Bentonite: Industrial Minerals Laboratory Manual

British Geological Survey
TECHNICAL REPORT WG/93/20

Mineralogy and Petrology Series
Industrial Minerals Laboratory Manual
BENTONITE
S D J Inglethorpe, D J Morgan,
D E Highley andA J Bloodworth
T T
T T
Mineralogy and Petrology Group

Keyworth
Nottingham
United Kingdom NG12 5GG

TECHNICAL REPORT WG/93/20
Mineralogy and Petrology Series
Industrial Mberals Laboratory Manual
BENTONITE
S D J Inglethorpe, D J Morgan, D E Highley andA J Bloodworth
A Report prepared for the Overseas Development Administration under the
ODABGS Technology Development and Research Programme, Project
91/1
ODA Classzjkation:
Subsector: Geoscience
Theme: G 1 - Promote environmentally sensitive
development of non-renewable resources
Project title: Minerals for Development
Reference number:E541
Bibliographic reference:
Inglethorpe, S D J, Morgan, D J, Highley, D E & Bloodworth, A J
Industrial MineralsLaboratory Manual:
Bentonite
BGS Technical Report WG/93/20
Subject index:
Industrial minerals, bentonite,laboratory techniques
Cover illustration:
Schematic representationof the
crystal structure of smectite group minerals
0 NERC 1993
Keyworth, Nottingham, British Geological Survey, 1993
CONTENTS
Page
1. INTRODUCTION
2. GEOLOGICAL OCCURRENCE
3. MINING AND PROCESSING
4. INDUSTRIAL APPLICATIONS
13
5. LABORATORY ASSESSMENT OF BENTONITE
25
6. USE-SPECIFIC TESTS
48
REFERENCES
61
APPENDICES:
1. Release of extractable cationsfrom bentonite by
ammonium acetate leach
65
2. Cation-exchange capacity(BaClrngS04 method)
68
3. Methylene blue cation-exchange capacity
72
4.2-ethoxyethanol surface area method
78
5. Bentonite swelling test
82
6. Bentonite liquid limits
84
7. Plastic limit and plasticity index
90
8. Drilling fluid properties
92
9. Mechanism of acid activation and assessment

of bleaching
performance of bentonite for use in edible oil clarification
98
10. Water absorbency of pet litters
115
Preface
Industrial mineral raw materials are essential
for economic development.
Infrastructureimprovementandgrowthofthemanufacturingsector
requires a reliable supply of good quality construction minerals and a
wide range of other industrial mineral raw materials.
Althoughmanylessdevelopedcountrieshavesignificantpotential
industrial mineral resources, some continue to import these materials
supply their industries. Indigenous resources may not be exploited (or
areexploitedineffectively)becausetheydonotmeetindustrial
specifications, and facilities and expertise to carry out the necessary
evaluation and testwork are unavailable. Unlike metallic and energy
minerals,thesuitabilityofindustrialmineralsgenerallydependson
physical behaviour, as well as on chemical and mineralogical properties.
Laboratory evaluation often involves determination of a wide range of
inter-related properties and must be carried out with knowledge of the
requirementsofconsumingindustries.Evaluationmayalsoinclude
investigation of likely processing required to enable the commodity to
meet industry specifications.
Overthelast
10 years,fundingfromtheOverseasDevelopment
Administration has enabled the British Geological Survey
to provide
assistance to less developed countries
in the evaluation of their industrial
mineral resources. This seriesof laboratory manuals sets out experience
gainedduringthisperiod.Themanuals
are intended to be practical
bench-top guides for use by organisations such as Geological Surveys
and Mines Departments and
are not exhaustivein their coverageof every
test and specification. The following manuals have been published to
date:
Limestone
Flake Graphite
Diatomite
Kaolin
Bentonite
Construction Materials
A complementary series of Exploration Guides isalso being produced.
Theseareintended
to pr6videideasandadviceforgeoscientists
involved in the identification and field evaluation of industrial minerals
in the developing world. The following guide has been published to
date:
Biogenic Sedimentary Rocks

A J Bloodworth
Series Editor
D J Morgan
Project Manager
Industrial Minerals Laboratory Manual
Bentonite
1. INTRODUCTION
Bentonites, which consist essentially

of clay mineralsof the smectite
A particular featureof this
group, have a wide range of industrial uses.
group of mineralsis the substitutionof Si4+and Al3+ in the crystal
structure by lower valency cations. This leaves unsatisfied negative
charges which are balanced
by loosely-held exchangeable cations such
as Na+, Ca2+, Mg2+ and
H+located mainly on the interlayer crystal
surfaces. The structure, chemical composition, exchangeable ion type
and small crystal size
of smectite are responsible for several unique
properties, including a large chemically active surface area, a high cationexchange capacity, interlayer surfaces having unusual hydration
characteristics, and sometimes the ability to modify strongly the flow
behaviour of liquids (Odom, 1984). The crystal structure and chemistry
of smectites are summarized
in Table 1 and Figure1.
Depending on the dominant exchangeable cations present the clay may
be referred to as either calcium bentonite or sodium bentonite, the
two varieties exhibiting markedly different properties and thus uses.
The terms nonswelling bentonite and swelling bentonite are
synonymous with calcium bentonite and sodium bentonite respectively.
When mixed with water, swelling bentonites exhibit a greater degree
of
dispersion and better plastic and rheological properties than nonswelling
bentonites. Natural sodium bentonites, such as thosein Wyoming,
USA (Wyoming or Western bentonite), are comparatively rare
although the cation-exchange properties
of smectite enablethe more
widespread calcium form to
be easily converted to high-swelling
sodium
bentonite by a simple sodium-exchange process.In some countries,
notably Britain, calcium bentonite
is referred to asfullers earth,
although elsewhere,and particularly in the USA, this termis applied to
any clay that has the capacity
to decolourise oil and may consist
of
smectite orattapulgite. The latter is mineralogically distinct but has
similar propertiesof adsorption to calcium bentonite and can substitute
in certain applications. Sepiolite (the magnesium analogueof
attapulgite) is also used asan alternative to calcium bentonite,
particularly in Europe (Singer& Galan, 1984).
Mineralogy and PetrologyGroup, British Geological Survey 0 NERC 1993
Bentonite
The physical and chemical properties of bentonites typically vary both

within and between deposits due to differences in the degree of chemical
substitution within the smectite structure and the nature of the
exchangeable cations present, and also due to the type and amount of
impurities present. No bentonite is universally acceptable for every
application. In this context a distinction can be made between the
grade
and quality of bentonites. The grade is defined as the smectite content
of the bentonite, whilst its quality is related to the inherent physicochemical properties of the clay, either its
in natural or modified form,
and isa measure of likely industrial performance. However, there
is no
recognised minimum grade or smectite content below which
a clay is no
longer considered to bea bentonite. Commercial bentonites rarely
contain less than60% smectite and usually more than
70%, associated
minerals typically being quartz, cristobalite, feldspars, zeolites, calcite,
volcanic glass, and other clay minerals such as kaolinite. Amounts and
type of associated minerals are related to the origin of the bentonite.
The aim of this manualis to show how data gathered during initial
mineralogical and chemical examination of
a bentonite may be usedto
indicate the suitability of the clay for different applications. Following
on from this, some physico-chemical tests are described which can be
used to screen large numbers of exploration samples for bentonite grade
and quality. These physico-chemical tests are all relatively simple and
can be carried out in
a reasonably well-equipped mineralogical or
chemical laboratory. Finally, some use-specific test procedures are
described which could be carried out
in the same setting.
This manual is one
of a series produced as part of the BGS/ODA R&D
Project Minerals for Development.
Mineralogy and PetrologyGroup, British GeologicalSurvey 0 NERC 1993
Bentonite
Table 1.
Crystalstructureandchemistry
of smectite-groupclays.
STRUCTURE
*
Classedas 2:l Layerphyllosilicates

Composed of alternatmg octahedral and tetrahedral sheets
Ratio of tetrahedral :octahedral sheetsis 2 : 1
CATION COORDINATION
X positions - exchangeablecations
Y positions - structural octahedral cations
2 positions - structural tetrahedral cations
*
*
Structuralcations - fixed
Exchangeable cations (surface cations) available for chemical exchange
CHEMICAL COMPOSITION
General formula of smecfitegroup:
Chemical composition of thesmectite

Chargei
Pyrophyllite
Dioctahedral smectites:
Montmorillonite
Beidellite
Nontronite
Si8
Talc
Trioctahedral smectites:
Saponite
Hectorite
Si8
group
Exchange
Octahedral
Y
(ca. Na, Mg)

(ca, Na, Mg)
(capNa, Mg)
0.2-0.6
0.2-0.6
0.2-0.6
Mg6
Negative charge per formula unit layer [Ole (OH)2]

Trioctahedral all 3 octahedral sites (perunit cell) occupied by divalent cations
Dioaahedral 2 of 3 octahedral sites (per unit cell) occupied by trivalent cations
Isomorphous substitution of of lower valency cations for Si4+ and Al3+ results ina
negative crystal charge which is balanced by exchangeable cations
Mineralogy and Petrology Group, British Geological Survey 0 NERC 1993
Bentonite
n
2
c
.
P
6
tif
0,
n
X-SIT
Z-SITE
INTERLAYER
Figure 1.
Crystalstructure
TETRAHEDRAL
Y-SITE
OCTAHEDW
and chemistry of smectite-groupclayminerals.
Mineralogy and Petrology Group, British Geological Survey0 NERC 1993
Bentonite
2. GEOLOGICAL OCCURRENCE
Smectite is the essential and active component of bentonites on which
their economic importance is based. The majority of commercial
bentonite deposits contain Ca2+ and Mg2+ asmain
the exchangeable
cations. However, smectite clay minerals become unstable
with
increasing age, depthof burial, and diagenesis, and alter to mixed-layer,
illite-smectite clays, sometimes referred to as
K- or meta-bentonites,
in which their valuable properties have been largely destroyed.
Consequently, pure smectite clay minerals are essentially absent
in rocks
of pre-Mesozoic age (Moorlock& Highley, 1991). Whilst Jurassic
bentonites areknown, most economic deposits are Cretaceous or
younger in age and this factis an important exploration criterion.
Most bentonites have formed

by alteration of igneous material. Such
deposits areof two markedly different types:(i) those resultingfi-om
sub-aqueous alteration of fine-grained volcanic
ash and (ii)those
resulting from in situ hydrothermal alteration of acid volcanic rocks
(Grim & Guven, 1978).
2.1 Sedimentary bentonites
These bentonites are formed

by the alteration of volcanic ash deposited
in the sedimentary environment.This material may have been
subsequently reworked and concentrated
by sedimentary processes.
This type of deposit may be found associatedwith a wide range of
lithologies, mainly of shallow, marine origin, although occurrences
in
non-marine environments have been reported. Most bentonites this
in
category have formed from ash of mainly rhyolitic to trachytic
composition. Beds vary in thickness froma few millimetresup to 10 m
and whilst they are often lenticular, in some cases markedly
so, some
deposits may extendover hundredsof square kilometres,a feature
consistent with their formation from airborne volcanic ash. Typically
bentonites exhibit sharp contacts
with the underlying sediments but their
upper surfaces may be both erosive, and therefore sharp, or gradational
into the overlying sediment. The most important deposits of this
type,
accounting for a major proportion of world production of bentonite, are
those in the westernUSA High-swelling or sodium bentonites occur
in
the Northern BlackHills district straddling the Montana-WyomingMineralogy and PetrologyGroup, British Geological Survey 0 NERC 1993
Bentonite
South Dakota borders and in the Hardin district of south-central

Montana and north-central Wyoming. Numerous bentonite beds
ranging from a few millimetres
up to several metres in thickness occur
in Cretaceous strata over a stratigraphical interval
of over 1000 m.
However, only seven beds are sufficiently thick and extensive
to be of
commercial interest. The best knownis the Clay Spur Bentonite within
the Mowry Shale. The bed, whichis between 1-1.5 m thick,is the
source of most of the sodium bentonite
with very high colloidal
properties for which the areais famous (Harben& Bates, 1990).
Commercially exploited bentonites generally contain less than
30% nonclay mineralsbut exhibit varying properties, which influences their
ultimate use. The source of the volcanic ash
is considered to be the
volcanic centres of the Rocky Mountains and
the beds thus thin towards
the east. Since the exchangeable cations present
in bentonites are easily
replaceable, Na+ is readily replaced by Ca2+ and Mg2+ under leaching
conditions. Locally this has happened
in Wyoming, where groundwater
leaching of the overlying overburden has provided the source of Ca2+
and Mg2+. Only rarely are Ca2+ and Mg2+ replaced by Na+ (Odom,
1984).
As sedimentary bentonites are not usually associated with volcanic

rocks, the ultimate source of the volcanic ash may be several hundred
kilometres away and no longer exposed. This
is the casein Britain
where Cretaceous bentonites occur as a number of isolated deposits
of
varying size (Figure2) but where thereis no evidence of
contemporaneous volcanic activity onshore.A volcanic sourcein the
North Sea is most likely. However, primary ash falls from volcanic
centres some hundreds
of kilometres distantare unlikely to be more than
a few centimetres thick. The processes which lead
thetoformation of
this type of commercial bentonite deposits are complex. Moorlock
&
Highley (199 1) recognised five genetic stages
in their formation:
e
e
e
0
Eruption of ashanditsairbornetransport.
Watersortingandconcentration of volcanic ash in shallowmarine environments to give thick accumulations.
Conversionofthevolcanicashtosmectite.
Protection of the bentonitebedsfromsubsequenterosion.
Nosubsequentthermalalteration of thesmectite to other clay
mineral phases.
Mineralogy and Petrology Group, British Geological Survey

0 NERC 1993
Bentonite
2.2 Hydrothermal bentonites
Some bentonite deposits have formed the

by in situ hydrothermal
alteration of volcanic rocks, normally of acidic composition. Such
by fault andjoint
deposits maybe irregular in shape and controlled
systems andthey may also be highly variable in quality due to partial
alteration of the parent rock. Often they may be associated with recent
volcanism, which shouldalso be regarded asan important exploration
criterion. Many of the important bentonite deposits
in the Mediterranean
region are related to the recent volcanism and associated hydrothermal
activity produced by the subduction of the African plate under the
Eurasian plate. The important deposits on the island of Milos, Greece,
are of this type and have formed
in the recent geological past (since
Pliocene times)by the alteration of acid volcanic rocks and associated
tuffs in a marine environment. The degree of alteration is variable with
the main impurities being quartz, feldspar, unaltered volcanic glass and
kaolinite.
2.3 Field characteristics
Bentonites rangein colour from black through to white but most

frequently are bluish-green when fresh, weathering to a yellowishbrown colour at or near outcrop duethetooxidation of ferrousiron.
Material from near outcrop often exhibits enhanced swelling properties.
Despite their often characteristic appearance
at outcrop, where they tend
to exhibit a 'frothy'or 'popcorn' texture due to successive wetting and
drying, deposits may be easily overlooked during field mapping,
In
particularly in tropical areas where this feature may be obscured.
addition, because bentonite deposits sometimes exhibit a highly
no surface expression withno outcrops.
lenticular form, some may have
Detection then can prove extremely difficult.
Bentonite
AGE
BIOZONE
WSUSSEX / SURREY
HANTS
LC-
fuller's earth
.-.-
unconformity
Limestone
EAST BEDFORDKENT
SHIRE
WEST
KENT
F l Sandy clay
d
Cloy
[ml
No sediment present
Figure 2. Geologicalsectionshowingoccurrences
in southeastEngland
LowerCretaceoussediments
of fuller'searth(Ca-bentonite)in
(from Moorlock & Highley, 1991).
Bentonite
3. MINING AND PROCESSING

3.1 Mining
Bentonite is almost always extractedin open pit workings, usually

by
opencast methods in which the overburden
is dumped into the worked
out sections of thepit and rapidly restored. This method can be applied
to stratified deposits which are either flat-lying
or dip at an angle less
than the safe angle of repose of waste rock.
The relative proportion of
overburden to mineral (the overburden ratio). Overburden ratios may be
as high as20: 1 for high quality bentonites andin Britain up to 45 m of
sand overburden is removed at one operation to extract
2-3 m of
bentonite. In stripping overburden, care must be taken to prevent
contamination and in some operations the top of the bentonite bed may
be separately recoveredfor lower quality uses. Variationsin the
properties of bentonite within the same bed, as well as different beds,
means that selective mining
is often necessary to match different
qualities with specific applications. Underground mining
is rarely used
but was practised in Britain until
1979 to recover Jurassic bentonite
from beneath a thick
cover of limestone.
3.2 Processing
Bentonite is rarely usedin the raw form but undergoes processing

essentially to modifyits properties for specific industrial applications
rather than to increaseits smectite content. The major product groups
are listed below.
e
e
e
0
Ca-bentonite(finepowdersandgranules)
Na-bentonite
and
Na-exchanged
bentonite
Acid-activated
clays
Specialityclays(whitebentoniteandorganoclays)
A simplified flow diagram for the processing of Ca-bentonite

is given in
Figure 3. Initial processing consists of drying and grinding, the dried
clay being either screened and marketed in the granular
fonn or milled to
a fine powder, size grading being carriedby
outair-classification. Fines
powders may be pelletized and crushed to produce
a higher yield of
granules. Granules may be lightly calcined
to make them water-stable.
10
Bentonite
I Raw Ca-bentonite I
Grinding to fine powder
IGranulesI
/I
/1
Calcination
to
produce
\ pi-zzGGl
Sodium carbkate addition
Figure 3. Typicalprocessingroutes
for Ca-bentonite.
i\
I
11
Bentonite
It is common practice, particularly

in Europe, to attempt to convert
Ca-bentonite to the Na-variety, and therefore extend greatly the number
of potential outlets for the clay.The ion exchangeis usually effected by
mixing sodium carbonate (soda ash) with the crude, moist clay using
various mechanical methods. After the soda ash
is added, the clay is
generally stockpiledfor several days or weeksto allow maximum
exchange to occur. In Europe, clays are often extruded as part of the
sodium-exchange process. In addition to increasing the intimacy of
mixing, extrusion shears the clay aggregates and particles making more
A number of mechanical
interlamellar surfaces accessible for exchange.
processes used to help sodium exchange
in bentonites have been
described by Alther (1982). This process is sometimes referred to as
activation, but should not be confused with acid-activation.
The production of valued-added acid-activated clays involves more
complex processing but the starting raw material
is calcium bentonite, as
sodium bentonites do not respond to the same extent to acid treatment.
The clayis weighed into mixing vesselswith water and mineral acid
(either sulphuric or hydrochloric acid). The clay-acid slurry
is pumped
to agitated reaction vessels which can be heated to near boiling by steam
or other means until the desired degree of activation or leaching has been
achieved. The clayis then washed and dewatered to yield
a filter cake
which is subsequently dried, ground and sized. A.wide range
of grades
are produced for different applications. Product quality and
perfomance can be modified by control of the following parameters:
e
e
e
e
acid-clay
ratio
degreewashing
of
degreedrying
of
particle
size
is considered in more detail

The mechanismof activation is complex and
in Section 6.4. Other proerty modifications of smectite, usually
involving acid pretreatment and often followed by precipitation
of AlOH
pillars in the interlayer space,canied
is
out to prepare catalysts for
small- or large-scale organic syntheses (Adams, 1987).
Although most bentonites are produced bydry processing methods,
modest quantities of high-value white bentonite,in both the calcium
and sodium form, are wet-refined using centrifuges to remove coarser
impurities such as quartz, cristobalite and feldspar, and to improve their
Mineralogy and Petrology Group,British Geological Survey 0 NERC 1993
12
Bentonite
rheological properties. These speciality and highly-priced bentonites are

used in water-based paints, cosmetics, a range of pharmaceutical
products, detergents and certain ceramics, but only clays with
an initial
high brightness are suitable for these applications.
Through the exchangeof inorganic cations, usually sodium, with
positively charged long-chain ammonium compounds, a range
of
organophilic (and thus hydrophobic) clays can be produced which are
known generically asorganoclays. They are effective gellantsin a
wide rangeof organic fluids, suchas paint, grease, ink and oil-based
drilling muds (Jones,1983). They are based on natural and sodiumexchanged bentonites, as well
as hectorites (a lithium-bearing smectite)
which provide greater gel strength.

0 NERC 1993
13
Bentonite
4. INDUSTRIAL APPLICATIONS
Bentonites have a wide range

of industrial applications. Based on
production data for the
USA, by far the largest producer, the major uses
of bentonite have always been considered toinbebonding foundry
sands, drilling fluids, and iron ore pelletising (Vista,
1990). These uses
accounted for75% of total US production (3.5 Mt) in 1988, although
total usageis at much lower levels
than in the late 1970s and early1980s
due to a downturnin oil drilling activity, as well
as in the steel and
foundry industries. Demand for bentonite varies significantly from
country to country. In western Europe, the largest marketfor bentonite
is currently pet litter. Itis also used as a clarifying agent for oils and
fats, in agriculture (asa carrier for pesticides and fertilizers and as a
coating for seeds), in civil engineering,
in papexmaking, andin paints,
pharmaceuticals and cosmetics. Descriptions
of these and many other
applications have been given byRoss (1963, Grim & Guven (1978)
and Odom (1984).
Relationships between the physico-chemical properties of bentonite and
commercial applicationsare summarised in Table 2. Major application
areas of the main bentonite product groups are summarised in Figure
4.
14
Bentonite
Table 2. Commercialapplicationsofbentonite
(after
Highley,
1972).
Sorptive properties(may be increasedby acid treatment)

In glyceride
A:bleaching
of suspension
and
Refining
B: In dry state (or paste)
Sur$ace area (may beincreased by acid-activation)
Rheological properties
A: Viscosity and suspending powers
B: Thixotropy
in relationtophysico-chemicalproperties
oils
Clarification and purification
of sugar solutions,
syrups and wines
Water purification, sewage and effluent treatment
Pharmaceutical and therapeutic preparations
Absorbent (pet and animallitter oil spillage on
factory floors)
Catalytic action, carrier for catalysts
Carrier for insecticides and fungicides
Mineral filler and extender
Drilling fluids
Paints (oil and water-based)
Fertilizer sprays
Bitumen emulsions
Formulation of ceramicglazes
Wall support for boreholes
Civil engineering (diaphragm wall construction)
Non-drip paints
Impermeability, coating properties
Civil engineering (grouting, impermeable

membrane)
Drilling in permeable strata
Bonding properties
Bonding foundry moulding sands

Pelletising iron ore concentrates
Pelletising animal feedstuffs
Plasticity
Formulation of mortars, putties, adhesives, some

ceramic bodies
Bentonite
Activated
Alkalino
active
Naturally
with acid
b l u clh
aicntg
lvatd
omrthl
Foodstuffs
industry
Forest and
water conservation
Crude bentonite
mctivatod
(N@-oxchongodbentonitel
Organically activated
(orgonophilic bentonite)
Refining, decdorising, purifying and stablising of vegetaMe

and
animal oils and fats
Powder fire-extinguishing agenlslbindmg agents for oil on water
Refining, decolorising andpurifying of mineral oils, fats. waxes,

mraffin/cstalysts for oil cracking
I
I
Beverages and
suaar industry
Fining of w
n
i e, must
and
juiceslbser stabibtion/purifying of saccharine

juice
syrup
and
Pigment and colour d e w l m r for carbon- copying

of impurities in white water system
Paper industry
Regeneration or organic
for fluids
drv cleanina
Pharmaceutical
industry
paper/adsorptbn
Pobhm mtd dressings/additives for w a s h i i and cleaning agents
and for moo nroduetion
Starting m a t e r U for heding earths and medicaments/bases

for creams and cosmetics
Ore production
Binding agents for ore pelletising
Building industry
Supporting suspensionsfor cut-off diaphragm wall constructions and

shield tunndling/subsoil s e s l i (eg dumps)/anti-friction agents for
pipejacking and shaft sinking/additive for soil concrete, concrete and
mortar
Ceramics industry
Plesticidng of ceramic compoundslimprovement of

strength/fluxing agents
Horticulture, agriculture.
animal husbandry
Drilling
Tar exploitation
Paint and varnish industry
ISoil improvement/compostinglar,imal.leedpeIkt&ing/~~d-ma&~e I-treatment/cat litter
1I
industry
Catabts/cetalvst carriers. insecticides and fungicideslfillers, dehydrating agentslwater and

waste-water purification/adsorbennfor radioactive materials
industry
Cleaning and
detergents
Grease thickening
Borehole scavenging
for saltwater
1-
coatinos
II
I
I
Thixotropic suspensions for borehole scavenging
Emukifiition and thixotroping of ter-&ter e&ioGpter

asphalt
.
and
Thickening, thixotroping, stabilising and anti-setting agents for

paints, varnishes. coating materials. sealing cements, waxes,
adhesives
Foundries
Figure 4. Major applicationareas
of bentonite (from Sud Chemietechnicalliterature).
Mineralogy and Petrology Group, British Geological

Survey 0 NERC 1993
16
Bentonite
4.1 Foundry moulding sands
One of the largest applications

for bentonite worldwideis the bonding of
silica sand for the production of greensand moulds
in foundries. Both
calcium and sodium bentonite are used
in the foundry industry and
typically between5-10% bentonite is mixedwith sand and water to
prepare a plastic and cohesive material that can be compressed around
a
pattern to produce a mould. The bentonite must give the sand sufficient
strength to maintain the shape of the pattern before, during and after
pouring of the molten metal. After casting the moulding sand
is recycled
with small additions ofnew silica sand and bentonite to replace losses
and restore the bond. Properties of bentonite/sand mixtures that are
dry
crucial for foundry usage are green compressive strength,
compressive strength, shatter index, and compactibility; properties such
as wet tensile strength, hot compressive strength, flowability and
durability may also be quoted in specifications. The nature of these
specialised testsis discussed in Section 6.2.
4.1.1 Behaviour sf different types of bentonite in foundry sand
mixes
Sodium bentonite, both natural and sodium-exchanged, and calcium

bentonite are usedby the foundry industry, but they exhibit quite
different properties. Natural sodium bentonites have a medium green
strength anda high dry strength which increases their resistance to
molten metal. They also have good high-temperature durability which
means that bonding propertiesare not destroyed by moderate heating.
When molten metalis poured into a mould a proportion
of the bentonite
is heated above its dehydroxylation temperature with the ofloss
structural water. This loss is associated with a loss
in bonding power
(green anddry compressive strength) and new clay additions are
required to restore the strengthof the moulding sand. Most bentonites
lose structural water in the range 50O0-75O0C anda as
general rule the
higher the temperature of
OH loss the greater the durability
of the clay.
An assessment of the durability of bentonites can be obtained from
differential thermal analysis(see Section 5.1.2).
Calcium bentonites have a lower durability than sodium bentonites,
although this property canbe improved by sodium-exchange. Because
0 NERC 1993
17
Bentonite
of the higher casting temperature of steel, natural sodium bentonites are

the preferred material for steel castings. The hot and
dry strengths and
thermal stability of sodiumbentonites-are preferred
for the production of
steel and heavy iron castings. However, high dry strength
is not
usually wantedin the majorityof iron foundries. Mould breakdown
becomes more difficult where
a high dry strength bentoniteis used with
resultant high sand losses.
Sodium-exchanged bentonites have high green strengths and moderate
dry strengths, whilst calcium bentonites produce moulds with a medium

green strength and a lowdry strength. However, greensands mixed
with calcium bentonites tend to have
a low resistance to erosion by the
molten metal and are prone
to giving scabbing and expansion defects.
For most foundry purposes

it is necessary to produce a sand mixture
with a high green strength and lowdry strength with the minimum
amount of clay. For this reason calcium bentonites are rarely used alone
and most foundries use a blend of calcium and sodium bentonites to
- achieve the desired combination of properties.
In summary:
0
Sandmixturesproduced from natural Na-bentonites have

medium to low green strengths but high
dry strengths, which
increase the resistance to erosion by molten metal. Wet tensile
strengths are high. Na-bentonites usually show good
high-temperature durability and the bonding properties are not
in casting steel and
destroyed by moderate heat. These are used
high-duty iron.
Sandmixturesmadefrom
Ca-bentonites havemediumgreen
strengths and lowdry strengths. They have low resistance to
erosion by molten metal and are likely to cause scabbing and
expansion defects in the moulded metal.
Sand
mixtures
made
from
sodium-exchanged Ca-bentonite
have high green strengths, low
dry strengths and improved
resistance to scabbing and expansion defects. These are inused
casting iron, non-fen-ous metals and light-section steel.
18
Bentonite
Natural Na-bentonite may beblended with a Ca-bentoniteor an

activated bentonite to give a specific set of properties
in the sand.
Such blends are used where high clay levels are necessary
to
produce strong sands at low moisture contents,
for instance in
high-throughput mechanized casting of iron and steel products.
When a greensand mould is poured the steam flashed off from the
molten metaVsand surface recondenses on cool sand
just behind the
interface. If the bentoniteis unable to hold this additional water, the
mould will looseits strength and fail. Liquid limit, which is a measure
is a useful
of the ability ofa clay to hold water without flowing,
indicator of the suitabilityof a clay for bonding purposes. Sodium
bentonites have a greater capacity for adsorbing water and thus have
much higher liquid limits than calcium bentonites. The Cast Metal
Technology Centreof the UK has recommendeda minimum liquid limit
of 525 for bentonites for usein steel casting (see Section
5.2.2).
Typically, bentonites from the north-west
USA have liquid limitsof
between 600-700. Table 3 shows typical foundry moulding sand test
values for a range
of commercial bentonites.
Table 3. Typicaltestvaluesforcommercialbentonitesusedinfoundrymouldingsands.
Compactibility
Liquid
Shatter Dry Green
index strength
strength
(kN/m2)
(kN/ma)
Natural Na-bentonite
Wyoming, USA
655-897
(med)
41-49
80-83
(high)
Fully-activated Ca-bentonite
IdY
(high)
55
Na- treated Ca-bentonite
m (high)
80
Natural Ca-bentonite
mssissippi, USA448(med) 41
( W
No.
482 (low)
79
62.5(low)
240
78
(low)
78
(%)
NA
600-620
NA
530
NA
NA
All figures basedon a 5% addition of bentonite to a standard silicasand at 3.5% moisture content
limit
118
19
Bentonite
4.2 Drilling fluids
The most important functions of bentonite

in a drilling fluid are:
e
To increasethecarryingcapacityofthedrillingfluidthrough
increased viscosity at low solids concentrations.
To suspendweightingagentsandcuttingswhendrillingfluid
circulation ceases for any reason.
To impedelossoffluidintopermeable,low-pressurestrataby
the formation ofan impermeable filter cake on the sides of the
borehole. The filter cake not only prevents fluid lossalso
but
acts as a wall-stabilising membrane.
To lubricatethedrillstringandbit.
in water to producea fluid

The easeof dispersion of sodium bentonite
with a high viscosity and thixotropic properties (the development
of a
rigid structure when shear stress
is removed) is widely employed
in
preparing water-based drillingfluids particularly for the petroleum
industry. Bentonites used for drilling fluids must meet specifications set
by the American Petroleum Institute
(MI),which is based on Wyoming
or natural sodium bentonite, and the Oil Companies Materials
Association (OCMA), which is used for lower quality clays, including
Na-exchanged bentonites. Specifications relate to the viscosities of
suspensions of fixed solids content, requiring the measurement
of
apparent viscosity, plastic viscosity and yield value, and the loss
filtrate
of a suspension at the same solids content. Specifications are shown
in
Table 4.
20
Bentonite
Table 4. Specificationsforbentonitefordrillingfluids.
Measurement
max
3,
Viscometer dial reading at

600 rpm*
Yield pointjplastic
ratio*
viscosity
Filtrate volume*
Residue > 75 pm
Moisture
API
OCMA
30, min
30, min
15.0 ml
4%, max
10%max
6, Max
16.0 ml
2.5%, max
13%max
* Measurements made on suspensionsof 22.5 g bentonite in 350 ml water.

Consumption of bentonite in drilling fluidsis related to drilling activity
(number of holes and depth) and ultimately this
is related to the price
of
0-il.There appears to be no direct correlation with meterage drilled, but
in the USA consumption is between3.3 to 4.6 tonnes for each300 m
drilled.
In areas where salt horizons are persistently encountered during drilling,
then the drilling fluid must
be salt-saturated. In the presence ofan
electrolyte, such as salt solution, smectite clays flocculate itand
is
impossible to maintain viscosity. Attapulgite and sepiolite are not
flocculated by these conditions and are used as alternatives.
4.3 Civil engineering and waste management
The properties of sodium bentonite

that are desirablein its use in drilling
fluids, that is ease of dispersion in water, viscosity, thixotropy and
impermeability, also find application ina wide range of civil engineering
applications. Slurries containing 4-8% bentonite are used in grouting
fissures in rocks. It is alsois used in diaphragm wall construction to
provide nonmechanical support for the walls of trenches, during piling
and in other excavations, and to lubricate caissons and piles. Bentonite
improves the pumpabilityof concrete and has been used in soft ground
tunnelling by the formationof a gel ahead of the tunnel face which can
21
Bentonite
then be excavated and the bentonite suspension separated and recycled

for further use. Only sodium bentonite is suitable for these applications.
Natural sodium-bentonites and sodium-exchanged calcium bentonites
are used toimprove the performance of clay liners in engineered landfill
sites for solid and liquid waste (Bath, 1993). Current practise for
landfill isto contain and treat leachates to protect nearby aquifers
and/or discharges to surface water courses, rather than dilute and
disperse asin the past. Clay liners must have maximum hydraulic
conductivitiesof 10-9m.s-1 (UK) or 10-6m.s-1 (USA) and are generally
used in conjunction with a plastic geomembrane. Some natural clays
may be acceptable for this purpose, although the use of bentonite
is
increasing since the consistency and high-swelling capacity of this clay
allows for a much thinner lining. Natural clay liner performance is
improved by rotovating-in bentonite granules to produce a compacted
bentonite-enriched soil (Harries-Rees, 1993). Alternatively, bentonite
may be incorporated in a geocomposite fabric. This materialis easy to
lay, flexible and has low permeability.
It also has the ability to self-seal
if punctured. Sodium bentonites used for landfill liners are generally
treated witha polymer (anionic polyacrylamide) to prevent flocculation
where solute concentrations
in leachates are likely to be high(>lo00
PPm).
Much researchis being conducted at present into the possible use of
compacted sodium bentonite as backfill
in radioactive waste repositories
(Pusch, 1992). The main properties relevant to this application are the
low hydraulic conductivity of the compacted bentonite (which serves
to
isolate the radioactive waste canisters
from circulating groundwater) and
the cation-exchange capacity (to capture any radionuclides escaping
from the canisters). Further information is given
by Bucher & MullerVonmoos (1989).
4.4
Iron ore pelletizing
Some ironore concentrates consist

of finely divided particles and must
be pelletized with a binder before they can be used as a blast furnace
feed. The conventional binder(0.5% addition) is high-swelling
Wyoming bentonite, although sodium-exchanged bentonite may
also be
used. The mixture ofiron ore and bentoniteis rolled to form pellets
22
Bentonite
which are sintered at about

1250C to develop enough strength to avoid
breakage during handling. A proportion of olivine
is added to some
pellets to improve their high-temperature properties. Bentonite
in
pellets:
e
e
e
e
Absorbsexcesswaterfromtheiron
ore fines.
Providessufficientdropandcompressivestrengthtothegreen.
pellet to withstand handling.
Provides
adequate dry strength.
Improvesthemechanicalpropertiesofthefiredpellets,reducing
the quantity offine particles produced.
Other than testing the strength the

of pellet, swelling volume and Enslin
value (water absorption) are the best clay characterisation techniques
for
predicting the efficiency of clay samples to make pellets with high
compressive strengths. Although bentoniteis a relatively inexpensive
binder it does add to costs
by increasing handling requirements and
contamination by an aluminium silicate gangue. Bentonite usually
decreases the iron content of the pellet
by 0.8%. As a result pellets have
been produced usinglime, and some investigations have been carried
out on the use of organic binders. However, other binders have not
received widespread acceptance.
Bentonites are also used to pelletize animal feeds, to whichalso
they
impart some nutritional benefits.
4.5 Acid-activated clays
Acid-activated clays find application in three main market areas;

e
e
e
Refining(bleaching,ordecolourising,andpurifying)edible
vegetable and animal oils,fats and solvents
Catalysis
Colourdevelopersforcarbonlesscopypaper
70-80% of the
The fxst of these is the most important, accounting for
total market. Acid-activated claysare used in the bleaching of colouring
pigments and the adsorption ofimpurities such as phosphatides, gums,

0 NERC 7993
23
Bentonite
trace metals and free fatty acids.

A review of applications in this market
area is given by Griffiths (1990).
Acid-activation (or bleaching) enhances the adsorptive and catalytic
activity of the clay by increasing
its surface area and particularly
its
surface acidity. During refining the coloured pigmentsthe
in oil are
'captured by the donation of a proton(H+)from the acid cations,
yielding a positively charged organic cation which is attracted and
in the same way as
effectively bound to the surface of the clay
exchangeable cations. The large surface area of the clay can easily
accommodate the large organic cations. Similarly catalytic activity
is
promoted by proton donation andin carbonless copy papers the
colourless dye encapsulated
in the paper is converted to a coloured dye
on protonation.
4.6 Absorbents
Natural Ca-bentonite is used asa granular absorbent and particularly

as
the basic ingredient of many of the popular types of pet litter.
This use
has emergedas onethe largest applications for bentonite in Europe and
America, althoughthe mineral is in direct competition with other
granular absorbent minerals, particularly sepiolite, attapulgite and
diatomite. However, Ca-bentonite behavesin quite a differentway to
the other minerals when wetted, forming clumps which can easily be
separated and removed for disposal. There
are no rigid specifications,
the requirements being for
a high liquid and odour absorbency, freedom
from dust and uniformity in size. Granules are generally
in the size
range 2-5 mm and the bentonite used must have some inherent strength
to prevent dusting. A review of market developments in this area
is
given by Santarh (1993).
As Ca-bentonite tends to slakein oil and grease, producing a slippery
surface, attapulgite and sepiolite are the preferred granules
for use as oil
absorbents on factory floors where spillage
is likely.
In the calcined form Ca-bentonites are water stable and can be used as
carriers for pesticides and herbicides. They are abrasion resistant, free
fiom dust, uniformin size and havegood mechanical and flow
Mineralogy and Petrology Group, British Geological

Survey 0 NERC 1993
24
Bentonite
properties providing a safe carrier from which highly toxic pesticides

can be formulated.
4.7 Other Uses
Bentonite has numerousother applications (Figure4), for example in

cosmetics and pharmaceuticals (Gamiz
et al., 1992). However, a
relatively new application which has appeared
in recent years and which
is showing high growth rates,
is in thepaper industry. Na-bentoniteis
used in combination with water-soluble polymers in the papermaking
process whereit acts as a filler and fibre retention aid. More
importantly, however, it improves the wet permeability
of the paper
web, allowing improved dewatering and thus savings on drying costs.
to work by microparticle flocculation which
The process appears
improves the porosityof the paper web. Detailed specificationsare not
available but coarse impurities such quartz
as
must be kept toan
absolute minimum becauseof abrasion tothe papermaking machinery.
Consequently bentonites are subjected to air classification to remove
oversize particles.

0 NERC 1993
25
Bentonite
5. LABORATORYASSESSMENT
OF BENTONITE
The laboratory assessment of bentonites involves a variety

of
mineralogical, chemical and physico-chemical techniques. These
are
used to characterizethe clay, and to assess grade and quality.
A more
detailed investigation programme of testing related
to specific
applications on materials which have met certain minimum grade and
quality criteria might may
be carried out following this initial resource
assessment phase. Figure5 sets outan idealised laboratory
investigation scheme which includes all these elements. Examples of
simplified resource assessment schemes
for the laboratory screening of
relatively large numbers of suspected bentonites are setinout
Figures 6
and 7. Figure 6 illustrates a scheme which might be used
by a
laboratory with fairly basic facilities whilst a scheme which utilises more
sophisticated equipmentis shown in Figure7.
5.1 Mineralogical and chemical examination
A number of mineralogical and chemical techniques be

may
used to
characterize bentonitic clays, including X-ray diffraction
(XRD),
differential thermal analysis(DTA), infrared (IR) spectroscopy,
scanning and transmission electron microscopy, optical microscopy
(mainly to identify textures relevant to origin), and major- and
minor-element determinations, including those for exchangeable cations.
Some of these techniquesare discussed in more detail below.
26
Bentonite
GRADE
MB dye absorption (appmxCEC)

2-ethoxyethanol surfam area (%smectile)
Bulk XRD analysis (wholerock mineralogy)

Q
XRD analysis(claymineralogy)
XRF analysis(majorand nace element chemistry)
'True' CEC
Exchangeable cations (clay surfacechemistry)
Thermal anatysis (dehydroxyhtinbehaviour. quantitatiiemineralogy)
Elearon microprobe (smeaite cyaalchemistry)
Scanning electronmicroscope (petrography8 smectite texture)
Transmission electron microscopy (smectite crystalsize, shape 8
aggregation)
NATURAL CLAY
Liquid limit (LL) 8 plastic limit(PL) (plastic properties)
_s
-ty
Plastic vlscwity
Yield point
Gel strength
Grit content(>75 pm)
Filtrate volume
Green 8 dry strength

Wet tensile strength
Shatter index
Conpactability
Green permeabilty nun
AClD-ACllVATlO~
Acid treatment
Surface area
= Crystal structure
OIL-BLEACHING
Bleaching performance
Figure 5.
Idealschemeforlaboratoryassessment
of bentonites.
Mineralogy and Petrology Group, BritishGeologicd Survey 0 NERC 1993
SODIUM
CARBONATE
27
Bentonite
.................................................................................................................
LOW CEC
as bentonites
~ ~ . ~ . ~ . ~ . ~ . ~ . . ~.....................
.~...~.....~.~..
...................................................
Plot resuls on a
$Aasticity chartto 'confm'
: the presence of smectite.
Identify whether
;
Ca-montmorillonite
I or Na-montmorillonite
is present.
.
e
"r'
I
I
I
Assess quality of
bentonite by comparison
ofmaximumliquidlimit
: andswellingindex values
: with those ofcommercial
bcntonites
_.--.......-_...
POOR
QUALITY
swelling index SAMPLES

and liquid limit .
values after
additions of 1.5%
sodium carbonalc
? Reject samples
as bentonites or
use in low-value
applications
i
i
....................... ...........................
.................................. ...................
i
Add optimum
addition of
FAILS OCMA
hcological
andwithdata Compare
tcsl
OCMA specs. for
drilling fluids.
.....
.
.
e
I
.
.
.
.
.
.
iluate loss ESIS
? Bentonite for
non-drilling fluid
applications
MEETS W M A
SPECS
? Bentonite for
drilling fluid use
..................................................................................................................
Figure 6. Example of a scheme used in Costa Rica for screeninglarge

suspected
bentonites
(Inglethorpe,
1990)
numbers of
28
Bentonite
....................................................................................................................................................................................................................................
STAGE 1 i
; 'Screening test'
: All samples aretested using this

: procedure. A characteristicof
: smectite-groupclay minerals (the
i principal constituents of fuller's

j
earths) is their very high surface

area comparedto otherclayand
i non-clay minerals.Moderate and

: high surface area valuesinfer the
' p r e ~ e n of
~ esme~tite
and - by
reference to a standard - enable a
i maximum possible smectite
; contenttobecalculated.
;
'
Although the testis sensitive to

the presence of smectite, it does
not definitelyindicae its
presence
.............
Inferred
smedite
content
~30%
Calculate
Reject samples
% smectite
smedite
content
>30%
..........................................................................................................................
Mlneraiogkalanaiysls
......................................................................................................
STAGE 2
bw-grade of
smectite with
high levels of
impurities
the relativeproporlions of nonclay mineral constituents.

High-gradeof
smectite with
low levels of
impurities
?Possiblefurther testing
(e.g. examinatlonof response to
Na-exchange, userelatedtests etc.)
.......
Figure 7. Example of aschemeused

by BGS for initial screening of largenumbers
suspectedbentonites(Moorlock
& Highley,1991).
of
29
Bentonite
5.1.I X-ray diffraction

X-ray diffraction(XRD) provides definitive information on the
mineralogical compositionof a bentonite, bothin terms of clay and
non-clay constituents.In the first instance, the sample
is examined as a
random powder mount. From this, using standard JCPDS search
procedures, the bulk mineralogy of the bentonite can be determined
of particular minerals with those
(Figure 8). By comparing peak heights
on diffraction chartsof artificial mixtures, semi-quantitative
data can be
obtained. At this stage, impurities which may be a problem
in use can be
identified: e.g. calcite, whichis an acid user during acid-activation,
gypsum, the presenceof which can lead to poor rheological properties,
and cristobalite, whichis a possible health hazard
in certain applications,
and which may also act asa cementing agent, thus leading to poor
physico-chemical performance.
XRD examination of an 'oriented mountof the smectite constituent will
show whether this contains mainly divalent (Ca2+,Mg2+)
or monovalent
(Na+) exchangeable cations. Under normal relative humidity, the basal
spacing, dWl,of a divalent cation-saturated smectite
is -15-4,8,, whereas
for a monovalent cation-saturated smectite
it is 12-6A. Subscquent
basal spacings are exact sub-multiples
of either 15.4 or 12.6A. With
smectites having a mixed monovalent/divalent exchangeable cation
assemblage, the doolspacing is between 15-4and 12.6A and
subsequent ordersare not exact sub-multiplesof dool. All
A with ethylene glycol or to
cation-saturated varieties expand to 17.2
17.8A with glycerol. Identification of mixed monovalent/ divalent
cation-saturated smectites may be significant
if an application involving
viscosity is likely, as it has been demonstrated that 'optimum'
rheological properties are given
by a bentonite having
an exchangeable
Na+ to Ca2+@Ig2+ratio
of 3:2 (Alther, 1986).A d oolspacingof between
10 and 15-4A in the air-dried state, together with
an irrational series of
peaks from both the air-dried and glycerolated mounts, would indicate a
mixed-layer illite-smectite clay. 'Oriented' XRD curves of bentonites
from Thailand are illustrated in Figures 9a and 9b.
XRD examinationof powder mounts ofa bentonitemay also provide
limited information on the nature of the smectite species. The
d&,
spacing will show wheteer the smectite
is dioctahedral(1-49-1-50A) or
trioctahedral(l.52-13 3 A). Dioctahedral smectites include
Mineralogy and Petrology Group, British GeologicalSurvey 0 NERC 1993
30
Bentonite
montmorillonite, the most common species, and beidellite, and contain

predominantly A1 in octahedral structural sites. Trioctahedral smectites
are less commonin general and large deposits are consequently
relatively rare. Hectorite,a smectite containingMg and Li in octahedral
sites, occursin the westernUSA and is marketed mainly forits
gel-forming and thixotropic properties. Saponite contains almost
exclusively Mg in octahedral sites, and a deposit
in central Spain has
recently been described (Galanet al., 1986) which shows certain
physico-chemical properties equal to those of the more common
montmorillonitic bentonites. The b-dimensionof the smectite unit-cell,
which can be determined
by XRD from powder mounts, has been
An
linked to the degreeof swelling exhibited in suspension.
investigation into this relationship
is described by Low (1980).
31
Bentonite
Peak intensity
Anicr
An
Sm
il
Figure 8. Whole-rock (random) X R D curvesoftwo
bentonitesfromThailand.Sm:
Qz: quartz; Cr: ctistobalite; Hm: hematite; Ca: calcite;
smectite; An: calcicplagioclase;
At: anatase.
32
Bentonite
glycol
air-dried
Peak intensity
OOI ( I 6.70A)
I\
glycol
air-dried
Figure 9. XRD curves of oriented e2 pm fraction of twoThailandbentonites

in air-dried
and
glycol-saturated
states.
Smectite
basal
spacings
are
labelled. Note
low-angle
(b) which may berelatedto
shoulder on 001 peak ofair-drytraceofbentonite
exchangeable Na content,
Mineralogy and Petrology Group, British Geological Swrvey0 NERC 1993
33
Bentonite
5.1.2 Thermal analysis
In the absenceof XRD, differential thermal analysis (DTA) can

be used
to a limited extent to characterize the smectite constituenta of
bentonite
and to identify impurites suchas calcite and quartz.
DTA curves of smectites are usually divided into three regions:

e
thelow-temperatureregion (<300"C) withinwhichadsorbedand

exchangeable-cation coordinated water are released;
the dehydroxylation region(400"-75OoC);
thehigh-temperatureregion (>800"C), wherenewphases
crystallize from the dehydroxylated clay.
In the low-temperature region, smectites containing monovalent

exchangeable cations show only a single endothermic peak, whereas
those containing divalent exchangeable cations show
a well-defined
-200C representing expulsion of water loosely
shoulder to this peak at
bound (the 'hydration shell') to these cations (Figurelo).
Smectites are often describedas showing 'normal' or 'abnormal'
dehydroxylation behaviour depending on the temperature range
in which
dehydroxylation occurs (Mackenzie, 1970). Normal smectites show a
single dehydroxylation endotherm between650"-72O"C, abnormal
varieties show either a single endotherm-550C
at
or a dual
endothermic systemwith peaks at-550C and -65OOC. The
dehydroxylation behaviourof a smectite is important in foundry sand
applications. When metal is poured into a bentonite-bonded sand, the
heat drives adsorbed and hydroxyl water from the clay nearest the
sand-metal interface. As moulding sands are recycled many times, the
structure of the smectite is gradually destroyed,with consequent
deterioration of bonding performance. Smectites showing high
dehydroxylation temperatures exhibit greater durability although,as
Odom (1984) has pointed out, this also depends on the naturethe
of
exchangeable cations.
34
Bentonite
Figure 10. DTA curves of bentonites

showingdifferentdehydroxylation
behaviour.
Note
the
well-defined
shoulderat -200 "C onthelow
temperatureendotherm of sample 5-2-70
representingtheexpulsionofwater
looselybound
todivalentexchangeable
cations.
Other thermal methods such as thermogravimetry

(TG) or evolved gas
analysis (EGA) can give accurate quantitative information on impurities
such as carbonates and sulphides (Morgan,1978).
5.1.3Chemical analysis
Before determining the chemical composition of a smectite
it is fxst
necessary to remove impurities by separatinga <2 pm (ideally a e1 pm
or smaller) fractionby either sedimentation/decantation or
centrifugation. Prior to separation, the clay must be saturated
with Na
ions to provide a stable (i.e. non-flocculating) suspension, and after
separation excess salt must be removed
from the clay productby
sequential water and alcohol washing.
A good description of the
methodology for clay separation is given
by Bain & Smith (1987); these
authors also describe methods appropriate
for major-element analysisof
35
Bentonite
the clay product. Distributions of atoms

within the different structural
sites of the smectite can then be detennined by calculating its structural
formula from the chemical analysis; this procedureis describedby
Newman & Brown (1987).
As indicated in Table 1,smectite-group minerals show considerable
variation in chemical composition through substitutions
within
tetrahedral and octahedral structural sites. Members of the solid-solution
series montmorillonite-beidellite are the most common species found
in
commercial bentonites. In this solid-solution series, up to one of the
eight Si atomsin tetrahedral sites can be replaced
by A1 atoms, and up to
one of the fourA1 atoms in octahedral sites can be replaced
by Mg and
Fe atoms. Variations in structural chemistry within members of the
montmorillonite-beidelliteseries can cause differences in physical
properties such as viscosity in suspension,but in commercial practice
other factors such as the nature and amount of impurities, variations
in
exchangeable cation assemblage, and state of aggregation of the clay
particles have far more influence on behaviour.
Nearly all chemical analyses of bentonites quoted
in the trade literature
are of unseparated, production-run materials and, as such, are of limited
value for relating to behaviour
in use. Likewise, major-element analyses
of impure bentonite exploration samples are unlikely to provide
information of value in relation touse. Only in the latter stagesof a
laboratory exploration programme when promising material has been
identified by other more appropriate methods, would chemical analysis
of a purified smectite product be justified.
However, some chemical determinations are essential
in assessment
programmes. The most importantare determination of the
cation-exchange capacity and the composition of the exchangeable cation
assemblage (see next section). The presence of trace elements such as
lead and arsenic could mean that
a bentonite was unsuitable for
pharmaceutical useor as a carrierfor agricultural chemicals. Gamizet al.
(1992) discuss the suitability of Spanish bentonites in relation to
existing pharmaceutical specifications. Because certain trace elements
are usually retained when an igneous rock alters to, clay, plots
ratios
of
of these trace-elements ona geochemical grid (Figure 11) can often
indicate the compositionof the parent igneous material, and thus can be
of use in bentonite exploration.
36
Bentonite
""I1
o a1
0:10
NblY
10
Figure 11. Plots ofbentonites

from Thailand (A)9 Malaysia k) and
Indonesia (a) on a geochemicalgrid.
5.1.4 Cation-exchange capacity and exchangeable cations
The cation-exchange capacity

(CEC)of a smectite isof fundamental
significance to applied properties and is often quoted in
use-specifications. The compositionof the exchangeable cation
assemblage isalso of practical significance as this is
a prime criterionof
suitability for most major applications. Discussions on the relationship
between exchangeable cations and hydration/swelling of bentonites are
given by Odom (1984), Alther (1986) and Elzea
& Murray (1990).
Effects of differences in bentonite exchangeable cations on
khaviour in
foundry moulding sands are describedby Grim & Guven (1978) and
Stephens & Waterworth (1968).
ExchangeabZe cations Exchangeable cations are usually releasedfrom

the bentoniteby ammonium acetate (Appendixl), and the leach
solutions analysed for Ca,Mg, Na and K by, e.g., flame photometry/
atomic absorption spectrometry. Table5 gives values for exchangeable
cations of two bentonites fromThailand However, totals for
'exchangeable cations' releasedin this way may be greater than 'true'
cation exchange capacity of the clay, because fine-grained calcite and
gypsum are partially dissolvedby this treatment and release calcium ions
into solution. Erroneously high values for individual cations may result
from the presence of these minerals (sample 'B'in Table 5 shows
anomalously high Ca because ofthe presence of calcite).
37
Bentonite
Table 5.
A
B
Exchangeablecations
12.2 51.5
99.9
of twobentonitesfromThailand.
9.5
11.5
20.6
1.9
3.2
C0.1
CO. 1
True CEC Common methods for determinationof cation-exchange

capacity are discussed in
Van Olphen & Fripiat (1979) and Bain
&
Smith (1987).A method for measurementof CEC using barium as the
index ionis described in Appendix2. It is useful to distinguish between
true CEC methods described above and the methylene blue method
6 gives values for
commonly used to determine bentonite grade. Table
true CEC, and methylene blueCEC for some bentonites from
Thailand.
Table 6 . True CEC andmethyleneblue
fromThailand.
73.7
74.4
CEC of two bentonites
50.2
44.5
T: True CEC
* CEC by methylene blue method.

5.2 Physico-chemical tests
A number of use-related physico-chemical test procedures can
be
applied to a bentonite as part of a laboratory assessment programme.
These can be dividedinto tests which measure either the
grade or
quality of the clay (see Figure5).
38
Bentonite
5.2.1 Grade of bentonite
Methylene blue cation-exchange capacity For a numberof reasons

mainly connectedwith the large sizeof the methylene blue ion,this test
does not measure the 'true' CEC of a bentonite. CEC values obtained
by the methylene blue method are usually lower than 'true'CEC values
(Section 5.1.4). However, this testis sensitive to the smectite content
and has the advantageof being relatively rapid.As a consequence, itis
useful in estimating the grade of large batches of samples such as might
be encountered in an exploration context (Figure6). The method
involves dispersing a known weight
of clay in water and adding a
methylene blue solutionof known concentration in 1- or 2-ml
increments to the clay suspension. Uptake of dye
by the clayis
monitored by 'spotting' a small portion
of the clay-dye complex onto a
filter paper (Figure 12a). While the dye
is still being adsorbed by the
clay, the 'spot'is blue andis surrounded by clear water (Figure 12b).
At and beyond the end-point, the blue spot
is surrounded by a haloof
free dye (Figure 12c). The methylene blue CEC is calculated
from the
amount of dye adsorbed at this end-point andis normally about 80% of
the true CEC. To ensure efficient adsorptionof dye, a waiting period
of
5 min or so is necessary after each addition and the method
thus lends
itself to batch testing;20 samples can easily be dealt
with in a working
day. Step-by-step instruction for this testare given in Appendix 3.
Figure 13 illustrates the rangeof methylene blue CEC values expected
from bentonites and other clays. Background to this test
is given by
Nevins & Weintritt (1967) and Taylor (1985).

0 NERC 7993
39
Bentonite
Figure 12a. Filterpapershowingmethyleneblue

quality@a-bentonite.
Figure 12b.
Appearance of methylenebluedye
Figure l2c.
Appearanceofmethylene
dyespotsfollowingtesting
spot beforeend-point
blue dyespot
atend-point.
Mheralogy and Petrology Group, British Geological Survey El NERC 1993
of a poor-
is reached.
40
~~
Bentonite
0
10
20
30
40
0.
425
50
120
Figure 13. Range of methylene blue CEC values shown by bentonites and other clays
1985).
(afterTaylor,
41
Bentonite
2-ethoxyethunol [ethyleneglycol monoethyl ether (EGME)] surface area

This test measures the total available surface area
of a sample, in
contrast to the conventionalBET nitrogen adsorption procedure which
measures only 'accessible' surface area. The procedure followed
is that
of Carteret al. (1965)and involves monolayer formationof EGME on
the clay surface under vacuum. Detailsof the method are givenin
Appendix 4; some typical values are given
in Table 5. Weighing the
clay-EGME complex, and knowing the cross-sectional area of the
EGME molecule, allows the surface area
of the clay tobe calculated.
The standard material usedis one for which the surface area has
originally been determined, e.g.a pure smectite which has been
analysed chemically, the structural foxmula calculated, and the surface
area determined from the unit-cell parameters.As pure smectites have
surface areasof the orderof 800 m2/g, other clayminerals such as
kaolin <40 m2/g, and non-clay minerals<5 m2/g by this method, the
surface area ofan unknown bentonite can easilybe converted to a
reasonably accurate % smectite figure. The method was originally
developed using Ca-bentonite and some difficulties may be experienced
when assessing Na-bentonites as surface area values appearbeto
influenced by exchangeable cation-EGME reaction well
as as by the real
extent of the clay surface.A discussion of this aspect is given in
Kellomaki et al. (1987).
Table 5. EGME surfaceareavaluesfortwobentonitesfrom

Thailand;threeseparatedeterminations(figuresinparentheses
representestimatedsmectitecontent).
540 582
505
547
507
Mineralogy and Petrology Group, British Geological Suwey 0 NERC 1993
53 1
556 (90)
514 (64)
42
Bentonite
5.2.2 Quality of bentonite
Tests which are coveredby this heading are those which can
be used to
assess the likely performance of
the bentonite in use. They measure
indirectly the extent to which the bentonite disperses
into 'individual'
smectite particles, and thus the efficiency with which the large active
surface areais utilized. Factors that can lead to poor dispersion
in
bentonites are compaction due to overburden and cementation
by
secondary silica.
Sodium carbonate exchange The production of sodium-exchanged

bentonites involves the addition of small amounts of sodium carbonate
(usually 2 to 4%) prior to drying and grinding.On subsequent addition
of water, the calcium bentonite converts to sodium bentonite. The
amount of sodium carbonate required
for optimum property
development is usually determined by preliminary laboratory trials. It
may vary from2% for a mixed Ca,Mg,Na-bentonite to
5% for a
completely Ca,Mg-saturated clay. The tests described below can also be
used to assess the response of a bentonite to sodium exchange.
Swelling test The generally accepted test for measuring the extent
of
swelling of a Na-bentonite consists of sprinkling a small amount of clay
into a graduated cylinder filled
with distilled water and measuring the
volume of the swollen bentonite after 24 h. A detailed procedure
is
given in Appendix 5. Typical swelling values for bentonites
are given
in Figure 14. A moderately swelling bentonite will produce15-20 ml
gel, agood variety about25 ml and an excellent grade will produce
30
ml or more. By progressively mixing amounts of
1 to 6 wt% sodium
carbonate to a Ca-bentonite and drying gently, the swelling test can be
used to give an indication of the ease with which the bentonitebecan
converted to the Na-form,as shown in Figure 14.

0 NERC 7993
43
Bentonite
"Or
I30 -
FULLERS EARTH
BAULKING BH.1
140
120
cg
2 110-
E
CI,
100
90-
0
t 80a
70-
60-
FULLERS EARTH
FERNHAM F.11
I1
COMMERCIAL
BENEF!CIATED
FULLERS EARTH
FULLER'S
EARTH
from F 1
REDHILL SURREY
ADDITION OF SODIUMCARBONATE
Figure 14.
c.r.c
65
0 1 2 3 4 5 6
(96 by welght ol a1r-dt-y clay)
Typical
swelling
values
for
sodium-exchanged
bentonites.
Atterberg limits The Atterberg liquid limit (LL) an

is indicator of the
bonding property ofa bentonite. It is the minimum% water that will
cause a bentonite-water mixture to flow when testeda in
prescribed
manner using the Casagrande liquid limit apparatus, or the
% water
relating to a penetration depth of20 mm using a cone penetrometer. Of
the two tests, the cone penetrometer method
is considered to be
fundamentally more satisfactory since
it is essentiallya static test
depending on the shear strength
of the clay. It is also easier to perform
and more reproducible than the Casagrande technique (British Standard
1990).
The LL of a bentonite can formpart of the specification for foundry use
and is commonly mentioned on specification sheets of bentonites
offered formany other applications. Generally, Ca-bentonites give
LEs
in the range 100-200 and Na-bentonites values between550 and 750. In
the higher range, LL values are markedly affectedby the methodof
preparation used. The LL specification developedby the UK Cast
Metals Technology Centre(minimum LL 525) is based on values
obtained with minimum mixing between clay and water. In contrast, the
Steel Founders Societyof America's LL test is based on
a bentonite
which has been dispersed'in water using a high-speed mixer and then
allowed to dry from a slurry. Consequently, LLs are higher: values up
to 900 are quoted by Alther(1986).
The LL test can bea sensitive indicator of the response of
a
Ca,Mg-bentonite to sodium exchange. The procedure developed
in the
laboratories of the British Geological Survey involves determiningLLs
after addition of1-6% sodium carbonatein a similar manner to that
44
Bentonite
described for the swelling test above. Detailed methods for LL

determination using both the Casagrande apparatus and the cone
penetrometer apparatus are given in Appendix
6. Figure 15 showsLL
results for fourUK Ca,Mg-bentonites (all containing >90% smectite)
subjected to Na-exchange. Maximum LLs are obtained after
4-5%
sodium carbonate addition, but these vary from
340 to just over600.
This difference is caused by variations
in the extent of disaggregation of
the clays, this being provedby subjecting sample4 to high-shear
dispersion which increased the maximum LL to 750.
Although primarily used for the assessment of bentonite quality, LL can
be used in conjunction with Atterberg Plastic Limit (PL) as
a simple
indicator of bentonite grade (Bain, 197 1).
PL is defined as the moisture
content of a clay at the point where it becomes plastic.
By plotting PL
against the Plasticity Index (PI) (LL value minus
PL value), an
indication of bentonite grade and response
to Na2CO3 additionis
obtained (Figures 16 and 17). In the absence of more sophisticated
techniques, this method may be useful
in providing additional
complementary data for (say), a screening exercise on suspected
bentonites using methylene blue CEC.
A method for plastic limit
determination is given in Appendix 7.
45
Bentonite
-800
-700
-600
-500
E*
-400
E
-.
g.
-300
-200
-1 00
4
5
percentage Na2C03added
Figure 15. Liquid limitresponse

offourCa-bentonites(allmore
than 90% smectite) to Na2C03 addition. High sheartreatment of
sample 4 induced aggregate breakdown andresulted in improved
response to Na2C03 addition.
46
Bentonite
Holloysile
e Kaolinite
0 Plastic Kaolins
Illite
A Ca-Montmorillonite
A No-hlontmorillonite
X
Sepiolire
x Atrapulgile
x
*
>
I
I
I
A
I
i
/
,/
60
Trace of
A
Casagrandes
Kline
,A
C/
40
0,
A
A
30
----
Plasticity index
Figure 16. Clayidentificationchartusingplasticlimitand

plasticity index asparameters.Note
thecleardistinctionbetween
naturalNa-bentonites(montmorillonites)andCa-bentonites
(from
Bain, 1971),
47
Bentonite
A (C)
Colcium
Montmorillonite
Sodium
Montmorillonite
*!dl
(e)
A
!t
Plasticity index
Figure 17. Location of bentonitesand.smectite-bearingclays

on the
PL/PIchart(fromBain,
1971). (a),(b) WyomingNa-bentonite;(c)
saponite(Tanzania); (d),(e) NorthAfricanNa-bentonite;
(9
Wyomingbentonite;(g),(h)
UK Ca-bentonites; (i) smectite-bearing
soil, Nevis Island; u),(k) UK Ca-bentonites; (1) Ca-bentonite,
Hungary; (m) smectite-bearing soil, Mauritius;(n)Ca-bentonite,
Botswana; (0) LondonClay(smectite-bearingmixed-assemblage
clay). Arrows indicatethe effect on Na-saturation on naturalCabentonites.
48
Bentonite
6. USE-SPECIFIC TESTS
6.1 Foundry moulding sands
Properties of bentonite/sand mixtures that are crucial

for oundry usage
are green compressive strength,dry compressive strength, shatter
index, and compactibility; properties such as wet tensile strength, hot
compressive strength, flowability and durability may
also be quoted in
specifications.
Factors such as sand:clay mix milling time, moisture content and
sand:clay ratio have considerable influence on some of these properties
(Figures 18a, b,c). For a preliminary evaluationof the suitabilityof a
bentonite for foundry use, it is sufficient to determine the green
dryand
compressive strengths ofa 5% mixture of the bentonite with
a standard
sand at a fixed moisture content, typically
3.5%. Green and dry
compressive strength values indicate the ability of a mould to retain its
shape during forming, handling and casting. Shatter index indicates the
cohesiveness of the greensand during emplacement and subsequent
removal of the mould from its pattern. Compactibilityis the volume
occupied by a fixed amount of greensand during moulding and indicates
both mould density and greensand requirement. Permeability indicates
the susceptibility ofa greensand mould to gas and metal penetration
during casting; slow/moderate gas permeability is needed to prevent the
formation of porosity within the metal cast, but
if permeability is too
high then metal will penetrate into the mould. Some typical foundry
moulding sand test results for bentonites from Thailand are in
given
Table 6.
BOND DEVELOPMENT
MILLING TIME (MINUTES)
Figure18a.Rate
time.
of development of greenstrengthwith'milling
m i n g sodium
Activated bentonite
Colcium kntonite
Activated bentonite
Calcium bentonite
Wyommq sodium
201
7
Water '1.
Water *I.
Figure 18b. Relationship between green strength(left)anddrystrength(right)andwater

content for mixtures of standardsand and 5% clay.
lCOt
Figure 18c. Effect of increased claycontent

(right) of mixturesof standard sandandclay.
on greenstrength(left)anddrystrength
. 49
50
Bentonite
Table6.Foundrymouldingtestresults
Sample
for twobentonites
from Thailand.
Green
permeability
Green
strength
Dry
strength
Shatter
index
Compactability
No
Wh2)
W/m2)
Thailand bentonites
SDI 144 (145)130
(59) 63 (68) 73 (648)669
66 (63)
(57) 58 (140)SDI
130 145
62 (69) 572
67 (662)
Commercial bentonites
80
(A)
155
62.5
80-83
655-896 NA 1-48
4
No.
(%)
(64)
713
NA
A) Na-treated natural Ca-bentonite

(B) Natural Na-bentonite, Wyoming,USA
Values in parentheses areafter N a 2 Q addition.

The tests were conducted using a mixture
of 92.5% Chelford 60 (silica) sand,5% clay and 2.5% moisture
(figures in parentheses indicate results after addition
of 2% sodium carbonate).
Detailed test methods for the determination of these physical properties

in clay sand mixes are not given in this manual, as they require
equipment whichis not generally found outside specialized laboratories.
Preparation of test pieces of the clay/sand mix and procedures
for these
specialized tests are described
by Parks (1971) and in a series of method
sheets publishedby the British Casting Industries Research Association
(1985).
6.2 Drilling fluids
The main properties of bentonite that

detennine its suitability for drilling
fluids are its ability to form viscous suspensions
in water or other fluids
at low solids concentrations, the thixotropic behaviour
of these
suspensions, and the impermeabilityof thin filmsof the dispersed
particles. Determinationof these properties forms the basis
of the
51
Bentonite
American Petroleum Institute (API) testing procedures for drilling fluid

bentonites. These tests are also used to determine suitability of bentonite
for civil engineering applications.
6.2.4 API
and OCMA specifications for bentonites
Two specifications exist- the main API specification whichis based on

the performanceof Wyoming bentonite, and one that
is less rigid, based
on an earlier Oil Companies Materials Association (OCMA)
specification aimed at bentonites that, although providing satisfactory
oil-well drilling mud performance, could not meet that
of Wyoming
bentonite. Viscositiesof suspensions of fixed solids content are
determined on a direct-reading Fann viscometer (Figure 19) and require
the measurementof apparent viscosity, plastic viscosity
and yield value
(although thisis not immediately apparent from the specifications);
10-second and lo-minute gel strengths also
are usually measuredin a
comprehensive evaluation ofa bentonite for drilling mud applications.
Filtrate lossof a suspensionof the same solids concentration also forms
part of the specifications, as does the amount of material retained on
a
75 pm screen and the moisture content of the clay.
Step-by-step test procedures are described
in Appendix 9 (OCMA tests)
and in API (1990). A useful discussionof the rheological propertiesof
bentonite suspensionsis given by Brandenburg & Lagaly (1988).
Some typical APYOCMA test resultsare given in Table 7. Table 8
details typical gel strength values for a number of commercial-grade
bentonites and other clays.
52
Bentonite
Table 7. OCMA/API test resultsofbentonites

bentonitesusedindrillingfluids.
(3300
(3600
(cm3)
OCMA specs
(Cps)(Cps)
KPS)
>30
~
Thuiland bentonites
A (0% Na2C03)
A (5% Na2C03)
B (0% Na2C03)
B (5% Na2C03)
Commercial bentonites
C
~~
3
60
Apparent
viscosity
(CPS)
fromThailandcomparedtocommercial
Plastic
Yield point Filtrate
viscosity lbs/100sq ft volume
>75 /un Moisture

(mass %) (mass9%)
<(6*p.v.) c l 6
c2.5
~13.0
~~~
1.5
51
1.5
1.5
38
30
30
1.5
19
45
31
34
20
22.5
15.5
1.5
1.5
9
8
11
11
27
0
42
0
22
22
6.8
19.6
8.4
23
9
13
11.5
13.7
7.8
5.3
3 -2
(C) Na-activated bentonite, Mexico (Alther,

1986).
@) Cedars type bentonite, Wyoming (Alther,1986).
. (E) Wyoming & Montana (Elzea & Murray, 1990)
Table 8. Typicalgelstrengthvalues
for commercial-gradebentonitesandotherclays.
Values in parenthesesafter Na2C03 addition.
I3
10 sec gel
I3
(lbs/100 ft2)
(lbs/lOO ft2)
1.5
Wyoming bentonite
UK Ca-bentonite
Ca-bentonite (Morocco)
London Clay
(UK smectite-rich
mixed-assemblage
clay)
10 min gel
Mineralogy andPetrology Group, British Geological Survey 0 NERC 1993
53
Figure 190 Fann viscometer.
54
Bentonite
6.2.2 Measurement of viscosity of bentonite suspensions using

direct reading Fann viscometer
Preparation of suspensions The bentonite suspensionis prepared in a

high-shear mixer (theAPI specification requires that this hasa
sine-wave impeller of approximately
25 mm in diameter which rotates at
11 000 rpm). Total mixing time should be 20 minutes. The bentonite
suspension is then stored overnight (sealedto prevent evaporation) to
allow it to 'age'. This is very important as the viscosity of a bentonite
suspension does not develop fully without
a sufficient ageing period
After ageing, the suspension should be mixed under the same conditions
for 5 minutes immediately before viscosity determination.
Viscositymeasurement Starting with 600 rpm, the dial deflection
on the
Fann viscometer should be recorded5at
min intervals until a constant
reading is reached. This may take up to30 minutes whilst the
suspension adjusts to the new shear conditions
of the viscometer rotor.
Once this constant reading is achieved, the speed
is changed to300 rpm
and dial deflections again noted at
5 min intervals. A constant reading
will be obtained sooner than for600 rpm. These two readings give
sufficient information for theMI specification, butif a 'consistency
curve' is required then the same procedure should be followed for
200,
100and 6 rpm.Dial deflections for a typical bentonite are given
in Table
9.
Table 9. Typicalreadings
on Fannviscometerforbentonitesuspensionduring
Viscometer dial readings (" deflection)

0 min
Rotor speed
600 rpm
40"
300 rpm
200 rpm
100 rpm
6 rpm
21
31
30
26
23
36
34*
5 min
10 min
30
33
31
28
26
34
34
31
29
26
* readings used to calculate apparent and plasticviscosities and yield value.
15 min
29
API test.
30 min
55
Bentonite
Gel strength mayalso be measured using theFann instrument. This

property is not required
by the API specification, but is nonetheless an
important property of a drilling mud. Gel strength is measured by
recording the dial deflection at the momentof gel break. The
suspension is allowed to standfor a set period before restarting
the
motor at very low revolutions. 10 second and 10 minute gel strength
valuesaregenerallydeterminedusingthismethod.
.
Calculations The design of theFann viscometer and experimental

of the rotorand bob, rpmsused, and torsion
conditions (the geometry
of the bob spring) are such that direct readings be
can
made of apparent
(in lbsjft2). Thus:
and plastic viscosity (in cp) and gel strengths
R600/2 = apparent viscosity
R600 - R300 = plastic viscosity
R300 - plastic viscosity = yield value (lbs/lOOft2)
10
20
30
40
50
Figure 20. Curveshowingtheeffect

of clayconcentration
on flow
properties of abentonitesuspensiondetermined
on a direct-reading
Fann viscometer.
56
Bentonite
Consistency curves obtainedfrom Fann viscometer If the rotor speeds

(= shear rate) are plotted against maximum
dial deflection at the
particular speed(= shear stress) then a consistency curve can be drawn
for a particular bentonite concentration. Figure
20 shows consistency
(or flow) curves for suspensions
of 5 , 6 and 7% bentonite
concentration. These curves well illustrate the Bingham flow nature
of
bentonite suspensions, i.e. that the suspensions only begin to yield
to an
applied stress above a finite value (the Bingham yield stress). This
is
conventionally measured by extrapolating the linear portion of the flow
curve to the horizontal axis.
Figure 21 shows the effect
of adding (a) calgon (a dispersing agent) and
(b) sodium carbonate to a 6% bentonite suspension. Calgon breaks
down the electrostatic (+ve edge
/ -ve face) interaction of the bentonite
of this the flow behaviour of
particles (cardhouse effect) and because
the suspension approaches thatof a Newtonian liquid (in other words
the suspension has been thinned). Sodium carbonate addition,
however, thickens the suspension and
apparent viscosity (R600/2)
increases. However, the slopeof the upper part ofthe flow curve does
not increase, i.e. theplastic viscosity remains the same. Bentonites
which are below drilling mud quality can be treated with sodium
carbonate to increase the apparent viscosity to meetOCMA
the
specification, but because of the yield point constraint they are unlikely
to meet the main API specification.
57
Bentonite
------77
10
30
20
40
50
Vip#nnaepdial&g
10
20
30
40
50
60
ViQiatrcatiing
Figure 21. Curvesshowing the effectof sodiumcarbonate(a)and

calgondispersingagent(b)
on flowproperties of 6% bentonite
suspension.
58
Bentonite
6.2.3Measurement of filtrate volume

This is measured on the suspension used
for viscosity determinations,
which is re-mixed for1 min and then immediately poured
into afiter
is the
press cell. The model most commonly used for laboratory tests
Baroid @area cell whichfilters over 21/2-in
a
diameter areaat 100
lb/in2. Filtration takes place overa 30-min period but only the volume
of filtrate emerging after the last 22.5 min is collected, multiplied
by 2,
and matched to specification.
6.3 Iron ore pelletizing
As in foundry sand applications, testinga bentonite for iron ore

pelletizing requires specialized equipment, therefore detailed methods
are not given in this manual. Tests are conductedby the industry on
iron ore pellets containing between
0.5 and 2% bentonite, these pellets
having been formed bya process that simulates the actual process
as
closely as possible (Aueret al., 1978; Bankset al., 1962). The green
drop test involves dropping each of 10 freshly prepared pellets a
distance of 18 in on to a steel plate until it breaks; the drop number is the
average number of drops before breaking. Green, dry and fired
compressive strengthsof the pelletsmay be measured witha standard
foundry compression apparatus equipped
for pellets, or with a specially
designed pellet tester. Pellets are dried at 105C for
dry testing, and
heated to 1300C and cooled or fired strength determinations.
An
important test of the dried and fired pellets
is the 'tumble index', where
they are rotated ina drum for 200 revolutions at24 rpm; the percentage
of material retained ona designated screenis the tumble index.
As well as acting asa binder, the bentoniteis required to absorb excess

water that is not removed from the ore during processing. For this
reason, Na-bentonites having a high moisture adsorption capacity are
preferred by iron ore pelletizing companies and a minimum moisture
adsorption capacity is often specified. This can be determined using the
Enslin apparatus (White& Pichler, 1959) and a simplified test
procedure is givenby Auer & Thayer (1978).
59
Bentonite
6.4 Bleaching/decolourizing of oils

.
..
The use of acid-activated bentonite

in the physical and chemical refining
of fats and oils such as palm, coconut, soya bean and rapeseed is a
. .
widely accepted process (Morganet al., 1985). Evaluation of the
suitability of a bentonite for this application involves
two.operations:
0
response oftheclaytoacidtreatment;
measurementofthebleachingefficiencyoftheproductstowards
the raw oils.
Methods for laboratory acid-activation of bentonites and assessment

of
bleaching perfomance are given in Appendix9.
6.4.1 Acid activation
a
Although the laboratory procedure for acid activation

is relatively
simple, the optimization of activation conditions may abe
timeconsuming procedure in which a number of experimental parameters
must be adjusted. A small sampleof clay is heated under reflux with
sulphuric or hydrochloric acidsof known but varying strengths for
varying periods of time. Variation in acid type, strength, and reflux
time will affect the degree of activation of the clay (Appendix
9).
Considerable difficulties maybe encountered in trying to optimise these
conditions. Relatively high concentrations of acid might be necessary
if
the clay was knownto contain calcite.
6.4.2 Measurement of bleaching efficiency
Bleaching efficiency of a bentonite can

be measured in the laboratoryb
mixing heated palm oil with
a small amount of activated
earth for afme
time period. The change in red colour of the filtered
oil is then measured
using a Tintometer. Using the decrease
in red colour as a guide, the
be identified. Usually
most appropriate acid strength for activation can
there isa very rapid initial development of good bleached colour as acid
strength increases, followed
by a slower improvement at higher levels
of treatment; bleaching properties can deteriorate above
a certain acid
level due to breakdown of the pore structure
of the clay.A summary of
60
Bentonite
the relationship between acid activation and bleaching performance of

bentonites is given in Appendix.
9 and also in Taylor& Jenkins (1986).
Bleaching earths perform many functions besides the removal of
coloured impurities from the oils and fats and thus the above
is only
test
a preliminary indication of suitability. Comparison of bleaching
performance of the activated clay with that
of a commercial product isan
essential part of the testing procedure.A variation of the test applied to
mineral oils involves heatinga mixture of oil and4% clay at23OOC for
15 min, filtering, and measuring the transmittance
of the oil.
6.5 Absorbents
A standard test for water absorbency of bentonites for use in pet litter
applications has been developedby MNOR (the National Standards
Organisation of France). Details of a water absorbency test based on
this standard are given in Appendix10. Typical values for bentonite are
100-140%. However,the suitability of materials for materials usedfor
how
pet litter isnot a function of moisture absorption alone, but also on
moisture absorption takes place, and also on odour absorption.
Bentonite-based pet litters tend to clump when moisture absorption
takes place. This allows the clogged lumpsto be removed, giving a
lower overall consumption rate compared to other clay granules used for
this purpose such as sepioliteor attapulgite.
61
Bentonite
REFERENCES
Adams J M (1987) Synthetic organic chemistry using pillared
cation-exchanged and acid-treated montmorillonite catalysts- a review.
Appl. Clay Sei. 2, 309-342.
of low grade
Alther G R (1982) Improvement of drilling mud properties
bentonites by simultaneous chemical activation and compaction.
Interceram 5,501-503.
Alther G R (1986) The effectof the exchangeable cations on the
physico-chemical propertiesof Wyoming bentonites.Appl. Clay Sei.1,
273-284.
American Petroleum Institute (1990)
Specificationsfor Drilling Fluid.
(Spec 13A, 1 July 1990).
Auer D L & Thayer R L (1978) Bentonite update: production, reserves,
quality control and testing.
SOC.Min. Eng. AIME preprint 78-B-59
( I 978 meeting) 8 pp.
Bain D C & Smith B F L (1987) Chemical analysis. 248-274in: A
Handbook of DeterminativeMethods in Clay Mineralogy (M J Wilson,
editor). Blackie, Glasgow & London.
Bain J A (1971) A plasticity chart asan aid to identification and
assessment of industrial clays. Clay Miner. 9, 1-17.
Banks G N, Campbell R A & Viens G E (1962) Iron ore pelletizing- a
literature survey. Trans. Can. Min. Metall. SOC. 65,428-433.
Bath A H (1993) Claysas chemical and hydraulic barriersin waste
disposal: evidence from pore waters. 3 16-330 in: Geochemistry of
Clay-PoreFluid Interactions. (D A C Manning,P L Hall & C R
Hughes, editors).Chapaman & Hall, London.
Brandenburg U & Lagaly G (1988) Rheological propertiesof sodium
montmorillonite dispersions. Appl. Clay Sei. 3, 263-279.
62
Bentonite
British Casting Industries Research Association

(1985) Broadsheets on
Test Proceduresfor Moulding Sand. BCIRA, Alvechurch, Birmingham
B48 7QB, UK.
British Standards Institution (1990)
Soilsfor civil engineering
purposes, BSS 1377 Part 2.
Bucher F & Muller-Vonmoos M (1989) Bentonite as a containment
barrier for the disposalof highly-radioactive wastes. App. ClaySei. 4,
157-177.
Carter D L, HeilmanM D & Gonzalez F L (1965) Ethylene glycol
monoethyl etherfor determining surface area of silicate minerals.
Soil
Sci. 100, 356-360.
Elzea J M & Murray H H (1990) Variationin mineralogical, chemical
and physical properties of the Cretaceous ClaySpur bentonite in
Wyoming and Montana (USA). Appl. Clay Sci. 5,229-248.
Galan E, Alvarez A & Esteban M A (1986) Characterizationand
technical propertiesof a Mg-rich bentonite.Appl. Clay Sci.1,
295-309.
Gamiz E, Linares J & Delgado, R (1992) Assessmentof two Spanish
bentonites for pharmaceutical uses. App. Clay Sci. 6, 359-368.
Griffiths J (1990) Acid-activated bleaching clays. Ind. Miner. 276. 5567.
Grim R E & Guven N (1978) Bentonites: Geology, Mineralogy,

Properties and Uses. Developments in Sedimentology.24, Elsevier.
Harben P W & Bates P L (1984) Clays. Pp 62-89 in:Industrial
Minerals: Geology and World Deposits. Metal Bulletin, London.
Harries-Rees K (1993) Minerals in waste and effluent treatment.
Ind.
Miner. 308, 29-39.
Highley D E (1972) Fullers Earth. Miner. Resour. Consult. Comm.
Mineral Dossier3. HMSO, London.
63
Bentonite
Inglethorpe S D J (1990)A visit to San Jose,Costa Rica, to

demonstrate laboratory methods for assessing bentonites.
Tech. Rep.
Brit. Geol. Surv. WG/90/22R.
Jones T R (1983) The properties and uses
of clays which swellin
organic solvents. Clay Miner. 18,399-410.
Kellomaki A, NieminenP & Ritmaki L (1987) Sorption of ethylene
glycol monoethyl ether on homoionic montmorillonites.
Clay Miner.
22, 297-303.
Low P F (1980) The swellingof clay: II. Montmorillonites. Soil Sci.
SOC.Am. 44, 667-676.
Mackenzie R C (1970) Simple phyllosilicates based on gibbsiteand
brucite-like sheets. Pp 498-534 in:Differential Thermal Analysis I (R
Mackenzie, editor). Academic Press.
Moorlock B S P & Highley D E (1991) An appraisal of fullers earth
resources in England and Wales.Tech. Rep. Brit. Geol.Sum.
WG/9 1/75
Morgan D J (1978) Evolved gas analysis of minerals and natural mineral
mixtures. J. Thermal Anal. 12,245-263.
Morgan D A, Shaw D BySidebottom M J, SoonT C & Taylor R S
(1985) The function of bleaching earths in the processing of palm, palm
kernel and coconut oils. JAOCS 62,292-299.
Nevins M J & Weintritt D J (1967) Determination of cation exchange
capacity by methylene blue adsorption.Am. Ceram. SOC. Bull.
46,
587-592.
Newman A C D & Brown G (1987) The chemical constitution
of clays.
Pp 1-128 in:Chemistry of Clays and Clay Minerals (A C D Newman,
editor). Mineralogical Society, London.
Odom I E (1984) Smectite clay minerals: properties and uses.
Phil.
Trans. R. SOC.Lond. A 3 l l , 391-409.
64
Bentonite
Parkes W B (197 1)Clay-Bonded FoundrySand. Applied Science

Publishers, 367 pp.
Pusch R (1992) The useof bentonite in the isolation
of radioactive
waste products. Clay Miner. 27, 353-361.
Ross J S (1964) Bentonite in Canada. Dept. Mines & Techn. Surv,

Ottawa, Monograph 873.
Santarkn J (1993) European market developments
for absorbent clays.
Ind.Miner. 304. 35-47.
Singer A & Galan E (1984) Palygorskite and Sepiolite:Occurence,
Genesis and Uses. Developments in Sedimentology.37. Elsevier.
StephensH A & Waterworth A N (1968) Significance of exchangeable
cation in foundry bentonite. Brit. Foundryman May, 202-219.
Taylor R K (1985) Cation exchange in clays and mudrocks.
J . Chem.
Biotechrzol. 35A, 195-207.
Taylor D B & Jenkins D B (1986) Acid activated clay.Am. SOC.Min.
Eng. Mtng.Preprint 86-365.
Van OlphenH & Fripiat J J (1979) Data Handbookfor Clay Materials
and other Non-MetallicMinerals. Pergamon Press.
Vista R L (1992) Clays. Annual Report 1990, US Bureau of Mines.
White W A & Pichler E (1959) Water sorption characteristics of clay
minerals. Illinois State Geol. Sum. Circular 266.

0 NERC 1993
65
Bentonite
Appendix 1: Release of exchangeable cations from

bentonite by ammon.ium acetate leach
Apparatus & reagents
50 ml graduated centrifuge tube

100ml volumetric flask
1 litre volumetric flask
Magnetic stirring plate/magnetic followers
Centrifuge
Balance 0.01 g readability, 1 kg approx. capacity
Ammonium acetate, analytical grade
Distilled/deionised water
Method
1.
Dissolve 75 g of ammonium acetate in 1 litre of water.Check

that pHof solution is neutral(7) and adjustwith a dilute acidor
alkali if necessary.
2.
Weigh out 1 g of clay into a centrifuge bottle. Add a magnetic

follower.
3.
Add 30 ml of 1M ammonium acetate solution and stir the

suspension on a magnetic stirring plate
for 30 minutes.
Centrifuge for15 minutes at 2000 rpm approx. Decant the
supernatent liquid into 100
a ml volumetric flask (leach
solution).
4.
Carry out the operation described in step 3 three times in total.
5.
Make the leach solution in the volumetric flask up to the 100ml

mark with distilled water.
66
Bentonite
Appendix 1 (continued)
6.
Determineexchangeablecationconcentration(Ca, Mg, Na, K)

of an aliquot of the leach solution using standard chemical
methods (e.g. inductively-coupled plasma optical emission
spectroscopy [ICP-OES]or emission flame photometry/atomic
absorption spectroscopy).
NOTE
Gypsum, calcite and dolomiteare all to some extent solublein ammonium acetate
solution and therefore can produce erroneous exchangeable Ca and Mg results. If
these minerals are suspected be
to present then a barium
chloride/triethanolaine
2 for preparation) should be substituted for ammonium
solution (see Appendix
can notbe determined
acetate as the leach solution. However, exchangeable Na Kand
using the latter solution
as barium chloride contains significant amounts both
of
these elements. Therefore, if either carbonates
or gypsum are present, two
determinations may need to be carried out using different leach solutions: an
K and a bariumchloride/triethanolamineleach for
ammonium acetate leach for Na,
Ca and Mg.
Calculation
~2
= (V
* C)/(10000 * M1)
= C/lOO
CEC [meq/lOOg]
= (M2/A)* 1000
M2:
V:
M1:
C:
A:
Exchangeable cation content of clay [%]

(M2 is sometimes quotedas mass of exchangeable cation (g) per
100 g of clay)
Volume of solution [ml] = 100
Mass of clay [g] = 1
Cationconcentration in solution[ppm]
Atomicmass of cation [ m u ]
67
Bentonite
Example
C
M2
= 230 ppm Na
= C/lOO
= 2.3% exchangebleNa content [2.3g exchangeable Na per
100 gof clay]

A
= 23
CEC = (M%/A)*l000
= 100 meq/100 g
68
Bentonite
Appendix 2: Cation exchange capacity (BaCIz/MgS04

method)
Equipment & reagents
250 ml wide-necked polythene bottles
250 ml measuring cylinder
5 ml pipette
100 ml pipette
Magnetic stirring plate+ magnetic foliowers
Centrifuge
pH meter (+ pH calibration solutions)
Analytical balance, 200g capacity, 0.1 mg readability
100 ml conical flask
50 ml burette
100 ml stoppered flaskbottle
PTFE/glass rod
Distilled or deionised water
Triethanolamine, general purpose reagent
(GPR) quality
Barium chloride dihydrate (BaC12.2H20), analytical (Analar) quality
Magnesium sulphate heptahydrate (MgS04.7H20), Analar quality
Ammonium chloride,Analar quality
Ammonia 880 solution (specific gravity0.88)
Solochrome black6B
Ethanol, GPR grade
Concentrated hydrochloric acid (HCl) solution, Analar quality
Di-sodium EDTA (ethylene-diamine-tetra-acetic-acid), Analar quality
Preparation of solutions
1.
Dilute (2M) HC1 solution: slowly add 18 ml of concentrated HCl to

75 ml of distilled water (Caution: DO
NOT dilute by adding water
to concentrated acid, always dilute
by adding concentrated acid to
water). Dilute to100 ml with moredistilled water.
2.
Triethanolamine solution: dilute90 ml of triethanolamine to 1 litre

with distilled water. Add dilute(2M) HCl (approx.180 ml) until a
69
Bentonite
pH value of8.1 is obtained and dilute to 2 litres with distilled

water.
3.
2M barium chloride solution: dissolve244 g of BaC12.2H20 in 1

litre of distilled water.
4.
Buffered barium chloride solution:

mix equal volumes of barium
chloride and triethanolamine solutions.
5.
0.02 M EDTA solution: dissolve 3.723 g of disodium EDTA in

1
litre of distilled water,or use ampoules of concentrated EDTA
solution available commercially (e.g.BDH Convol) and dilute
according to the manufacturers instructions.
6.
Ammonia buffer: dissolve g7 of ammonium chloride in 57

ml of
ammonia 880 solution, and make up to100 ml with distilled
water (caution: carry out in
a fume cupboard and DO
NOT inhale
fumes from ammonia880 solution).
7.
Indicator: dissolve 0.25g of Solochrome Black6B in 50 ml of

ethanol.
Method
1.
Weigh 5 g of sample into a250 ml polythene bottle and add

a
magnetic follower.
2.
Note weight of bottle and contents

(MI).
3.
Add 100 ml of buffered barium chloride solution and agitate

mixture for1 hour on a magnetic stirring plate. Ensure that
all the
sample is dispersed
- it may be necessary to dislodge some of the
sample usinga PTFE/glass rod. This stage can be omitted
if
samples are non-calcareous and non-saline.
4.
Centrifuge at 1500 rpm for 15 minutes and discard the supernatant

(if it is difficult to remove the majority
of the solutionby
decantation then removeby a suction method instead).
70
Bentonite
5. Add a further 200 ml buffered barium chloride solution, agitate the

mixture for 1 hour on magneticstining plate and then leave
overnight.
6.
Centrifuge at 1500 rpm for 15 minutes and discard the supernatant.
7.
Add 200 ml of distilled water and agitate for afew minutes on a

magnetic stirring plate. Centrifuge at 1500rpm for 15 minutes and
discard the supernatant.
8.
Note weight of bottle and contents (M2).
9.
Pipette 100 ml of MgS04 solution into the bottle, mix well and
leave for approx.2 hours, occasionally agitating on magnetic
stirring plate.
10. Centrifuge at 1500 rpm for15 minutes and decant the supernatant
into a stoppered flask or bottle.

11. Pipette a 5 ml aliquot of this solution into a 100ml conical beaker
and add 5ml of ammonia buffer, plus6 drops of indicator.
12. Titrate with standard EDTA (titre A1 ml).

13. Titrate a 5 ml aliquot of 0.05 M MgS04 solution (titre B ml). The
end-point is indicatedby a blue to pink colour change.
Bentonite
Calculation(s)
The titration end-point(Al) must be corrected for the volume
of residual
water (retainedby the sample after washing with distilled water). The
corrected value (A2) can then beused to calculate theCEC value.
CEC = 8(B-A2)
-
meq/lOO g
M1: weight of bottle plus dry contents (g)

M 2 : weight of bottle plus wet contents (g)
A2: corrected end-point = [A1*( lOO+M2-M1)]/100ml
Al:
titrationend-point of sample (ml)
B:titrationend-point
of MgS04 solution (ml)
M1
Wt of bottle
+ contents
Sample code DRY
(8)
M2
Wt. of bottle
+ contents
WET
(8)
M2
M1
Wt. of residual
water
(8)

0 NERC I993
A1
Titration
end-point
(ml)
A2
72
-~
Bentonite
Appendix 3: Determination of methyleneblue

exchange capacity
cation
Equipment, reagents& materials

500 ml plastic screw-top bottle
Analytical balance,lmg readability, 200 g capacity
Drylng oven set at 105-110C
50 ml burette
100 ml flask
Glass stirring rod
541 filter paper
1 litre volumetric flask
Crystalline methylene blue chloride dye
5 M sulphuric acid solution
Air-dried clay ground to approximately
4 2 5 pm
Determination of dry weight of clay samples and methylene blue

chloride
1.
Label a small aluminium dish with sample code and weigh.

[Record asA.... weight of dish]
2.
Weigh out 1 g of sample (clay or methylene blue) into the dish.

[Record asB....weight of dish + sample before drying]
3.
Place in a 105C oven and leave overnight. Weigh again the

following morning. [Record asC.... weight of dish +sample
after drymg
J
Preparation of 1 litre of nominally 0.01 M methylene blue chloride

solution:
1.
Weigh out 3 g of methylene blue. [Record as D.... actual

weight of methylene blue]
73
Bentonite
2.
Place in a 1 litre volumetric flask and add approximately 250 ml

of warm distilled water (alternatively add
250 ml of cold distilled
water and warm usinga water bath).
3.
Gently agitate flask until all the dye has dissolved and no solids
remain on floor of flask. Allow to cool and add distilled water
up to the 1 litre mark.
Determination of CEC value

1.
Weigh out 1.5 g of sample [record as E.... weight of sample as

received] and place ina wide-necked plastic screw-topped
bottle. Add 20 ml distilled water and disperse the sample
by
agitating for1-2 hours in a reciprocal/end-over-endorbital
shaker. Leave overnight.
2.
Using as little wateras possible, wash contents of bottle into

100 ml flask, ensuring that all clay is transferred.
3.
Add 1 m15 M sulphuric acid: this stageis optional but increasing

acidity is believed to give a sharper titration end-point.
4.
Add 2 ml of the nominally0.01 M methylene blue chloride

solution from a 50 ml burette and gently rotate the flask
to mix
the contents. After each
2 ml addition, place a drop of the
suspension onto a filter paper using a glass stirring rod
(spotting). Repeat until the end-pointis reached.
5.
Spotting initially produces dstinct

a
dark blue spot of clayabsorbed dye surrounded by aclear halo of water. However,
near the end-point spotting produces adark blue spot of clayabsorbed dye surrounded by a pale blue halo of excess dye
(see Figure 12 in Section 5.2.1).
6.
When this pale-blue halois obtained leave to stand for

5 minutes
and then repeat spotting. Ifthe pale-blue halo disappears add a
further 2 ml increment of dye.
74
Bentonite
7.
If after 5 minutes the pale blue halo persists, allow to stand for a
further 20 minutes and repeat spotting.
If the pale bluehalo then
disappears cautiously add further dye.
8.
If the pale blue halo is still present after a periodof 25 minutes

then the end-point has been reached.
9.
Record volume of dye added at the end-point [F.... volume of

methylene blue]. Calculate the methylene blue cation exchange
capacity as shown, quoting the CEC value to the nearest whole
number.
NOTES
(i) Typical
CEC values for pure clay minerals obtained using the methylene
blue method are shown in Figure 13.
(ii) The resolution
of the method can be improved by changing to 1 ml
of the testis typically of
additions of dye near the end-point. Repeatability
the order of& 1 meq/lOOg.
(iii) The overall rate
of dye addition should be approximately30 ml of dye in 2
hours. An excessive rateof dye addition may produce
a premature end-point.
(iv) Moisture content can
be determined by a standard method if preferred, such
as Test 1(A)of British Standard BS1377: 1990.
(v) Maximum efficiency can
be achieved in this test by dealing with samples in
batches of 10-12.
75
Bentonite
Worksheets and calculations

Calculation of percentage dry weight of sample
% dry weight (Ps)
= [(C-A)/(B-A)]*lOO/l
A:
B:
C:
weight of dish
weight of dish + samplebeforedrying
weight of dish+sampleafterdrying
Calculation of concentration of methylene blue chloride solution

Concentration of methylene blue chloride solution (MBCONC)
= (D*PMB)/~
19.9
M
D
actualweight of methyleneblue(g)
PMB: % dry weight of methylene blue
Molecular weightof anhydrous methylene blue= 319.9
Calculation of cation exchange capacity(CEC) values
Ps:
percentage dry weight of sample

Concentration of methylene blue chloride solution
weight of sampleasreceived
volume of methylene
blue
MBCONC:
E:
F:

0 NERC 1993
76
Bentonite
Wt. of dish
Sample
(8)
P
B
C
Wt. of dish + sample Wt. of dish + sample Percentage dry weight
BEFORE DRYING A F E R DRYING
(wt.%)
(8)
(g)
a
LO
Methylene Blue

0 NERC 1993
77
Bentonite
Sample
~~~
F
E
PS
Wt. of sample Percentage dry wt, Volume of
Methylene Blue
as received
of sample
(ml)
(%I
(g)
5
7
78
Bentonite
Appendix 4: 2-ethoxyethanol (ethylene glycol

monoethyl ether [EGME]) surface area method
I

Rotary vacuum pump (e.g. Edwards model5 single-stage rotary pump)
Analytical balance, 200g capacity, 0.1 mg readability
2 glass or polycarbonate vacuum desiccators, small, approx. 15
cm
&meter, including desiccant traywith a perforated cover
10 Aluminium weighing dishes,6 cm diameter, labelled 1,2,3,4,5 &
A, B, c, D, E
Dropper pipette
8-16 mesh, fused, granular anhydrous calcium chloride (CaCl2),
desiccant, GPR grade (ground to
e100 mesh and storedin an airtight
container; canbe recycled after useby placing in 105C oven)
Anhydrous phosphorus pentoxide(P2O5), GPR grade
2-ethoxyethanol (ethylene glycol monoethyl ether, EGME), Analar
quality
Control sample - pure Ca-montmorillonite standard.
Method
1.Weighaluminiumdishtofourfigures.Recordweight
(Ml).
Add approximately 1.1g of clay. Record weight(M2). Repeat
this operation for a further
four clay samples, including the
control sample (in dishNo 3 orC).
2.
Place approx. 70 g of anhydrous phosphorus pentoxide in the

tray of the first desiccator and replace desiccant tray cover.
Arrange the five aluminium dishes in order
(1,2,3,4,5 or A,
B, C, D, E) around the circumference of the tray cover. Replace
desiccator lid ensuring that no dishes are placed directly below
air inlet valve.
3.
Evacuate for approx. 45 minutes and allow to stand for 3-4

hours.
Bentonite
4.Graduallyreleasevacuumby
SLOWLY openingair-inlet.Weigh
dishes as quickly as possible (M3, 1st weighing). Replace
immediately in desiccator and arrange the dishes
in order 3,4,5,
1 , 2 (or C, D, E, A, B) so that the control sampleis in the first
position. Evacuate for approx.45 minutes and stand overnight
under vacuum.
5.
Nextmorning,graduallyreleasevacuumandrapidlyweigh
dishes again(M3,2nd weighing). Immediately after weighing,
add approx. 3 ml of
EGME reagent to the dry clay in each dish
and transfer samples to second desiccator containing
dry calcium
chloride desiccant. Arrange &shes
in original order around
circumference of the desiccant tray cover. Replace desiccator lid
and allow to stand for1-11/2 hours. Evacuate for approx 15
minutes with air-ballast settingof vacuum pump turned on, then
evacuate for a further 45 minutes
with the air ballast turned off.
Allow to stand overnight under vacuum.
6.
Nextmorning,graduallyreleasevacuumandweighdishes
rapidly (M4).
Mineralogy and Petrology Group, British Geological Survey 0 NERC I993
80
Bentonite
Calculation
M1
M2
M3
M3
M4
K
Weight of dish(g)
Weight of dish + sample(8)
Weight of dish + dry sample (1st weighing) (g)?
Weight of dish + dry sample (2nd weighing) (g)?
Weight of dish + dry sample + 2-ethoxyethanol (g)
Weight of EGME required to form a monolayer over 1 m2 of
surface
= 2.86*10-4 g/m2
3.
Selectlowestvalue
of M3
NOTES
(i)Beforeattemptingroutinesurfaceareaanalysis
of samples, the surface area
of the control sample should be determined repeatedly (approx.
10-20
analyses) until a relatively stable surface area value
is obtained. This enables
calculation of an average surface area value
for the control sample.
If, during routine analysis of a batch of samples, the surface area of the
(ii)
surface area
control sample exceeds+lo m2/g of the average value then the
values of samples shouldbe multiplied by a correction factorX [X =
(average surface areaof control sample/measured surface area
of the control
sample)].
If, during routine analysis of a batch of samples, the surface area of the
(iii)
control sample exceeds+50 m2/g of the average value then theanalysis
should be repeated.
of samples can be calculated using the following
(iv) The moisture content
equation:
Mineralogy and Petrology Group,British Geological Survey 0 NERC I993
(9)
...Wt. of containersample
+ dry
weighlng
2nd
M3,
sample
wt. of dry
Surface area (m2/g) (above value divided by0.000286)
by
2-ethoxyethanol
divided
Wt.
M4...Wt . of container + dry sample + 2-ethoxyethanol (9)
(9)
... Wt. of containersample

+ dry
2
I s
l 4
I '
... Wt. of container t sample (9)
weighing
1stM3,
M2
M1.
~~~
~~
~~~~~
I tI *
~~~~~
.. Wt. of container (9)
Sample
Weighing
tor'>(') by (multiply
(m2/g) area surface
Corrected
description
dish
Worksheetforthe2-ethoxyelhanolsurfaceareamethod
l 4
1 3
I s
82
Bentonite
Appendix 5: Laboratory procedure for bentonite

swelling test

Analytical balance,0.01g readability, 200g capacity
6 watch glasses
6 10 ml measuring cylinders
Filter funnel
Drymg oven (60C)
Spatula
Analytical balance,0.01g readability, 200g capacity
Anhydrous sodium carbonate (Na2CO&analytical grade
Method
1.
Take seven4 g portions of 4 2 5 pm dry clay, and to six of

these add 1,2,3,4,5 and 6% by weight of sodium carbonate.
Gently grind the clays to
mix in the sodium carbonate, add1.5
ml distilled water andmix to apaste.
2.
Dry at 60C in oven overnight.
3.
Crush the clay gently and screen through

500 and 250 pn.
Weigh out 1 g of 500-250 pm material onto a watch glass.
4.
Fill a 10 ml measuring cylinder to the mark

with distilled water
and placea filter funnel
in the neckso that the tipis about 1cm
from the surfaceof the water.
5.
Divide the clay sample roughly into

8 portions with a spatula and
slowly add one portion every
5 minutes.
6.
of the cylinder to settle

After each addition, lightly tap the bottom
the clay. Thefinal surface of the clay shouldbe level.

0 NERC 1993
83
Bentonite
7.
Leave the sample for 24 hours and read the volume of the clay to
the nearest 0.1 ml. Multiply the resultby 10. Samples of good
10 ml. In such cases,
bentonite should swell in excess of
addition of clay should be stopped when the swollen clay
approaches the 9 ml mark. The amountof clay leftis then
,weighed and the swelling volume
for the total1 g calculated.
NOTES
(i)
Therelativequantities of clayandNa2CO3requiredtoobtain
& 6% concentrations in4 g of material are as follows:
% Na2C03
0
1
Wt. ofNa2C03 (g)

0
0.04
2
3
4
5
6
0.08
0.12
0.16
0.20
0.24
Typicalswellingvolumes(seealsoFigure
(ii)
Non-swelling material
Kaolinitic clays
UK Ca-bentonite:
+ 1% Na2C03
+ 2% Na2CO3
+ 3% Na2CO3
+ 4% Na2C03
+ 5% Na2C03
+ 6% Na2CO3
Natural Na-bentonite
(iii)
1,2,3,4,5,
Wt. of clay (8)

4
3.96
3 -92
3.88
3.84
3.80
3.76
13, Section 5.2.2):
10-12 ml
15-20 ml
25-35 ml
40-60 ml
50-90 ml
70-105 ml
70-130 ml
70-100 ml
70-90 ml
100-150 ml
Maximumswellingvolumesareobtainedwithhigh-gradeCa-bentonites
after artificial Na-exchange
with 4-5% Na2C03 additions.
84
Bentonite
Appendix 6: Laboratoryprocedurefor
the
determination of bentonite liquid limits
2 large palette knives
1 small palette knife
Wash bottle
500 ml beakers
Large watch glass
Casagrande apparatus/Cone penetrometer
Glass weighing bottles
Analytical balance,0.01 g readability, 1 kg capacity
Drying oven(110C)
Large square glass plate (400by 400 mm approx.)
Anhydrous sodium carbonate (Na2C03), analytical grade
Preparation of clay pastes

1.
Take six 100 g portions of d 2 5 m dry clay, and to five of these

add 1,2,3,4 and 5% by weight of sodium carbonate. Mix
thoroughly witha smallmount of distilled water on the glass
plate using the palette knives for at least
15 minutes to obtain a
stiff paste.DO NOT add an excessive amountof distilled water
as the resulting paste must be not be too fluid.
2.
Place each clay paste in a beaker, cover with a watch glass to

prevent evaporation and allow to 'age' overnight.
Determination of liquid limit:Conepenetrometer method

1.
Remove the clay paste from the beaker and work the clay on the
glass plate with the palette knives
for about 10 minutes.
2.
Place a portion of the clay into the cup with a palette knife taking
care not to trapany air. Strike-off excess clay with the straight
edge of palette knife to obtain a smooth level surface.

0 NERC 1993
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3.
Position the cupin the centre of penetrometer base plate. Lower

the penetration cone until the oftipthe conejust touches the
surface of the clay: if the cone
is correctly positioned a slight
movement of the cup willjust mark the surface of the clay.
Gently lower the dial gauge stem until
it contacts the topof the
cone shaftby using the INNER knobat the centreof the gauge.
Set the dial gauge reading to zero by adjusting
OUTER
the knob
at the centreof the gauge.
4.
Release the conefor a period of5 seconds using either the

automatic or manual release
(if using manual release, avoid
jarring the instrument during this action). After locking the cone
in position, gently lower the dial gauge stem ituntil
contacts the
top of cone shaft
by using the INNER knob at the centre
of the
gauge. Record the gauge dial reading (penetration depth)
to the
nearest 0.1 mm.
5.
If penetration depthis less than 15 mm, add more water to the

clay and repeat steps2-4. If the penetration depthis greater
than 15 mm proceed to step6.
6.
Repeat steps2-4 until two subsequent dial readings are within

+1 mm. This ensures consistent results.
7.
If the conhtions in step6 are satisfied remove a small amount of

clay paste(10 g approx.) from the area penetrated the
by cone
and place in a weighing bottle (mass
M1) and replace airtight lid.
Weigh the bottle containing the wet clay (mass
M2).Open the lid
and place overnight in an105OC oven. The bottle plus
dried clay
is then weighed the following morning (mass
M3). Moisture
content is then calculated as percentage ofdry
themass of
sample (see worksheet).
8.
Repeat steps 1-7 at least three more times adding additional

increments of distilled water. Mix very thoroughly each time
more wateris added. Amounts of water added should be such
that penetration valuesin the range15 mm to 25 mm are
obtained. Moisture content/penetration depth co-ordinates are
plotted on the graph paper on the worksheet and
are then
connected by a straight line best fit (the flow curve).
9.
The liquid limit is reported as the moisture content, expressed to

the nearest whole-number, corresponding atopenetration depth
of 20 rnrn on the f l ~ w
curve.
Mineralogy and Petrology Group, British Geological Survey 0 NERC 7 993
86
Bentonite
Determination of liquid limit: Casagrande method.

1.
Remove the clay paste from the beaker and work the clay on the
glass plate with the palette knives
for about 10 minutes.
2.
Place a portion of the remixed clay in the cup of the Casagrande

apparatus and level-off parallel to the base
of the apparatus,
ensuring that there are
no entrapped air bubbles. Carefully draw
the grooving tool supplied through the paste, keeping
it noma1
to the surfaceof the cup withthe chamfered edge facing the
direction of movement.
3. Having first ensured that the counter

is set to zero, steadily turn
the crank at the rate two
of revolutions per second until the paste
at the bottom of the groove
closes up over a lengthof 13 mm.
This distance may be measured with a ruler
the or
end of the
grooving tool. Record the number
of bumps at which this
occurs.
4.
If the number of bumps is greater than 50, add more water to the
clay and repeat steps2 and 3. If the numberis less than50
proceed to step6.
5.
If the conditions in step 4 are satisfied remove a small amountof

clay paste(10 g approx.) from the area of the groove and place
in a weighing bottle (mass M1) and replace airtight lid. Weigh
the bottle containing the
wet clay (massM2).Open the lid and
place overnightin an 105C oven. The bottle plus dried clay
is
then weighed the following morning (mass M3). Moisture
content is then calculatedas percentage of thedry mass of
sample (see worksheet).
6.
Repeatsteps 1-5 atleastthreemoretimesaddingadditional

increments of distilled water. Mix very thoroughly each time
more wateris added. Amounts of water added should be such
that bump valuesare evenly scattered above and below
25.
Bump values ofless than 10 are discounted. Moisture
content/bump value co-ordinates
are plotted on the semilogarithmic graph paperon the worksheet and are then connected
by a straight-line bestfit (the flow curve).
87
Bentonite
7.
The liquid limit is reported as the moisture content, expressed to

the nearest whole-number, corresponding to
25 bumps on the
flow curve.
NOTES
(i) The results obtained by using the two methods
do differ (see Section 5.2.2).
Where the liquid limit is less than 100 differences are not considered
significant as theyare within the normal variation typically obtained using
the Casagrande method. However, for liquid limit values above 100 the cone
penetrometer methodis known to giveLOWER values in comparison to the
Casagrande test. Because high-grade bentonites have liquid
limit values
>>lo0 it is therefore important to record which
of the methods was used
when quoting results.
(ii)Typicalliquidlimitvalues(determinedusingtheCasagrandemethod):
clay)
(ball
kaolin
UK plastic
61
UK mixed-assemblage
clay
(common
clay-26%
smectite)
84
UK commercial
Ca-bentonite,
S teetley
Berkbond
1
150-200
Commercial Ca-bentonites, artificially Na-exchanged (alkaline
treated):
SteetleyBerkbond2(Wobum,
UK, partiallyNa-exchanged)
250-300
Steetley
Berkbent
D.M. (drilling
grade)
mud
300400
Steetley
Berkbent
(civil
engineering
C.E. grade)
400-450
(Ponza,
Berkonite
Steetley
Italy)
500-600
Natural Na-bentonite:
bentoniteyAquage1
Wyoming
600-700
Steetley

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Bentonite
LIQUID LfMIT: CONE PENETROMETER METHOD

Sample ...........................
Remarks
..........................
Operator .........................
Date ................
Penetration depth (mm)
Liquid limit worksheet (Cone penetrometer method)
89
LIQUID LIMIT: CASAGRANDE METHOD

Operator .........................
Sample ...........................
Remarks ..........................
Date ................
Determination No.
Bottle No.
M1 ...
Mass.ernpty bottle (9)
Mass water (9)=M2-M3

Mass dry clay (9)=M3-M1
Moisture content (VO)
(M2-M3)I(M3-M1)'100
Number of blows
10
1s
Number of bumps
20
LO
Liquid limit worksheet (Casagrande method)
so
90
Bentonite
Appendix 7: Determination of plastic limit and

plasticity index
Wash bottle
Glass weighing bottles
Analytical balance,0.01 g readability,1 kg capacity
Drying oven(1 10C)
(400 by 400 mm approx.)
Large square glass mixing plate
Polished glass test plate
Metal or glass rod,3 mm diameter, approx.100 rmn length
Method
1.
Take a sub-sample of approx 20 g of clay and place on mixing

plate. Using your hands mix water with the sample until a plastic
ball can be formed.
2.
Mould the ball between the fingers and roll it between the palm
of the hands until the heat
of the hands hasdried the clay
sufficiently for slight cracks to appear on the surface.
3.
Divide the ball into two sub-samples and set one of these aside.
4.
Divide the remaining sub-sample into four equal parts and carry
out steps5-8 separately on each part
5.
Mouldtheclayusingthefingerstoequalizethemoisture
distribution. Fom the clay into a thread
of about 6 mm diameter
between thefirst finger and thumb
of each hand.
6.
Roll the thread between the fingers of one hand (from the
fingertips to the second
joint) and the surface of the glass test
plate. Use enough pressure to reduce the diameter
of the thread
from 6 mm to 3 mm in five to 10 complete forward-and-back
hand movements. Use the rod to gauge the thickness
of the
thread. All clays tend to harden near the plastic limit; some
heavy clays may require
10-15 movements. It is important to
91
Bentonite
maintain uniform rolling pressure:

do not change hand pressure
as the thread diameter approaches
3 mm.
7.
On completing the operation in step 6, pick up the clay thread

and mould using fingers to
dry the clay further. Gradual drying
is carried outby alternately rolling on the test plate and moulding
with the fingers. Continual rolling should not
be attempted as
this only dries the surface
of the clay. Reform the clay into a ball
as described in step 5.
8.
Repeat steps 6 and 7 until the thread shears (cracks) both

longitudinally and transversely when it has been rolled to about
3 mrn diameter. Gather the cracked portions of clay and transfer
to an airtight bottle (mass M1)and replace the lid immediately.
9.
Carry out steps 5-8 on each of the four portions of the clay,
placing all the cracked pieces of clay obtained into the same
airtight bottle. The bottle and its moist clay contents is then
weighed (massM2). After opening lid of bottle, place overnight
in an 105C oven. The bottle and
Bry clay is then weighed the
following morning (mass
M3). Results can be recorded on the
liquid limit worksheets and the moisture content then calculated.
10.
Carry out steps 4-9 on the remaining material.
11.
Calculate the average of the two moisture contents obtained and

express to the nearest whole number. This
is the plastic limit.
12. The plastic index

(PI) can be calculated by subtracting the plastic
limit (PL) from the liquid limit(LL).
NOTES
(i) Test should be carried out on a polished glass surface.
If possible use
separate plates for mixing and testing as discrepancies will result from use
of a textured or scratched glass surface.
(ii)
If moisture content of each sub-sample differs by more than +I% repeat the
test.
92
Bentonite
Appendix 8: Determination of drilling fluid properties

Drylng oven set at 1O5"-11O0C
Balance, 0.01 g readability,1 kg load
High-speed mixer: e.g. Hamilton-Beach type, 11000rpm, single
corrugated impellerof approx. 25 mm diameter
Direct-reading couvette type viscometer: e.g. Model
35s Fann V-G
viscometer
Filter-press: e.g. NL Industries/Baroid Division1/2 area filter press
(includes 'sparklet' typeC02 bulbs, filter paper and 10
ml measuring
cylinder)
Wire cloth sieve, approx.
80 mm diameter, 75 pm aperture
Water spray nozzle attached to water line, water pressure ideally
regulated at 10 psi
Evaporating basins
Spatula
Stirring rod
500 ml measuring cylinder
500 ml beaker and watch glass
Anhydrous sodium carbonate (Na2CO3), analyticalgrade
Sodium hexametaphosphate 'Calgon' GPR grade
IMPORTANT NOTE: prior to carrying out this test the

% dry weight of
sample and optimum %Na2C03 at maximum swelling volume need to
be determined (see methylene blue cation exchange capacity method and
swelling volume test method respectively).
Mineralogy and PetrologyGroup,British Geological Survey 0 NERC f 993
93
Rheological properties
1.
Calculate the weight of ground clay and weight of Na2CQ

required for test (see calculations and worked example).
2.
Add 400 ml of water from measuring cylinder

to cupof highspeed mixer. Turn mixer on
and add theground clay and sodium
carbonate (in total 25.7 g).
3.
Turn off mixer after5 minutes and dislodgeany bentonite

adhering to sidesof cup using astimng rod.
4.
Turn on mixer and continue stirring

for an additional 15 minutes
(total mixing time of20 minutes).
5.
Transfer the suspension to 500

a ml beaker, cover with a watch
glass and allow to age overnight (16 hours).
6.
The following day, place the suspension

in mixer and stir for a
further 5 minutes.
7.
Pour the agitated suspension into viscometer test cup up to the

350 ml line inscribed inside the cup. Raise cup, immersing the
viscometer rotor sleeve and bob until the inscribed
line
on rotor
sleeve is level with the top of the suspension.
8.
Set viscometer rotor sleeve running

at 600rpm and record dial
reading at consecutive5 minute intervals. A stable readingis
indicated by two consecutive readings within 0.5 centipoise.
A good quality bentonite may take up30tominutes to stabilize
at 600 rpm [record value as 86001.
9.
Repeat step 8 with rotor sleeve running at300 rpm [record value
as 83001. The suspension should stabilize more quickly at
lower speeds. Calculate apparent viscosity (a.v.), plastic
viscosity (P.v.), yield value (Y.v.) and API specification values.
10.
(OPTIONAL) If, in additionto API specifications, a complete

consistency curve is required, repeat step
8 with rotor sleeve
running at consecutive settingsof 200, 100,6 and 3 rpm and
record dial readings [record as8200,e 100,06 and 831.
11,
(OPTIONAL) Determine gel strength as follows. Stir sample at

600 rpm until dial reading stabilizes. Turn viscometer off for 10
94
Bentonite
seconds and then switch to

3 rpm. Record maximumdial
reading which occurs at the instant of gel break [record value
as
e310set]. Repeat but this timeturn off the viscometer for10
minutes instead of10 seconds [record value as
8310muJ.
Filtrate volume of suspension
1.
Using the suspension preparedin method (A), stir suspension

for one minute using high-speed mixer.
2.
Pour the suspension into the rubber boot of the 1/2 area filter
press to within approx. 13 mm of the top. Place filter paper on
top of boot and screw-in bottomlidscreen assembly tightly
(ensure that gaskets are not distorted or worn and that screen
is
clean and dry). Mount 1/2 area pressin upright position and
place 10ml measuring cylinder under drain hole.
3.
Start timer: within 30 seconds close the air-vent valve and adjust
the gas regulator to100 25 psi.
4.
Wait for7.5 minutes and then empty the measuring cylinder

of
the water collected. Itis not necessary to record the volume of
water collected during the first
7.5 minutes.
5.
Immediately replace empty measuring cylinder and restart timer.

Continue the test fora further 22.5 minutes and record the
volume of water collected [record
as volume of filtrate].
6.
Calculate the filtrate-relative 30 minutes value as specified

in
Calculations section below.

0 NERC 1993
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Bentonite
Wet screen analysis

1.
Measure out 350 ml ofwaterusing a measuring cylinder. Add

350 ml of water tocup of high-speed mixer. Turn mixer on and
add log of bentonite and0.2g of calgon. Stir on mixer for
30
minutes
2.Agesuspension
for approx. 2 hours.
3.
Re-stir for 5 minutes and transfer suspension to the 75 pm

sieve. Wash the material on the screen for
2 minutes using water
from the spray nozzle set at approx.
10 psi.
4.
Transfer the >75 pm sieve residue into an evaporating dish and

dry in oven.
5.
Remove residue from ovenandweigh(recordasweightof>75

pm sieve residue.
6..
Calculate residue greater than 75 pm value as specifiedbelow.
Calculation of weight of ground clay and weight of sodium carbonate

required for test (includinga worked example)
Weight of gound clay (as received) required for test
= (100/ps) * (25.7 - [ 25.7 * %Na/100J)
Weight of Na2C03 required for test
= (%Na/100) * 25.7
Ps
percentage dry weight of sample
%Na optimum %Na2CO3 to obtain maximum swelling volume
(see methylene blueCEC and swelling volume methods respectively)
Mineralogy and PetrologyGroup, British GeologicalSurvey 0 NERC 1993
96
Bentonite
Example:
= 90%
%Na = 5 %
PS
Weight of ground clay(as received) requiredfor test

= (100/90) * (25.7 - [ 25.7 * 5/100])
= 27.128 g
Weight of Na2C03 required for test
= (5/100) * 25.7
= 1.285 g
Is this correct ?
check calculation as follows:
Weight of ground clay( d r y weight) + weight of Na2C03 should

= 25.7 g total
Equivalent weight ofdry clay
= 27.128 * 90%
= 24.415 g
Weight of Na2C03
= 1.285g
Total = 24.415 + 1.285

= 25.7 g Total correct!

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Bentonite
Calculation of rheological properties

Apparent viscosity (a.v.) [centipoise]
= e600/2
Plastic viscosity (P.v.) [centipoise]
= e600 - e300
Yield value(Y.v.) [lbs/100 sq ft]
= e300 - P.V.
8310 see= 10 second gel strength (as recorded)
8310mh= 10 minute gel strength (as recorded)
Filtrate-relative 30 minutes [cm3]
= 2 * volume of filtrate
Residue greaterthan 75 pm [%J
= (100 * weight of >75 pm sieve residue)/lO
Moisture [%]
= 100-Ps
8600: 600 rpm dial reading
86300: 300rpm dial reading
86:
6 rprn dialreading
83:
3 rprn dialreading
Ps:percentage
dry weight of sample

0 NERC 1993
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Bentonite
Appendix 9: Mechanism of acid activation and

assessment of bleaching performance of bentonite
for use in edible oil clarification
9.1 Background
Acid activationof bentonite is carried out commercially to provide

material for for three main applications:
e
0
Refining
oils,
fats
and
solvents
Catalysis
Colourdevelopersfordyesimpregnatedincarbonlesscopy
paper.
Further details are givenin Table 9.1. This account will deal only with
acid-activation of smectite- the clay constituent of bentonite
- for edible
oil clarification; descriptionsof smectite-catalysed reactions are given by
Atkins et al. (1983) and Gregoryet al. (1983), and the use
of smectite
in carbonless copy paperis excellently described byFahn & Fender
(1983).
The refiningof vegetable and animal oils
for edible purposes involves
the removalof a variety of impurities which include phosphatides, fatty
acids, gums and trace metals, followed
by decolourization and
deodourization. The various stagesin the edible oil refining process are
shown in Figure 9.1. It is the purification and decolourization stage that
employs an acid-activated bleaching earth which is later removed
from
the oil by filtration. A good description of the commercial processis
given by Richardson (1978).
99
Bentonite
Table 9.1. Majorapplicationsforacid-activatedclays(fromTaylor

Function Application
~~
Refiningagentfor
oils and solvents
90-130C
at
use
& Jenkins, 1986).
of
~~
Edible and inedible oils: decolourization and

stabilization by removal ofcoloured pigments and
impurities
1/4-4% clay dosage; heated

under vacuum for 15-30min
then filtered
Used lubricant oils: reclamation by removal

of degradation productsand contaminants
3 4 % clay dosage; heated

with steam to 390-575F for
10-30 min then filtered
BTX refining: olefin removal and decolourization Fixed bed contact

170-200C
Catalysis
Acid-catalysed reactions: polymerization,

alkylations, esterifications, isomerizations and
fatty acid dimerizations
Carbonless
paper
Colour developer: developing

colour
encpsulated
dye
beads onpaper
copy
COPY
at
Reagents either passed over

bed of granulated particles or
added to reagents in powder
form at moderate to high
temperatures
of micro20-30%
clay
dosage
in
coating
mixture;
coating
spread on front of bottom
(copy) sheet
100
Bentonite
DEGUMMING
PHYSICAL REFINING
POLISHING
EDIBLE OIL STORAGE
Figure 9.1 Edible oil refiningprocess

1986).
(from Taylor & Jenkins,
It is important to note that bleaching earths perform many functions

beside the removalof coloured impurities from oils and fats.
Traditionally, a simple oil bleaching evaluation
is regarded as a goad
initial sorting test to establish whether a bentonite
has the required
properties for commercial use, but before this be
cancarried out the clay
has to be acid-activated and this requires much experimentation
to
identify the best combination of acid strength, contact time and
temperature. Although the bleachedoil colour may be optimized for a
particular acid treatment, otheroil parameters suchas oxidative stability,
trace metal content and free fatty acid content may require different
levels of acid treatment to produce an optimum product,so even more
careful experimentation is required. This levelof investigation would
normally be beyond the resources and brief of a Geological Survey.
The following sections are intended to provide sufficient background

information to enable a Geological Survey laboratory
to set up a simple
evaluation scheme for bentonite acid activation and evaluation of
bleaching performance of the products. Enough key referencesare
provided to enable further detailed reading
on the subject.
101
Bentonite
9.2. Changes in properties of smectite with acid activation

Structure andX-ray diffraction patterns If any carbonate impurity is
present in the bentonite, this is dissolvedby the acid. The first effect of
acid attack on the smectite itself is that the exchangeable cations are
replaced by H+. Subsequently, the main structureis attacked, and Al,
Mg and Fe are removed from the octahedral sheet exposed at edges
the
of the smectite platelets. Someof these ions may then migrate to
exchange positions. As a result of acid attack the surface area
of the
smectite is increased and the pore-size distribution of theisclay
modified. The smectite layers take on the appearance
of bundles of used
bank notes, relatively unaffected in the centre
but separating at the
edges. The mechanism is illustrated in Figure9.2.;Figure 9.3. shows
the changes in XRD patterns resultingfrom structural deterioration.
2. STRUCTURE DISRUPTEDAREA INCREASES
1. ACID
ATYACKS
OCTAHEDRAL
LAYER
SURFACE
8'
0-
P
&d
3. AClDCCATlONS RELEASED FROM STRUCTURE

EXCHANQED FOR CALCIUM CATIONS
4. ACID ACTIVATED CLAY WITH ACID

CATIONS IN EXCHANQE SITES
Figure 9.2. Mechanism of acid attack on smectite(fromTaylor

Jenkins, 1986).
lk
102
Bentonite
Surface area andpore structure In general, surface area increases with

increase in seventy of acid treatment,but it does pass through a
maximum beyond which additional acid treatment actually reduces the
surface area. Figure 9.4. illustrates the important point that smectites
from different bentonite deposits respond individually with respect both
to the maximum surface area they achieve and
the acid requirement to
reach that maximum. Thus when assessing a bentonite for
oil-clarification applications a considerable amount of experimentation
is
usually necessary to determine optimum acid-activation conditions.
Maximum surface area is usually in the range
200-400 m2/g, and in
general the optimum bleaching properties
are found below the maximum
surface area obtainable.
103
Bentonite
o f
0
20
40
60
60
100
120
lncrearing A d d Treatment __c
Figure 9.4. Effect of aciddosage on the surfacearea

smectites (from Taylor & Jenkins, 1986).
of various
The physical changes in the structure

of acid-activated smectite maybe
examined quantitativelyfrom nitrogen adsorption/desorption isotherms,
from which surface area and pore volumes are calculated (a good
introduction to this topic is given by Greenland
& Mott (1978), and Fijal
et al. (1975) deal comprehensively withthe calculation and significance
of pore volume distribution in smectites). An adsorption/desorption
nitrogen isotherm for Ca-smectiteis shown in Figure 9.5a. This
isotherm corresponds to a surface area
of 70 m2/g, typical of
Ca-smectite (range 50-120 m2/g). The hysterisis occurring during the
104
Bentonite
desorption cycleis given by a capillary system consistingof a

combination of slit-shaped and wedge-shaped capillaries
with a closed
edge. The same clay when acid-activated gives the nitrogen
adsorption/desorption isothenn shown in Figure 9.5b. The total volume
of nitrogen adsorbed is three times greater and correspondsato
surface
area of 227 m2/g. The isothenn is also changed in shape; in particular,
the degreeof hysteresis is reduced, corresponding atogreater
contribution to the pore structure
by wedge-shaped capillaries.
original clay and acid-activated product

The change in pore type between
are emphasizedby computer treatmentof the nitrogen isothermto give
9.6.).
incremental pore-size distribution plots (Figure
200-
100-
0.5
1-0
01
0
0.5
I
1-0
1
RELATNE PRESSURE
Figure 9.5a-b. Nitrogenadsorption/desorptionisotherms

acid-activatedproduct
(from Morgan et al., 1985).
for Ca-smectiteand
105
Bentonite
50
AVERAGE PORE DlAMIER(A)
Figure 9.6. Pore-sizedistributionplots

for Ca-smestite and
acid-activatedproduct
(from Morgan et al., 1985).
These plots show that in natural Ca-smectite the surface

of the clay is
composed of relatively small pores<20 A in diameter. These pores
correspond to the smectite interlayer spaces. Following acid activation
the average diameterof the pores has increased and over
80% of the
available surface isin pores having diameters between20 and 60 A.
These are pores that begin to take
on a three-dimensional appearance
with less restricted openings.
Su@ace acidity Surface acidity, as shown
in Figure 9.7., measures both
the numberof acidic siteson the clay surface and their relative strength.
In this case surface acidity has been measured by base titration using
Hammett indicatorsof known pKa. The pKa value quantifies the
strength of the acid sites, the lower the number the higher the acid
strength. Acid sites possessing a pKa value
of -3 are approximately as
strong as sulphuric acid; those possessing a pKa value
of 5 are
considered weak siteswith the approximate strengthof acetic acid. As
with surface area, surface acidity also passes through a maximum with
increasing acid treatment. The trend also shows that
it is possible to
over-activate a clay and lose surface acidity entirely.
106
Bentonite
Figure 9.7. Effectofaciddosage
on surfaceacidity(fromTaylor
& Jenkins, 1986).
Cation exchange capaciry Figure 9.8. shows that the CEC decreases
with extent of acid treatment.
110
^o
100
0,
\
90
a
E
Y
-5u
eo
70
a
*n 60
a
0
a
0
50
540
s
0
30
C
,o
c
20
10
0
20
4.0
Figure 9.8. Effect ofaciddosage
80
60
Increeaing A d d Treatment
100
120
on CECofvarioussmectites(from
Taylor & Jenkins, 1986).
107
Bentonite
9.3. Laboratory activation trials and assessment of bleaching

efficiency of products
Measurement of surface area will often give

a good indication of the
bleaching potential of an acid-activated bentonitebut there isno
absolute correlation between bleaching
performance and surface area.
9.9. Although a rough correspondence is
This is illustrated in Figure
obtained between bleachingperfomance and surface areafor clay A, for
clay C the bleaching efficiencymaximum is achieved well after surface
area for that clay has begun to
drop off. Additional evidence that
surface area alone is inadequate
as the sole indicator of adsorptive
capacity canbe deduced from the fact thatA, which has a much higher
surface areathan C, is only about two-thirds as active C.
as
.OD
CLAY A
1
m
400
34,
1100
100
.Q
a0
0'
Incroaaing Acid froatmont
loo
0
120
20
.o
a0
.o
l o o l t o
Incroaslng A d d Troatmont-
Figure 9.9. Correlation of surfaceareawithbleachingefficiency(fromTaylor

1986).
& Jenkins,
For a bentonite froma new deposit there is, therefore,

no alternative to
carrying out acid-treatments
with different strengthsof acid and for
different contact times, and then measuring the oil- decolourizing ability
of the various products. Because there is no generally accepted
procedure for acid activation, these procedures
vary in detail between
different workers; some.of these are described briefly below.
108
Bentonite
Oxfordshire
Surrey
% Fe,O,
Oxfordshire
Surrey
15
'.
10
4
6
S
% H,SO, on slurry
io
12
%
Surface
area
5% SiO,
m:
70
Oxfordshire
Surrey
HSO. on slurry
X
Oxfordshire
-1
Surrey
400
66
300
62
200
58
10
54
6
8
10
% HSO, on slurry
4
12
Figure9.10a-d.Changes
in chemicalcompositionandsurfacearea
earthsfollowingsulphuricacidtreatment
(from Yates, 1986).
%
! H,SO, on slurry
for two UK fuller's
109
Bentonite
Procedure of Yates ( I 986) Raw materials were two fuller's earths

(Ca-smectite) from Oxfordshire and Surrey,UK. Slurries of the clays
at constant (but not given) solids content were reacted
in glass vessels
with sulphuric acid in amounts upto 11.2% of the total mix. The
reaction slumy was heatedto boiling point under refluxfor a standard
time (again not given) with continuous stining. After reaction, the
treated clays were filtered and washed with deionized water
to a low
residual acidity level and dried slowly to
10%moisture levels. Changes
in Al, Mg, Fe content and surface
area of the two clays with acid
treatment are shownin Figure 9.10a-d.
Oil-bleaching ability of the activated products was measured
on
neutralized soya bean oil.This was carried out ata contact temperature
of 95OC in a stirred open vessel, the contact time being
30 min. After
treatment, the oil/clay mixture was filtered and the colour
of the bleached
oils determined using a Lovibond Tintometer with a 51/4-in cell, the red
colours obtained being recorded. Results are plotted
in Figure 9.11.
o Surrey
lo
i2
% H,SO. on slurry
Figure 9.1 1. Decoloutizationofsoyabean

functionofacidtreatment(fromYates,
oil by fuller's earths as

1986).
There is a very rapid developmentof bleached colour as the acid

strength increases, followedby a slower improvement at the higher
levels of treatment.
Procedure of Kolta et al. (1976) Materials used were three medium- to
poor-grade bentonites from the Quasr-el-Sagha deposit, Egypt. 100 g
of bentonite was added to100 ml water in a three-necked flask,
with a
thermometer, a condenser and a stirrer.. The flask was placed in a water
110
Bentonite
bath, thermostatically controlled at 95C.

60 ml of 37%HCl was added
and the slurry subjected to leaching for various times ranging up to 10
hours. At the end of the treatment
the sluny was filtered, thoroughly
washed until an acid-free filtrate was obtained, and then dried at 110C.
of the
For determination of bleaching capacity, a fixed amount
acid-activated product was added 20
to ml of crude cotton oil
in a wide
glass testtube immersed in an oil bath to maintain the bleaching
temperature (100C). The bleaching process was conducted
for 30 min
with stimng. The slurry was filtered and the absorbance of the bleached
oil was measured at 460 nm using a Beckmann spectrophotometer. The
by
relative bleaching abilitiesof the activated products were measured
comparing the absorbances of
the oil bleached with each product and
that bleached with the same amount
of commercial bleaching clay Tonsil
AC, applying the following equation:
BA = (A1 - Az) / (AI - A3)
100
where BA is the bleaching ability,AI is the absorbanceof the crudeoil,

is the absorbance of the oil after bleaching with the activated product,
and A3 is the absorbance ofthe oil after bleaching with a similar amount
of Tonsil AC. The relationships between bleaching abilities and oftime
acid activation forthe three claysare shown in Figure 9.12a and
corresponding developmentof surface area in Figure 9.12b.
A2
Only sample C givesa conventional response to acid activation, after

360 min contact with HC1 givinga product with90% of the bleaching
ability of Tonsil AC. Sample
B cannot be usedfor activation because of
its low smectite content. SampleB still had not developedits full
bleaching potential even after10 hours' acid contact, which suggests
that an appreciable amount of kaolin
is also presentin this sample.
Procedure of Zaki et al. (1986) Materials were bentonites from three

further Egyptian deposits. Acid treatment involved adding
166 g clay to
1 litre of 1N HC1 in a two-necked flask equipped with a thermometer
and a condenser. The flask was placed
in a water bath at 95C. Contact
times, with continuous stirring, were60,90 and 120 min. Recovery of
products followed Novaket al., as did the assessment
of bleaching
ability, exceptthat a Lovibond Tintometer was used.
111
Bentonite
!20
240
360
480
Time of acid oetivolim (mid
600
I20
240
360
480
60C
Time of oeid oetiwtlonh)
Figure9.12a-b.Relationshipsbetweenbleachingability
(a) andsurfacearea(b)with
of Egyptianbentonites.Smectitecontents
of samples:
increasingacidtreatment
A 40%; 0 60% (from Novak el al., 1976).
33%;
Procedure of Srasra et al. (1989) This paper dealswith a bentonite from

Tunisia, the main component(80%)of which is an irregularly
interstratified smectite-illite. Acid activationwas accomplished by
stirring 10 g of bentonite with 100 ml of hydrochloric, sulphuric and
nitric acidsof different normalities (0.1-10 N ). After centrifugation and
filtration, the products were washed with hot water to6pH
and dried at
105OC. For assessment of decolourization ability,2 g of the activated
product was thoroughly mixed with100 ml rapeseed oil (previously
neutralized with NaOH) for20 min at 90C. Bleaching ability was
assessed by recording the absorbance at
430 nm of 2.5 ml of the treated
oil in 10 mi carbon tetrachloride on LMB
a
spectrophotometer and
applying the equation:
BE =
[ A430 (neurral oil) - 4 3 0 (treated oil)] I
A430
(neutral oil)
HC1 was found to be the best activator. Total absorption spectrafor the
untreated oil, that bleached
by the crude bentonite and that bleached
by
the product after a15 hour treatment with7 N HCl are shownin Figure
9.13.
112
Bentonite
Figure 9.13. Totalabsorptionspectra

for rapeseed oil (a)and for
productsbleached with crude (b) and HCI-activated (c) bentonite
(fromSrasra et af.,1989).
Procedures of Stoch et al. (1979a,b) These two papers describe the

effects of acid attack on surface area, pore structure, surface acidity and
other propertiesof impure bentonites from Poland and the bleaching
performance of the products to rapeseed oil. It would not be practical
or even necessary - to replicate all the various combinations
of
experimental conditions in a routine assessment
of a possible bleaching
earth, but these investigations provide an excellent example
of the use of
the various techniques and the type of interpretation possible.
113
Bentonite
References
Atkins M P, Smith D J H & Westlake D J (1983) Montmorillonite catalysts for
ethylene hydration. Clay Miner. 18,423-429.
Fahn R & Fender1 K (1983) Reaction productsof organic dye molecules with
acid-treated montmorillonite.Clay Miner. 18,447-458.
Greenland D J & Mott CJ B (1978) Surfacesof clay particles.Pp. 321-353 in: The
Chemistry of Soil Constituents (D J Greenland andM H B Hayes, editors). John
Wiley & Sons, Chichester, UK
Gregory R, Smith D J H & Westlake DJ (1983) The production of ethyl acetate
Clay Miner.18, 431-435.
from ethylene and acetic acid using clay catalysts.
Fijal J, Klapyta 2, KwiecinskA B, ZietkiewiczJ & Zyla M (1975) On the
mechanism of acid activation of montmorillonite:
11. Changes in the morphology and
porosity in the light of electron microscopic and adsorption investigations.
Mineralogica Polonica 6,49-57.
Kolta G A, Novak I, Samir 2 EL-T & Kamilia A EL-B (1976) Evaluation of
J . Appl. Chern. Biotechnol.
bleaching capacity of acid-leached Egyptian bentonites.
26, 355-360.
Morgan D A, Shaw D B, Sidebottom T C, SoonT C & Taylor R S (1985) The
function of bleaching earthsin the processingof palm, palm kerneland coconut oils.
J . Am. Oil Chem. SOC. 62, 292-299.
Richardson L L (1978) Useof bleaching clays in processing edible oils.
J. Am. Oil
Chem SOC. 55, 777-780.
Srasra E, Bergaya F,Van Damme H & Ariguib N K (1989) Surface propertiesof an
activated bentonite- decolorisation of rape-seed oils. Appl. Clay Sci. 4,411-421.
Stoch L, Bahranowski K & Gatarz 2 (1979a) Bleaching properties
of non-bentonitic
clay materials and their modification:
11. Bleaching ability of natural and activated
Krakowiec clays from Machow.Mineralogica Polonica 10,Zl-38.
Stoch L, Bahranowski K, Eilmes J & Fijal J (1979b) Bleaching propertiesof
non-bentonitic clay materials and their modification:
III. Modification of bleaching
properties of Kracowiec clays from Machow with some organic compounds.
Mineralogica Polonica 10,3947.
114
Bentonite
Taylor D B & Jenkins D B (1986) Acid activated clay.Am. SOc. Min. Eng. Mtng.
Preprint 86-365.
Yate M H (1986) Acid treatment of English montmorillonite
and its effect on clay
structure and properties. Unpublished paper (Luporte Inorganics, Widnes, UK).
Zaki M I, Abdel-Khalik M & Habashi G M (1986) Acid-leaching and consequent
pore structure and bleaching capacity modifications of Egyptian Colloids
clays. &
Surfaces 17,241-249.
Bentonite
Appendix I O :
Waterabsorbency
sf pet litters
Equipment and reagents

Stainless steel mesh(355 pm aperture) cone,75 mm high by 70 mm
diameter; with holes cutin rim to allow suspension from a stand.
1000 ml beaker
Analytical balance,0.1 g readability
Stopwatch or timer
Clamp and stand
Distillfldeionised water
Sample preparation
1.
Oven-drylumpmaterialat60Covernight.
2.
Jaw-crush and screen on 10 mm and 5 mrn, repass >10 rnm

through jaw-crusher.
3.
Retain 5-10 mmmaterial for testing (store in a sealed container).
Method
1.
Weighthemesh
2.
Add approximately 20 g representative sub-sampleof 5- 10 mm

bentonite to the cone and weigh cone
+ sample (W2).
3.
Suspendingthecone + samplefromtheclampandstand,
immerse the cone in the beaker filled
with distilled water for20
minutes.
4.
Remove the cone from the water and allow to drain

30 for
minutes.
5.
Weigh the cone+ saturated. sample (W3).
6.
Repeat the test twice further to give

a total of three
determinations.
cone (Wl).
116
Calculation
Absorbency as a percentage
of mass
= W3-W2
* 100
w2-w1
Quote the meanof the three results.
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British Geological Survey

TECHNICAL REPORT WG/93/20

Industrial Minerals Laboratory Manual

Mineralogy and Petrology Group

British Geological Survey

Industrial Mberals Laboratory Manual

Keyworth, Nottingham, British Geological Survey, 1993

3. MINING AND PROCESSING

5. LABORATORY ASSESSMENT OF BENTONITE

2. Cation-exchange capacity(BaClrngS04 method)

3. Methylene blue cation-exchange capacity

4.2-ethoxyethanol surface area method

5. Bentonite swelling test

6. Bentonite liquid limits

7. Plastic limit and plasticity index

8. Drilling fluid properties

9. Mechanism of acid activation and assessment

10. Water absorbency of pet litters

Biogenic Sedimentary Rocks

Industrial Minerals Laboratory Manual

Bentonites, which consist essentially

Mineralogy and PetrologyGroup, British Geological Survey 0 NERC 1993

The physical and chemical properties of bentonites typically vary both

Mineralogy and PetrologyGroup, British GeologicalSurvey 0 NERC 1993

Classedas 2:l Layerphyllosilicates

General formula of smecfitegroup:

Chemical composition of thesmectite

(ca. Na, Mg)

Negative charge per formula unit layer [Ole (OH)2]

Mineralogy and Petrology Group, British Geological Survey 0 NERC 1993

and chemistry of smectite-groupclayminerals.

Mineralogy and Petrology Group, British Geological Survey0 NERC 1993

Most bentonites have formed

2.1 Sedimentary bentonites

These bentonites are formed

South Dakota borders and in the Hardin district of south-central

As sedimentary bentonites are not usually associated with volcanic

Mineralogy and Petrology Group, British Geological Survey

2.2 Hydrothermal bentonites

Some bentonite deposits have formed the

Bentonites rangein colour from black through to white but most

Mineralogy and Petrology Group, British Geological Survey0 NERC 1993

Mineralogy and Petrology Group, British Geological Survey 0 NERC 1993

3. MINING AND PROCESSING

Bentonite is almost always extractedin open pit workings, usually

Bentonite is rarely usedin the raw form but undergoes processing

A simplified flow diagram for the processing of Ca-bentonite

Grinding to fine powder

Mineralogy and PetrologyGroup, British Geological Survey 0 NERC 1993

It is common practice, particularly

is considered in more detail

rheological properties. These speciality and highly-priced bentonites are

Mineralogy and Petrology Group, British Geological Survey

Bentonites have a wide range

Mineralogy and Petrology Group, British Geological Survey0 NERC 1993

Sorptive properties(may be increasedby acid treatment)

B: In dry state (or paste)

Sur$ace area (may beincreased by acid-activation)

Impermeability, coating properties

Civil engineering (grouting, impermeable

Bonding foundry moulding sands

Formulation of mortars, putties, adhesives, some

Mineralogy and Petrology Group,British Geological Survey 0 NERC 1993