
could be recommended for lubrication.
00
Spence, H. S., Bentonite : Canada Dept. Mines, Rept. 626, 1924, 35 pp.
Colling-s, W. A., Calcareous Plastic Material: United States Patent 16(}1295, Sept. 28,
1926.
6
33
PUTTY
Tests by the writers show that all types of bentonite are workable as putty with appreciably less linseed oil t han whiting. The
resultant bentonite putty is apparently as good as the other, except
that its clark color may make it objectionable for some uses. The
effect of weath ering will have to be determined before its value for
glazing can be known.
FOUNDRY WORK
The use of alkali bentonite as a bonding agent in molding sands,

especially the high-silica sands required in steel work, has been suggested as advantageous. Its use in peptizing the carbonaceous matter
in core washes is already well known.
Opinions differ as to the suitability of bentonite as a binder in
molding sand. Discussions of this subject have appeared recently 6 7
in which Hansen states that tests made with bentonite from Belle
Fourche, S. Dak., showed that although bentonite was about twice
as efficient as t he best clay in developing the green strength and
the dry strength (when baked at low temperatures) of molding
sand, it dehydrated very easily with an accompanying loss of bonding value so that it had no appreciable life in the molding-sand
h eap and its fusion temperature was very low. H e considers that
its disadvantages outweigh its advantages. Bird, however, considers
the properties of bentonite very desirable for a binder in a molding
sand, and Bull states that a steel foundry h as obtained very good
results by substituting Wyoming bentonite for clay, although the
former cost $42.50 per ton delivered. Bull thinks that the amount
of bentonite required in the mix is too small to noticeably affect the
refractory qualities, and Jones says that a foundry in Milwaukee
has been using bentonite for 2 or 3 years.
1'Vyoming bentonite has also been used quite successfully to
emulsify linseed oil for making cores with a saving of about onehalf in the quantity of oil required.
PHONOGRAPH RECORDS
A~D
ELECTRICAL INSULATION
The qualities desired for a phonograph record filler are that it

shall be finer than 200-mesh , free from grit, and have low absorption
for the binder used; the color is not important. Purified bentonite
would have possibilities for this use.
Similarly bentonite may be used as a filler for sealing wax or
molded electrical insulation , and its use in the preparation of elec111 Bird, R. M., Hansen, C. A., Bull, R. A., and Jones, E. L., "Mining and preparation of
eastern molding s ands" : Trans. A. I. M. M. E., vol. 7 3, 1926, pp. 388-393.
34
BENTONITE
trical insulation has been patented by McCulloch,68 who advocates

various mixtures of mica, bentonite, water, boric acid, and glycerin
for insulation in electrical heating equipment.
PENCIL LEADS, CRAYO::S, AND PASTEL COLORS
The clay for pencil leads must be absolutely free from grit, and to
achieve this long grinding or a costly refining by endosmotic means
is necessary. Purified bentonites would probably be admirably
suitable for the manufacture of pencil leads, and some of the large
pencil companies are understood to be using this material already
for indelible leads and crayon work, thus saving considerable in
grinding cost. The use of some other wetting agent would eliminate the excessive drying shrinkage resulting from the use of water
with alkali types. The manufacturers of indelible leads, crayons,
pastel colors, and the like, where grease or wax is used in the mix,
would find bentonite of considerable value as a constituent of their
products.
PLASTERS
Bentonite may have a place in gypsum and lime plasters, but its
value as a retarder in the former is doubtful. Alexander 69 found
that in commercial plaster of Paris bentonite increased the speed
of set, possibly due to the adsorption of contained organic retarder.
PASTE, GLUE, OR SIZE
Bentonite is reported of particular value as an adhesive for stick

ing labels on metal, as, for example, on tin cans. Tests by the writers
with different samples of bentonite showed that although such mixtures feel sticky they are much inferior to the usual adhesives.
However, bentonite might be used as a minor constituent of pastes
or glues, acting as a colloidal coagent. A patent has been granted
for the use of gum chicle dispersed with bentonite as a coating for
metals.70
Alkali bentonite adheres well to textiles wb,en used as a size and
imparts no harshness to the finished goods. Articles treated with
bentonite are less apt to mold than those treated with starch, as bentonite is inert. It can therefore be used for this purpose.
MISCELLANEOUS FILLER USES
The physical nature of bentonites has suggested their use as the

bonding agent for stove, shoe, and other polishes, to which they give
.. McCulloch, L., Electrical Insulatin g Material: United States Patent 1286043, Nov. 26,
1918; Electric Resistance Material: United States Patent 1365331, J a n. 11, 1921; Ins ulating Material: United States Patent 1386008, Aug. 2, 1921.
.. Alexander, J., "Bentonite": Colloid Symposium Monograph, vol. 2, 1925, pp. 99- 105.
70 Biddle, A., Gum Chicle Dispersed in an Aqueous Colloid :
United States P atent
1624088, April 12, 1927.
l'RESENT AND PROPOSED USES FOR BENTONITE
35
a pleasing texture. Alkali bentonite can be used as a leather dressing

and it is reported to have been in active use as an adulterant for
caramels and other candies since the time of the first shipments from
Wyoming in 1888.
r-
BENTONITE AS ADSORBENT, EMULSIFI
; OR. PEPTIZER
This section, although rather arbitrarily segregated as most of

the uses proposed for bentonite depend to a considerable extent on
its colloidal properties, brings together a number o related subjects
and simplifies their discussion. The colloidal properties of bentonite have been taken up in a previous section.
SOAPS AKD DETERGENTS
The Indians and prospectors of the Western States have known

for a long time that "soap clay" has valuable cleansing properties,
and tests by the authors showed that alkali bentonite had considerable detergent action and that it removed oil or grease from glass
surfaces and dirt from the hands and from cloth even in the absence
of soap. Comparatively recent research seems to indicate that bentonite may replace as much as 25 to 50 per cent of the soap substance,
at the same time increasing the lathering and detergent properties.71
Weston 72 states that soap containing colloidal clay produces more
]ather than pure soap, that the lather is firmer and more persistent,
that a larger quantity of water is converted into lather, that
the detergent properties of the soap are improved by the presence of this clay, and that the surface tension of the solution is considerably lowered when conoidal clay is add,ed.
However, the results of the authors agree with those of Weissenberger,73 who found that more soap was required to produce a lather
with bentonite, due doubtless to the adsorption of soap substance.
Further tests showed that the surface tension of distilled water as
determined by the capillary-tube method, the drop-weight method,
and the breaking-film method was not changed by alkali bentonite
and that the surface tension of a soap solution which at 25 was 28.5
dynes per centimeter was not noticeably changed by the addition of
small quantities of bentonite; more bentonite raised this value,
however, again indicating an adsorption of soap substance. The
l'ather produced with bentonite may be very stable because of its
adsorption and resultant strengthening of the bubble films. The
addition of typical bentonite (with an alkali base) to hard water
n Ladoo, R. B., Nonmetallic 1\llnerals; New York, 1925, p. 93. See also footnotes 5, 9,
13, and 25, pp. 1, 3, 4, and !l.
"Weston, F. E., "Colloidal clay in soap manufacture": Chern. Age, vol. 2, 1920, p. 58.
Wcissenberger. G., [ "The possibility of su bstituting inorganic colloids for soap"] :
Tech. Hochschule, Wien. Kolloid-Z., Jahrg. 27, 1920, p. 69.
36
BENTONITE
before soap is added will materially cut down the quantity of soap
required to give a froth because of the softening effect on the water;
but whether this action would take place on the simultaneous addition of the two substances was not certain, as sodium carbonate, toreduce the quantity of soap required for hard waters, must be added
and given time to r eact before the addition of the soap. Tests were
made to decide this matter. One solution of calcium chl'oride and one
of soap were prepared. When 5 c. c. of the calcium chloride solution
was used, 4.5 c. c. of soap solution was required to form a froth.
The authors added 3 c. c. of soap solution and 5 c. c. of distilled
water to each of two test tubes, then a little alkali bentonite to one
tube, and 5 c. c. of the calcium chloride sol'u tion to each test tube;
the tubes were then agitated violently. The test tube containing the
bentonite foamed, while the other clirl not, showing that bentonite in
a soap will reduce the quantity of soap required to give a froth with
hard water.
Alkali bentonite in cleansing seems to promote emulsions; it adsorbs dirt (both solid and liquid) and is in turn adsorbed by the
bubble films, coagulated, or suspended, thus preventing the dirt from
returning to its previous surface. Alkali bentonite also helps to
soften hard ''ater through its base-exchange property and may aid
the saponification of greasy material through the alkalinity produced
by its hydrolysis in water.
Bentonite is said to be especially va.luable for scouring textiles,
producing a more brilliant color in dyed goods and increased clarity
and sharpna.c:s in printed materials, having a superior " bottoming'~
effect on yarns and fabrics, and producing a better finish on all
goods than other scouring agents. Detergents containing bentonite
are being sold in the United States and on the British market. They
were also widely used in Germany during the war. Alkali bentonite
gives toilet soap a particularly velvety feel, 74 and its use in laundry
soap is indicated by the fact that investigations have shown it to be
u seful in practical' washing tests, both on a small scale and in a
commercial laundry.
Although various tests, such as Spring's peptization of lampblack/5 surface-tension measurements, and Chapin's graphite test,76
have been devi,sed to determine the value of different soaps, the most
satisfactory way to determine whether a particular bentonite will
prove beneficial when incorporated in a detergent seems to be to carry
out practical washing tests, with and without bentonite, comparing
the results as to cleansing effect and quantity of detergent required.
"Alexander, J., "Bentonite": Colloid Symposium Monograph, vol. 2, 1925, pp. 99-105.
,. i:>pring, W., The Chemistry of Colloids: llull. Acad. Roy. Belg., 1909, p, 187.
'" Chapin, R . M., " Fundamental principles of detergent action revealed by the graphite
test": Ind. and Eng. Chem., vol. 17, 1925, pp. 1187-1191.
37
The same water, temperature, time, agitation, fabric, and dirt should
be used as in the washing operation being investigated.
DEINKING PRINTED PAPERS
77
Alkali bentonites have proved ,successful and economical in actual

practice on an industrial scale in deinking old newspapers. The
adequate expansion of this industry would not only provide an outlet for bentonite but would also help reduce the timber cut by about
275,000 acres per year. This timber required about 100 years to
grow.
The process used in deinking newspapers, which was developed
and brought to its pre,sent successful stage at the Forest Products
Laboratory, Madison, w is., consists of cutting the varnish of the
ink by heating the old newspapers with a caustic solution at a temperature low enough that the paper stock is not di colored , aJding
alkali bentonite to peptize the carbon black, and washing with water
so that the carbon is washed through and the pulp retained on
screen,s.
Alkali bentonite in water apparently acts as a negative colloid,
whereas, as shown by Spring,78 lampblack in slightly alkaline solutions is positively charged. The carbon is therefore adsorbed by
the bentonite. The attraction of the bentonite :for carbon mu,st be
stronger than that o:f the paper fibers, as the carbon is held dispersed
in suspension and passes through the screens on washing. Other
results show that colloidality is important in thi,s treatment. China
clay and other finely divided noncolloidal clays were very poor in
removing the ink :from newspapers under the optimum conditions
for the treatment, but when heated to higher temperatures (too high
for practice, since the pulp was discolored) the clays were peptized
and removed the carbon.
From this, simple tests have been devised to evaluate claylike substances as to their usefulness in deinking newsprint. Using a
sample that will adequately represent .t he material being tested is
jmportant. The first test determines whether or not the product
is an alkali bentonite. It is easy to apply, requires no special equip
ment, and can be made quickly. This tes.t depends on the swelling
property o:f alkali bentonite. Twenty-five c. c. of distilled water is
placed in a 50-c. c. graduated cylinder. Five grams of a sample that
has been dried and prepared to pass a 12-mesh screen but to be
'' For more detailed information see Wells, S. D., "~faking paper trom old paper
stock" : Paper, vol. 30, 1922, p, 7, and Jour. Paper Trade, vol. 74, 1922, p. 47; The
Deinking of Old Newspapers: Forest Prod. Lab., U. S. Dept. Agriculture, mimeographed
report, 1922, 16 pp. ; Cost of De!nked Newspaper ; Forest Prod. Lab., U. S. Dept. Agriculture, Tech. Note 194, 1922, 3 pp.
'" See footnote 75, p. 36.
38
BENTONITE
retained by a 16-mesh screen is gradually added to the cylinder

through a funnel, and the cylinder is then carefully filled with
distilled water. The volume of the solid matter is read from the
graduations and after a definite time (30 minutes is satisfactory)
the volume is again noted, the difference between the two readings
being the volume increase. The swell.ing may continue for several
weeks, but satisfactory results can be obtained in the time specified.
The following typical r esults show the ability of this method to
differentiate between alkali bentonite and other claylike substances.
An alkali bentonite with an original volume of 5 c. c. swelled to 28
c. c. in 30 minutes, a bentonite with slight colloidal properties
increased from 5.5 to 12 c. c., and a subbentonitc (sample 5) attained a volume of 11 c. c. from an original 6.5 c. c. in the same
time. That some bentonites .t hat do not themselves disperse ~n
water may be made to do so by treatment with alkali solutions
shows the desirability of testing a substance which does not give an
appreciable osmotic effect and shows little swelling tendency to sel!
if it may be made to disperse under the conditions used in deinking
practice. One gram of a pulverized sample and 1 gram of sodium
carbonate are agitated with 250 c. c. of water at 70 to 75 C. for
30 minutes. The solution is then decanted and the residue washed
into a collodion membrane sac of about 30 c. c. capacity as in the
testing of bentonitelike clays. The osmos.is apparatus is fitted with
a glass tube 1 foot long with an opening 78 inch in diameter. If
the substance is suitable for deinking, a temporary osmotic pressure
(causing the liquid to rise 6 inches or more in the tube) will be
observed, after the substance has been dialyzed with fresh portions
of distilled water until excess sodium carbonate has been removed.
The bentonite will become uniformly dispersed throughout the sac.
The maximum dispersion depends on the hydrogen-ion concentration of the solution. This fact might be used in the deinking
process to save bentonite, the alkalinity of the solution containing
the pulp and bentonite being such as to give maximum dispersion of
the bentonite.
Several factors of importance indicate tha.t bentonite will be used.
more and more for the deinking of newspapers. The practicability
of its use has been proved. A mill operating at the rate of 40
tons of de;inked newspaper stock per day made an average yearly
saving of $15 per ton over the cost of using ground wood pulp. The
cost of equipping an ordinary 30-ton mill with additional washing
equipment and of a warehouse to hold three months' supply of old
newspapers is only about $10,000. This would be covered by the
extra profits realized on about 700 tons of deinked newspaper stock.
A survey of the waste-paper field showed that a collection of about
39
2,500 tons a day could be expec.ted as against a total daily countryw.i de consumption of about 7,000 tons of newsprint. Reclamation
plants situated at large cities would retard t.hc ever-increasing freight
charges caused by the depletion of the nearer forests supplying pulp
wood.
Since the use of bentonite for deinking old newspapers is successful both practically and economically and will help materially to
solve America's forest problem, the future production of bentonite
for this purpose will probably be of considerable importance.
According to the Forest Products Laboratory, Madison, 'Vis., the
development of this process will probably be s low since most mills
for making newsprint are located far from large cities, and plants
for a successful deinking of old newspapers would have to be close
to a large supply of old papers.
REFINING OF OU..S AND FATS
Probably most of the bentonite used at present is employed for

refining petroleum products in the Western States. Subbentonites
seem best adapted for this purpose; and although usually treated
with acid, some varieties are used in a raw state, the acid-treated
material being a more efficient decolorizer than the crude but not
so cheap. In the production of bentonite for this purpose it is
necessary to locate large bodies of material that will act uniformly
in treating oil.
There are three classes of petroleum products to be treated-light
oils, lubricating oils, and waxes. These may be produced by destructive, vacuum, or steam distillation. The former causes cracking, with
the resultant high proportion of higher hydrocarbons, dark color,
and more difficult refining. The others are considered better for producing lubricating oils. Some paraffin-base o.ils are ready for market
after distillation, but fractions distilled from asphalt oils or badly
cracked oils are usually treated with sulphuric acid. If the oil has not
been acid -treated, bentonite is called upon to remove carbon (either
colloidal or larger size), tarry complexes, and dissolved coloring
matter. Oil treated with sulphuric acid and washed with water
may contain sulphonates, esters, free acid, and the impurities listed
above, and oil treated with acid and neutralized with caustic may
contain the same substances with the difference that alkalies may be
present instead of free acid. Crude bentonite is sometimes preferred for the acid-treated oils to effect neutralization, and for treating gasoline. It is cheaper than acid-treated bentonite, but the
l atter is a much better decolorizer, being far superior to fuller's
earth. Arciniega 79 considers raw hydrous magnesium silicates better
"Arciniega, V. M., "Refinery clays mined in Nevada": Eng. and Min. Jour., vol. 121,
1926. p. 40i.
40
BENTONITE
than raw hydrous aluminum silicates (fuller's earth) for decolorizing

oil.
The acid treatment of bentonite is not difficult. In one method the
material is sun dried, crushed to 100-mesh, fed into a lead-lined tank
of 25 per cent sulphuric acid, and boiled with live steam; then it is
washed, filtered, dried, and crushed to 200-mesh. The acid treatment
apparently removes considerable alumina and the combined water
destroying the colloidal state. The residue resembles silica gel and
should contain little or no free acid.
Another method of treating bentonite with acid 80 consists of drying the material at 230 F., grinding it to an impalpable powder,
digesting it with 96 per cent sulphuric acid for several hours (using
about 9 parts of acid to 20 parts of bentonite, by weight), and finally
draining and washing with clean water.
Petroleum products are "clay" treated by the contact method but
percolation is ordinarily used for treatment with fuller's earth. In
the contact method the bentonite may be added wet to petroleum
products of high boiling point so that the steam evolved on heating
will produce agitation, but dry " clay " is more efficient for gasoline.
After heating at 200 to 300 F. to complete the decolorization, the oil
is run to settling tanks and then passed through presses. The amount
of " clay" required varies from about 1 pound per barrel ( 42 gallons)
for gasoline to as much as 100 pounds per barrel for dark heavy
lubricating oil. The "clay " m ay be used for treating several batches
of gasoline or light oils without rejuvenation, but for heavy oils it
must be discarded after one application. The residue is burned
beneath boilers but might possibly be used for surfacing roads. Used
fuller's earth and certain used acid-treated "clays" may be rejuvenated by igniting to remove carbonaceous matter. Other " clays,"
the bleaching properties of which are destroyed by heat, may be
rejuvenated by treatment with some solvent or solvents such as
gasoline, alcohol, or solvent naphtha.8 1
Various theories have been advanced to explain t he decolorizing
effect of acid-treated bentonite, and investigators have concluded that
the action may involve adsorption, filtration, possible chemical reaction, and catalysis. Rogers, Grimm, and Lemmon 82 decolorized
a number of kinds of oil with different adsorbents and found that
Freundlich's adsorption equatioo applied accurately, when the amount
60 Melhase, John, "Mining bentonite in California": Eng. and Min. Jour., vol. 121,
1926, p. 838.
"'Gurvich, L, and Gnrvicb, V., "New process for the regeneration of fuller's ear th ":
Chern. Abs., vol. 21, 1927, p. 4,033; Parsons, L. W., "Automotive lubricants" : Ind. and
Eng. Chern., vol. 19, 1927, p. 1,116; Prutzman, P. W., Revivifying Spent Oil Purifying
Materials: United States Patent 1633871, June 28, 1927.
"'Rogers, T. II., Grimm, F. V., and Lemmon, N. E., "Adsorption studies on the decolorl
zatlon of mineral oils " : Ind. and Eng. Chern., vol. 18, 1926, p. 164.
PRESENT AND PROPOSED U8ES FOR BENTONITE
41
of color removed was used as a measure of amount of material

adsorbed.
As the detrimental substances in each oil fraction differ greatly
(depending on the original crude and its treatment) , the particular
oil being treated must be used for evaluating a bentonite to treat it.
Furthermore, the color to which an oil is to be bleached may determine the most efficient bentonite; for example, one sample may be
more efficient in clarifying an oil to one color, but another sample
may be better to bring it to another color. Although adsorption
is important in decolorizing oils, probably no good method will be
devised for evaluating bentonites for oil refining by the use of dye
adsorption as a criterion. This is evident, as crude bentonites
which have little bleaching value may have a very high dye adsorption in comparison to excellent acid-treated bentonites; as tests
showed that although 200-mesh acid-treated bentonite adsorbed about
four times as much malachite green as 50-mesh material from the same
lot, the action of the two products in decolorizing oil was nearly
the same ; and as the conditions in oil decolorization are not those
of any single adsorption of a solute from any single solution.
L aboratory tests may be made to approximate plant practice and
are then of value in determining what bentonites are most efficient
in producing the desired decolorization in an oil fraction from a certain crude petroleum. For example, the relative value of different
bentonites for decolorizing a certain oil by the contact process, under
fixed conditions, may be determined by adding 2, 5, and 10 gram
samples of the dried pulverized material to 50 c. c. of oil heated to
125 C., raising the temperature to 150 C., agitating at that temperature f or 30 minutes, and then filtering through a filter paper.
(Some petroleum products require a high er temperature than this
to be effectively decolorized.) The resulting colors are then compared. A yello w color free from a reddish tinge is preferable.
The same procedure should be carried out with acid-treated bentonites to determine their action on the oil. To prepare an acid-treated
product, 200 grams of 100-mesh raw bentonite may be added to 600
c. c. of a sulphuric acid solution (25 per cent of H 2S0 4 by weight)
and boiled for 30 minutes, filtered, washed with water twice, dried
at room temperature, and pulverized.
Experiments by the writers indicated that bentonites in which the
alumina was readily attacked by the sulphuric acid treatment (subbentonites) produced the best adsorbents for decolorizing petroleum
products. The bentonites that retained their a.lumina contained considerable free acid after the treatment, dried very slowly, alid did not
lose their plasticity, but more drastic acid treatment might produce a
better product from such alkali bentonites.
42
BENTONITE
The most suitable direct use of alkali and alkaline-earth bentonites

in oil refining seems restricted to the field of vegetable and animal
oils and fats. Experiments have shown that acid-treated bentonite
is superior to either English or Florida fuller's earth in bleaching
and clarifying crude brown packing-house lard,83 and it has been
r eported that crude bentonite is being used to a considerable extent
for this purpose. The hot impure grease is percolated through
bentonite and comes out pure and colorless. After the bentonite
has become so filled with greasy impurities that it no longer functions
as a clarifier, both the grease and bentonite of the oil-filled bentonite
are used in making soap. This illustrates again the remarkable efficiency of packing-house methods. A deposit to be of value for this
purpose should contain a large amount of bentonite of uniform grade
that will properly do the work required of it.
HORTICULTURAL SPRAYS, ANIMAL DIPS, AND INSECTICIDES
Writers have pointed out various propert.ies that sprays and dips
should possess and have suggested the addition of agents to aid in
the formation of permanent dispersions, to increase adhesion, to improve the covering effect, and to promote the formation of a continuous coating of poison on surfaces on which spray usuaJly collects in drops. Such an agent must be ,i nert, causing no decrease in
the toxic action of the poison; it should not react to form compounds that would injure foliage and should be inexpensive.
English 84 determined that alkali bentonite has some of the desired
properties as an additional agent in emulsions. His preliminary
experiments with emulsions of kerosene, red engine oil, paraffin oil,
and furfural, using alkali bentonite as the emulsifying agent, showed
that these emulsions were satisfactorily stab.le and were less subject
to chem.ical influence than emulsions stabilized by soap but were
slightly less destructive to a species of aphid. H e found kaolin far
inferior to alkali bentonites as a stabilizer for these emulsions.
Y others 85 :fotmd that colloidal clays could be used in place of soap
for stabilizing emuJsions of mineral lubricating oils, that such emulsions were about as effective for spraying citrus trees against insect
pests as those made from soap, that they were no more likely to
cause spray burn, were easily made, kept indefinitely, could be prepared from any water or spray combination desired without special
treatment, and cost much less for material and labor than soap
emulsions.
'"Spence, H. S., Bentonite: Canada Dept. Mines, Rept. 626, 1924, 35 pp.
,. Engl!sb, L. L., "Preparation of insecticide emulsions with a colloidal cla y" : J our.
E con. Entomol., vol. 18, 1925, p. 513.
" Yothers, W. W., "Preliminary report on colloidal clays as emulsifiers for mineral
oils used in spraying citrus groves" : Jour. Agr. Res., vol. 31, 1925, p. 59.
43
In a series of experiments to determine the effect of alkali bentonite on the spreading of water on surfaces of dusty and clean
lle'aves and on oiled surfaces, the writers found no noticeable increase
in spreading caused by adding different amounts of benton,ite. The
~preading tendency was determined by noting the width and thickuess of drops of the substance being tested when placed on different
surfaces and left for definite time intervals and by observing the
wetness of the surfaces which had been dipped into and removed
from the Jiquids. Y others also noted that clay emuls.ions did not
spread on foliage but stood in drops, and although the addition of
.soap to such an emulsion caused the leaves to become uniformly wet
the same spotted effect was observed in both cases on drying. The
explanation of the spotting seems to be that the soap lowered the
surface tension of the water which, being the external phase, wet the
leaf surface; but the oil, being the internal phase, did not come in
contact with the leaf surface until the water had evaporated and
then stood in drops, except that some oil may have been thrown into
immediate cont.act with the leaf surface by the violence of the spray
striking it and by the breaking of the water film surrounding the
oil globules. As aJready explained, alkali bentonite tends to promote the formation of emulsions of water in certain grades of o.ils.
Emulsions in which oil wouJd be the external phase should prove
effective in causing a more uniform coating of the leaf with oil.
Therefore alkali bentonite will probably be used to some extent in
the preparation of oil emulsions for spraying against insect pests.
'l'he effect of bentonite on sprays that contain poison as finely
divided solid particles has not been investigated practically, but
laboratory tests showed that alkali bentonite aided in stabilizing
suspensions of calcium arsenate in water, both solids being negative
in this medium. Bentonite does not aid in spreading, nor does
it seems to aid adhesion of the poison to leaf surfaces. Moore 86
showed that a leaf surface acts as though negative, while the usual
arsenical poisons in water are either neutral or negative and therefore have small reason to adhere. In confirmation of this he prepared arsenates with a positive charge and found that they adhered
to leaf surfaces from 200 to 260 per cent better than the regular
arsenates. As satisfactory suspensions of arsenical poisons can be
made without dispersion agents there would seem to be no advantage in adding bentonite to them.
The use of alkali bentonite in animal dips would resemble its use
in emulsions for sprays. Where it would promote the formation
of emulsions containing oil in the external phase the skin of the
animal would become wet more readily by the oil than by the water.
"' Moore, William, "Adherent arsenical preparations ": Jour. Ind. and Eng. Chern., voL
17, 1025, p. 465.
44
BENTONITE
FUNGICIDES
A process has been patented 87 in which a fungicide is prepared

by melting sulphur and mixing it with bentonite (or other inorganic water-absorptive gel-forming medium) before it congeals.
USE IN PAINTS, ENAMELS, AND INKS
Since alkali bentonite has the power of adsorbing dyes and colors
and is in such a state of fine division that it forms a stable suspension, it should have a place in cold-water paints, calcimines, enamels,
printers' inks, and oil paint.88 The efficiency of alkali bentonite
in adsorbing and peptizing suspended lampblack has already been
shown; also its property of promoting emulsions o water in oil,
which is important in considering the formation of ready-mixed
paints, shown by Bancroft 89 to consist of emulsions of water in
linseed oil containing a pigment and peptized by rosin.
The writers made tests to study this effect of bentonite. Linseed
oil and barium sulphate were placed in a test tube (No.1), the same
mixture with a little alkali bentonite was put into another test tube
(No. 2) , part of mixture No. 1 and water were put into a third test
tube (No. 3), and part of mixture No. 2 and water were put into a
fourth test tube (No.4). The same procedure was followed, substituting white lead ground in oil for the barium sulphate, giving
tests Nos. 5, 6, 7, and 8. All test tubes were then well shaken and
left to settle. All remained uniformly mixed for about one hour,
then a layer of clear oil began to appear at the top of No. 1, which
gradually deepened until in 18 hours all of the barium sulphate had
settled to the bottom. No. 2 settled at a somewhat slower rate than
No. 1, but also settled completely. Nos. 5 and 6 acted similarly,
but the settling was much slower, 48 hours being required. No. 3
showed signs of separation after three hours, a layer of clear oil becoming visible at the surface and t he rest consisting of an emulsion of
oil in water with dispersed barium sulphate. The amount of clear
oil gradually increased until after five days there were three distinct
la:yers, the upper of clear oil, the middle of clear water, and the
lower of settled barium sulphate. No. 7 resembled No. 3 except
that it proceeded more slowly, a visible oil film appearing only after
18 hours and complete separation requiring about 15 days. Nos. 4
and 8 consisted of emulsions of water in oil with dispersed pigment
and alkali bentonite. These were very stable, no change being
noted during several weeks .
., Banks, II. W., 3d., Fungicide Containing Sulfur: United States Patent 1550650, Aug.
18, 1925 .
.. Spence, H. S., Bentonite: Canada Dept. Mines, Rept. 626, 1924, 35 pp.
*'Bancroft, W. D., Applied Colloid Chemistry: New York, 1921, p. 26~.
PRESEXT .!.~~D ?
i"'.SEn "CSES FOR BENTONITE
45
Bentonite colored by a& ~ dye \\ould apparently form a satisfactory pigment. 9 Fin~y dirided alkali bentonite free from grit
might therefore be used to a..:..-an~~e in tLe preparation of cold-water
paints, calcimines, enamels. ink:_ oil paints. and ready-mixed paints.
Ostwald 91 showed the importance of the external phase in an emulsion used for treating wood to pre>e!:t decay. H e pointed out that
in an emulsion of water and creosote. if creo::ote \\as the external
phase, the wood fiber would come in contact \\ith anJ absorb it. If
water were the external phase the \\OOJ fi'>er:- \\Ould become water
soaked and would repel the creosote.
in,e alkali bentonite acts as
an emulsifier promoting the formation of a water-in-oil emulsion
(except for light oils) its use in wood clips should pro,-e satisfactory.
ROOFING PREPARATIONS AND
WATERPRO"'~G
Although the extent to which bentonite h as been used in the

preparation of emulsions of asphalt, coal-tar residue,. and pit~h has
not been reported, such emulsions are thought to gi'"e ,.enice :for
roofing superior to that of the unpeptized substance, and considerable
alkali bentonite might be used in this way. 92 An investigation \\as
made of another similar use for alkali bentonite,93 in which asphaltbentonite and rosin-bentonite mixtures were ground in \\ater and
yielded excellent products for waterproofing paper board without
heat. Crude alkali bentonite could be used for these purposes.
COAL-MINE DUSTING
Recognition of the importance of rock-dusting coal mines to

pre>ent dust explosions is shown by the fact that, although at the
beginning of 1924 no companies had done real rock-dusting, by September. 1925. 102 companies in 12 States had rock-dusted 211 mines.94
The inert du...c:t dilutes the coal dust-air mixture and prevents the
propagation of an explos1on by absorbing the heat of the flame and
resisting its transfer :from one coal particle to another. The rock
dust also tends to pre>em the formation o:f a dense cloud o:f combus.., Gardner. H . .A., Labora.nry ::ou_ and l!b;;tract renew: .am. P aint and Varnish
).[nfrs. Assoc., Clrc. 306, 19 21. pp. !!H--~
1 Bancr oft, \\. D . Applied Col!o!d C"r.e:::usn-y: ~ew York. 1921. 3-!5 pp.
oo Kirsch braun, L., BituminoUE Co=poS.:;:Jon Sui :.able f.:.r Roofin;; or Other Cses:
United States Patent 1620900, lli:r. 1;;. 19!:7: ~q:: !011> B!t~I:linous Emu:~lons Containing
Bentonite: {;olted Stat es Patent 1620599 .M:!.:. :;;. 1927.
Spence, H. S .. Bentonite : Canada. De~. liines. Re;'t. 626. 1924, 35 pp.
"Owings, C. \\., and Dodge, C. H .. :llet!:od.;; sod Co>:s o! Rock-Dusting Bituminous
Coal Mines: Carnegie I nst. Tech. Bllil. 15. il.l:!.i. p. 4.
46
BENTONITE
tible dust. Bowles 95 summarizes the properties desired :for rockdusting as follows: A light color (to contrast with the coal and to
increase illumination), incombustibility, friability, low quartz content (to prevent silicosis), and cheapness. The fineness recommended
is through a 20-mesh and 50 per cent through a 200-mesh screen. 9 6
The cost of dust at the mine has varied :from $4.85 to $7.70 when
shipped in and from $2.60 to $5.50 when mined and pulverized at the
mine.
From the above considerations dry light-colored bentonite seems
peculiarly fitted for rock-dusting, but its cost would be prohibitive.
Pulverized bentonite could also be used in fighting fires in coal mines,
as rock dust has been found valuable for this purpose. 97
DUSTING AGENT FOR OTHER USES
If a finely divided material is mixed or rubbed with one not so

fine the finer material will coat the coarser. In grinding material
that tends to coalesce, a protecting colloid which coats the particles
as fast as formed and so prevents their sticking together again is
added. The Greeks ground gold leaf with honey and the Chinese
make their ink by grinding carbon black with a solution of gum.
Other applications of this method include the grinding of copper
ores with oil to prevent smearing, the addition of tannin when grinding deflocculated graphite, and the grinding of pitch with alkali,
casein, or rosin soap.98 Very recently the value of bentonite as
a dusting agent for the grinding of asphalt and rosin has been recognized and used commercially. Other uses based on fine division of
bentonite will doubtless be found.
DESICCATING AGENT
Alkali bentonite has been suggested as a laboratory desiccating

agent because of its high absorptive power for water. T ests were
made to determine its efficiency in this respect. A typical bentonite
(wilkinite) of about 10-mesh was dried at 105 C. and a 30-gram
sample was placed in a gas absorption bulb. Air, dried by passing it
through sulphuric acid, was passed in turn through the bentonite
and through a calcium chloride drying tube, the latter protected
by a Liebig bulb containing sulphuric acid. Moist air was then
., Bowles, Oliver, Sources of Limestone, Gypsum, and Anhydrite for Dusting Coal Mines
to Prevent Explosions: Bull. 247, Bureau of Mines, 1925, pp. 2-4.
90 Rice, G. S., Paul, J. W., and Sayers, R. R., Tentative Specifications for Rock-Dusting
to Prevent Coal-Dust Explosions in Mines : Repts. of Investigations, Serial 2606, Bureau
of Mines, May, 1924.
"'Jones, J. E., "Rock dusting at the Old Ben Corporation": Min. Cong. Jour., vol. 11,
1925, p. 226; Howarth, II. C., a nd Greenwald, H. P., Tests with Rock-Dust in Extinguishing Fire: Repts. of Investigations, serial 2801, Bureau of Mines, Apr., 1927 .
.. Bancroft, W. D ., Applied Colloid Chemistry: )lew York, 1921, 345 pp.
47
PRESEXT AXD P ROP OSED USES FOR BENTONITE
passed through the train. the alternate passing of dry and moist air
being repeated as shown in the table.
Bentonite a.s a de:siccant
Change in weight,
grams
Time, hours
C ond:t:on ol air
I Bentonite
1 . _- --------- ___ _.... _-- - ------ Dry-- --- . .. -----2. __ --- ----------- ----- ---- -- Moist .... ...... _ ....... -- -
1. ............ . ... .. ........ . .......... Dr:;................ --- ---------

6 -- ----- ----- ------------ - Moist.......... ...... - ---
10. ___ __ ___ ___ _.. _ -- - --- -- ---------- Dry------------- - -- - ............ .

8 1 _ _ do..... ... _.... _............
- 0.012
+ .615
-.026
+.431
- .334
Calcium
chloride
+ 0.009
+ .186
+ .030
+. 431
+.2"2?.
- . 047
' The bentonite tube was removed in this test.
These tests show that bentonite dried at 105 = i, much inferior

to calcium chloride as a laboratory drying agent. and that since alkali
bentonite dried in this way contains only about 6 per cent of moisture
that can be driven off by heat before the property of ab~orbinp: ''"ater
is destroyed, the possibility of using ignited bentonite for de.~iccation
is limited to the absorption of about 6 grams of "ater for e\ery 100
grams of this drying agent.
REMOVAL OF WATER FRO:r.1 PETROLEUM
In the production and refining of oils, emulsions of oil and water

are often formed that might be broken up by alkali bentonite because of its strong affinity for water. The authors have shov:n previously that air-dried alkali bentonites 'viii remove vmter from light
petroleum fractions, and also that the addition of the correct amount
of alkali bentonite should tend to neutralize the effect of the emulsifiers already present in crude oils and thus break up the emulsion.
The removal of the colloidal mat ter of crude oils by treatment with
acid-treated bentonites or fuller's earth should also tend toward the
same result.
IN MANUFACTURE OF DYXAMITE
..:Uthough bentonite absorbs twice as much nitroglycerin as diatomaceolli- earth. its use in t1Je preparation of Jynamit -will probably
not be popular because of the po~~ibiliry of gritty particles that
mighr ca!l..~ .U~ in handling the exp! sin~.
The
... of ga._.;;e~ ~-a' nN been

lr.; nil~ for the abrorp-
48
BENTONITE
tion of dyes, fertilizers, pigments, and the impurities in oils and fats
has been discussed elsewhere. Rohland 99 recommended the applica
tion of colloidal clays to the purification, deodorization, and decolorization of waste liquors from leather factories, dye factories, and
paper factories through the adsorption and coagulation of the impurities. Alkali bentonites would adsorb and tend to coagulate
particles that were positively charged in aqueous solutions.
BENTONITE AS CHEMICAL REAGENT
Although most of the uses of bentonite depend largely on its

physical characteristics, there are at least two in which its baseexchange properties are important. Base exchange is due eith er to
adsorption or chemical reaction as explained previously, but the
latter conception will be used in our classification.
W .ATER SOFTENER
The so-called zeolite water softeners, used extensively in this country, are made by a special treatment of bentonites (usually characterized by the mineral leverrierite), zeolites, or other mineral substances or are produced synthetically. In treating bentonite for this
purpose it is converted to dry granules, heated at a definite temperature such that the sliming properties are destroyed without complete
dehydration (since the latter result would destroy the base exchange
property), then treated with a solution of a sodium salt, and fina1ly
with a water wash. In softening water, the hardness of which is due
to the presence of calcium and magnesium salts, the sodium of the
prepared bentonite is exchanged for the calcium and magnesium,
which are thus removed from the solution. The equipment for
softening water by this method usually consists of a percolator containing the base-exchange material and a tank of strong brine solution. The water to be treated is passed through the percolator at a
rate determined by the hardness of the water and the size of the
percolator, the latter factor depending on the quantity of water to be
treated before the softener needs attention. When the percolator is
no longer efficient it is filled with brine solution to r egenerate the
softening agent through an exchange of its calcium and magnesium
by sodium. The solution containing salts of calcium and magnesium
is run to waste and t he percolator is again ready to function as a
water softener. This method of softening water, which is largely
used by laundries, offers many advantages over the usual chemical
treatments but may not be profitable if there is too much carbonic
acid or if the water contains finely dispersed material which stops
Rohland, P., "The colloidal clay process for trade waste purification" : CheW". Abs.,
vo!. 7, 1913, p. 4028.
49
the reaction and spoils the softening reagent. A softening reagent

contaminated in this way may sometimes be improved. Lime or iron
oxide may be removed by dilute hydrochloric acid and oil by burning. Water softeners made from natural products such as bentonite
are generally superior to artificial preparations, as the artificial preparations are more readily attacked by carbonic and hydrochloric acids
and are apt to lose their base-exchange properties on heating. However, recent synthetic preparations are said to be more rapid in their
action and to have a greater capacity than those made from natural
substances. 1
It has been reported that bentonite from South Dakota has been
used for the production of two of our best known zeolite water
softeners,2 so that bentonite from other deposits would seem to offer
possibilities for this use.
AS AN AID TO SOIL FERTILITY
The presence of colloidal matter and material capable of base

exchange has an important effect on the fertility of soil. The retention of the salts contained in the soil moisture necessary for p lant
growth and the retention of t he soil moisture itself depend on baseexchange properties and on absorption or adsorption by the colloidal
matter in the soil. Besides preventing the washing out of nutritive
substances, the colloidal matter forms fields of various concentrations
of these salts so that the assimilating root hairs may select the part
of the solution in which the concentration they require are best satisfied. Wiley and Gordon 4 showed conclusively t hat salts retained
by colloids are available for plants. They found that phosphoric
acid that was not removed by simple washing was taken up by
plants. Excess colloidal matter, however , is detrimental to plant
growth, and considerable matter capable of base exchange may, in the
presence of excess salts, cause some difficulty in the removal of the salts
nnless this base-exchange property is recognized and considered in the
Jreatment of the soil. Soils deficient in colloidal matter might be improved by the addition of bentonite, but its addition to other soils
would probably be detrimental. Bentonite might also be used as an
absorbent fo t liquid fertilizers or might replace the inert fillers
usually added to commercial mixed fertilizers and thus form a
t Behrman, A. S., "Recent developments in zeolite softening" : I nd. and Eng. Chem.,
vol. 19, 1927, p. 445.
Spence, II. S., Bentonite : Canada Dept. Mines, Rept. 626, 1924, 35 pp,
For more detailed accounts of the action of colloids and base exchange in soils see
Gedroiz, K. K., " Colloidal chemistry as related to soil science," translated by Waksroan,
S. A., mimeographed by the U. S. Dept. of Agriculture in 1923, 38 pp. ; Frankforter, C. J.,
and Jensen, F. W., " Chemical exchange reactions of a zeolite": Jour. Ind. and Eng.
Chem .. vol. 16, 1924, p. 621 ; and textbooks on soil science.
Wiley, R. C., and Gordon, N. E., "Availabll!ty of adsorbed phosphorus": Soil Science,
l'OL 15, 1923, p. 371.
50
BENTONITE
,superior article for the improvement of soils deficient in colloidal

matter by preventing the rapid leaching out of the soluble salts of
the fertilizer.
IK TREATMENT OF :M:OLASSES
The work of Bachler 5 gives another interesting possibility for

the utilization of the base-exchange properties of bentonite. He
found that if molasses was treated with a calcium zeolite before the
Steffens process, potassium was removed from the solution and sugar
liberated so t hat a higher recovery of the sugar resulted. A water
softener prepared from bentonite, in which the sodium had been replaced by calcium through its use or its treatment with a solution
of a calci urn salt, would seem well fitted for this and worthy of a
practical test.
BENrONITE AS A MEDICAMENT AND COSMETIC
Alkali bentonites when mixed with various liquids produce plastic

homogeneous bodies that have some cleansing and healing power.
This action seems explainable chiefly in the colloidal properties,
which act a,s a detergent and absorb moisture, salts, and poisonous
substances from the surface of the body. The beneficial action is
assisted by contact o the moist poultice with the skin, which opens
the pores, thus permitting a most thorough cleansing.
Knowledge of tllis action has led to the exploitation of bentonite
as a "cure-all." Bentonite has been put up in 4-ounce packages at
Seattle, Wash., and sold for $1 per package, as an internal and
external medicine for various diseases.
AS AN AKTIPHLOGISTIC
One of the earliest recorded uses of alkali bentonite was as a

medical dressing. Moistened with water under the name "white
rock," bentonite formed a dressing used in stuffing horses' hoofs to
relieve soreness and inflammation. :vfoistened with water or glycerin,
it has also been used, apparently with some success, for rheumati.c
and pulmonary affections, disorders of the scrofulous and eczematous
type, abscesses, and the cleansing and healing of sores and wounds.
IN DRUGS
Alkali bentonite has been used as a base for salves and ointments
and as a diluent for powerful drugs. It could also be used to advantage as a dusting powder in grinding adhesive substances and in
the preparation of various emulsions and suspensions.
Bachler, F. R., " Subjection of molasses treated with zeolites to the
lnd. and Eng. Cbem., vol. 18, 1926, p. 189.
Steffen~
proce.ss " :
PRESENT A.i."'<D PROPOSED USES FOR BENTONITE
51
IN COSMETICS
Most facial beauty clays consist of alkali bentonites made to a

paste with glycerin. Their use is preceded by the application of
hot towels to open the;pores. The pasty clay is spread on to form
a thick coating and left on for several minutes before being washed
~ off. The more probable claims for these preparations are the elimination of blackheads, pimples, and excess oil and the removal of
wrinkles and enlarged pores. Bentonite doubtless gives such preparations some of the properties claimed for them, due to its absorbent
and cleansing powers.
Massage creams are rubbed into the skin before and wiped off after
massaging. They are said to remove dirt qui.c kly and to invigorate
the skin. Alkali bentonite, whe~ used in such preparations, should
take an a.ctive and effective part in the production of the desired
results.
BentoniteJDight also be used as a dusting powder to absorb perspiration and associated body excretions with their attendant odors
and as a base for depilatories, lip stick, and rouge.

Bentonite C. W. Davis and H. C. Vacher

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Teclmical Paper 438

ITS PROPERTIES, MINING, PREPARATION,

C. W. DAVIS and H. C. VACHER

Thjs report represents work done under a cooperative agreement between

Mexico __________ --_____________________________________

D~cusmon_ __ _____ ___ __ ___ ____ _ ___ __ _ ______ __ ______ __ __ _ _

Conclusions___ __ __ __ ___ __ _____ ___ __ _____ _______ ____ ___ ___

Present and proposed uses for bentonite-Continued.

In drugs____________ __ ___ ____ ______ _________________ _____

In cosmetics___ - -----_____ ______ _____ _________ _________ ___

Scheme for classifying bentonites__ ______ ____ ________ __ ___ ______

BENTONITE: ITS PROPERTIES, MINING, PREPARATION, AND

At the time considerable interest in bentonite was aroused, but it

The authors acknowledge the kindness of Master Minerals Co.,

m " pockets " or irregular

Bentonite outcrops are unique and striking. As little vegetation

The bentonite of Wyoming is usually considered a standard ty"Qe

The largest known California bentonite deposits occur in the arid

DEPOSITS-MINING AND PRODUCTION

its analysis corresponds to that of montmoril!o~ Although ap-~~

See footnote 13, p. 4.

Other deposits of bentonite have been reported in Imperial, Fresno,

A material closely resembling Wyoming bentonite occurs at Belle

DEPOSITS___:_MINING AND PRODUCTION

A deposit resembling typical Wyoming bentonite has been found

There are deposits of bentonitic material 3 to 5 feet thick about

Material closely resembling Wyoming bentonite is found in Cassia

An enormous bed of clay classified as bentonite covers an area

Deposits of bentonite have been reported from Colorado County,

Washington, Oregon, Kansas, Oklahoma, Louisiana, Minnesota,

Bentonite occurrences have been reported at a large number of

After the study of a number of samples of bentonite from widely

Nearly all deposits of be-n tonite contain gritty or sandy inclusions,

INVESTIGATION OF PROPERTIES OF BENTONITE

choiclal fracture, but some varieties have a platy, shalelike f racture

Montmorillonite is designated as (Mg,Ca)O. Al 2 0 3 .5Si02 .nH2 0),

~~~o:::::::::::::::: 1: ~ --i~56 :::::: 4: lll::::::l:::::: :::::: :::::: :~ R 1'i ~: & __:_~

Bentonite, near Fallon, Nev. H. C. Vacher, analyst.

INVESTIGATION OF PROPERTIES OF BENTONITE

Different bentonites were studied to obtain a better understanding

In Bureau of Mines experiments a large number of samples of

To determine the action of water, small lumps of each type of

A study of the swelling of bentonite and its control 32 follows. In

which may be either very viscous or practically solid. as will be

INVESTIGATION OF PROPERTIES OF BENTONITE

occupied by bentonites and clays

- - - - - - - - - - 1- - - - - - --------------Dry volume. .. ----------- -- ----- -----

Volume in water---------- -- -- ------ Volume in !'laO! solution:

14.8 - ------- -------8. 5 -------- -------5. 7 ----- --- -------4. I

-------- --------------- --------------- --- ----------- - ---------- ----- --------

' The results are probably accurate to withil1 0.5 c. c.

These tests and others show that the addition of quantities up to

Two factors, temperature and hydrogen-ion concentration, which

ot t em peraJt!re ancl nydrogenrion concentration on tlbe sweavn.g

Volume of 2.5 grams at different temperatures,

- - - - - - - - - - - - - - -1--- - - - - - - - - - - - H CL. - -- - __ --- . __ .. __ . . ---- ------ - c -- - - -- ----

Do_ .... -- ---- - ____ . ..... .. .. ------.- -----. ___ ___

INVESTIGATION OF PROPERTillS OF BENTONITE

Increase in temperature apparently promotes swelling, but the

occupied by a typical b entonite

MgOJo_ ___ ___ ______

' A normnl solution contains 1 gram-equivalent of the solute in I liter of solution.

Many substances swell when placed in a suitable liquid. A large

INVESTIGATION OF PROPERTIES OF BENTONITE

Mexico --___________________________

D~cusmon_ _ _ _ ____ _ _ _ __ _ _

Conclusions_ _ ___ _ _ ___ _ ___

In drugs__________ _ _________ _

In cosmetics_ - -----_ __ _ _ _ _

Scheme for classifying bentonites __ _ ____

- - - - - - - - - - - - - - -1--- - - - - - - - - - - - H CL. - -- - --- . .. __ . . ---- ------ - c -- - - -- ----

Do_ .... -- ---- - __ . ..... .. .. ------.- -----. _ ___

MgOJo_ _ _ ______