AT T AP UL GI T E : P R O P E R T I E S A N D US ES

by
W. L. HADEN, JR.
Minerals and Chemicals Phi l i pp Corporation, Menlo ]?ark, New Jersey
ABSTRACT
The clay mineral at t apul gi t e derives i t s non-swelling needle-like morphology from i t s
three-dimensional crystal structure. The shape and size of t he needles result in unique
colloidal properties, especially resistance to high concentrations of electrolytes, and
give high surface area, high porosi t y particles when t hermal l y act i vat ed. Exampl es of
i ndust ri al applications of at t apul gi t e are reviewed with emphasis on how these character-
istic properties function in the various end-uses.
I N T R O D U C T I O N
At t a p u l g i t e h a d been us e d b y i n d u s t r y for mo r e t h a n 40 y e a r s bef or e i t
wa s r e c ogni z e d as a d i s t i n c t c l a y mi n e r a l . Che mi c a l c o mp o s i t i o n a n d s ome of
i t s p r o p e r t i e s wer e s uf f i ci ent l y s i mi l a r t o mo n t mo r i l l o n i t e t o caus e t hi s con-
f usi on. I n t h e 1940' s, t h e s t r u c t u r e was wo r k e d o u t b y Br a d l e y , a n d t h e
ne e dl e - l i ke p a r t i c l e s ha pe wa s l a t e r d e mo n s t r a t e d b y e l e c t r on mi c r o s c o p y
( Gr i m, 1953, p p . 77- 79) .
Wi t h t h e r e a l i z a t i o n t h a t a t t a p u l g i t e was i n d e e d a u n i q u e mi ne r a l , con-
s i de r a bl e ef f or t s h a v e be e n e x p e n d e d ove r t h e y e a r s b y i n d u s t r y t o t a k e
a d v a n t a g e of i t s c h a r a c t e r i s t i c p r o p e r t i e s i n i n d u s t r i a l a ppl i c a t i ons . Thi s
p a p e r s hows h o w t h e f u n d a me n t a l p r o p e r t i e s of a t t a p u l g i t e whi c h r e s ul t
f r om t h e c r y s t a l s t r u c t u r e l e a d t o a n u mb e r of c u r r e n t i n d u s t r i a l a p p l i c a t i o n s .
S T R UC T UR E OF AT T AP UL GI T E
The a t o mi c s t r u c t u r e of a t t a p u l g i t e i s de s c r i be d i n s ome d e t a i l i n a n o t h e r
p a p e r p r e s e n t e d a t t hi s Conf er ence ( Pr ei s i nger , 1963), a l ong wi t h t h e s t r u c t u r a l
changes t h a t a c c o mp a n y t h e r ma l a c t i v a t i o n t r e a t me n t s . F o r pur pos e s of
t h i s di s cus s i on, we ne e d o n l y c ons i de r t h e s t r u c t u r e i n a q u a l i t a t i v e ma n n e r ,
s i nce p a r t i c l e s ha pe a n d si ze gi ve a t t a p u l g i t e i t s u n u s u a l pr ope r t i e s .
I n a t t a p u l g i t e l ong doubl e c ha i ns of s i l i ca t e t r a h e d r a r u n p a r a l l e l t o t h e
f i ber axi s . Th e y a r e j o i n e d b y ma g n e s i u m a n d a l u mi n u m i n o c t a h e d r a l
c o o r d i n a t i o n t o p r o d u c e s t r i p s s i mi l a r i n s t r u c t u r e t o t h e t h r e e - l a y e r mi ne r a l s .
The s e t h r e e - l a y e r s t r i ps a r e j o i n e d a t t h e cor ner s b y S i - - O- - S i b o n d s i n t o a
s t r u c t u r e r e s e mb l i n g a c h e c k e r b o a r d i n cr os s - s ect i on, wi t h f r ee c ha nne l s of
284
ATTAPULGITE: PROPERTIES A N D USES 285
about 3.7 by 6.0 ~ in cross-section r unni ng t he l engt h of t he needles. Prei si nger
(1963) has shown how t hese channel s can collapse when at t apul gi t e is
dehydr at ed, for t he open-channel st r uct ur e is st abi l i zed by t he wat er of
composi t i on whi ch compl et es t he edges of t he oct ahedr al strips. Collapse of
t he channel s on dehydr at i on is t he pr obabl e cause of t he a br upt decrease in
surface area f r om about 190 t o 125 m2/g obser ved by Bar r er and Mackenzi e
(1954), since ni t r ogen molecules are i ncapabl e of ent eri ng t he collapsed
channels.
Fr om t he st r uct ur e of at t apul gi t e, i t is fai rl y obvi ous t h a t t wo of t he
unusual charact eri st i cs of at t apul gi t e shoul d exist. Fi rst , since t he s t r uct ur e
is t hree-di mensi onal , no mont mor i l l oni t e- t ype swelling can occur. Second, i t
is appar ent t ha t cl eavage will be easi est al ong t he Si - - O- - Si bonds hol di ng
t oget her t he t hr ee- l ayer s t r i ps - - hence t he needle-like r at her t han pl at e-l i ke
part i cl e shape.
P ROP E RT I E S
Structure of a "Needl e"
The i mpor t a nt i ndust r i al l y appl i ed pr oper t i es of at t apul gi t e are a di rect
resul t of t he st r uct ur e j ust discussed. The at t apul gi t e needl e is t ypi cal l y
about 1/ z in l engt h and appr oxi mat el y 0. 01/z across. A model of t he needl e
at a scale-up of one mi l l i on t i mes woul d l ook ver y much like a met er st i ck in
size and shape. The channel s r unni ng t he l engt h of t he model would, on t hi s
scale, be onl y about 0.5 mm in cross-section. Onl y in r ar e i nst ances ar e t he
t i ny channel s of i mpor t ance in det er mi ni ng t he pr oper t i es of at t apul gi t e.
The ext er nal surface of t he needles and t he ar r angement of t he needles in
gross part i cl es ar e of pr i ma r y i mpor t ance.
I t is conveni ent t o di vi de t he appl i cat i ons of at t apul gi t e i nt o t wo br oad
categories, colloidal and non-colloidal. Colloidal pr oper t i es resul t when t he
part i cl es are di spersed in a l i qui d medi um t o t he ext ent t ha t t he i ndi vi dual
needles are capabl e of mor e or less i ndependent mot i on rel at i ve t o one anot her .
I n t he non-colloidal case, t he needles are at t ached t o each ot her t o gi ve ri gi d
part i cl es, each of whi ch is made up of ma n y di scret e needles.
Structure of a "Particle"
Since at t apul gi t e is al ways suppl i ed t o users in t he f or m of powder or
granul es, regardl ess of whet her t he appl i cat i on is t o be colloidal or not , t he
st r uct ur e and pr oper t i es of t he aggregat es shoul d be considered first.
The aggr egat es ma y be considered t o have a hays t ack or br ush- heap
st r uct ur e, in whi ch t he needles are packed loosely in a mor e or less r a ndom
fashi on. Usi ng t he met er st i ck model agai n, i f met er st i cks are t hr own i nt o a
pi l e about 10 f t high, we t hen have a r ough model of a t ypi cal 3/ z part i cl e of
fluid-energy mi l l ed at t apul gi t e, t he finest gri nd avai l abl e commerci al l y. I t is
evi dent t hat , even in t he mos t fi nel y-ground condition, a part i cl e consists of
an aggr egat e of ver y ma n y i ndi vi dual i nt er meshed cryst al l i t es.
286 TENTH NATIONAL CONFERENCE ON CLAYS AND CLAY MINERALS
Non-col l oi dal Characteristics
The packi ng of t he needles in t hi s hi ghl y por ous fashi on resul t s in t he
pr oper t i es charact eri st i c of t he non-col l oi dal grades of at t apul gi t e. Al t hough
t he t r ue densi t y of t he cr yst al is about 2.5, t he part i cl e densi t y is close t o 1.0,
and t he por e vol ume will appr oxi mat e 0.6 ml / g (McCarter, Kr i eger and
Hei nemann, 1950). The aver age por e di amet er is of t he same order of
magni t ude as t he needle di amet er , about 2004. The surface ar ea of t he
part i cl es, whi ch is i n r eal i t y t he ext er nal surface ar ea of t he component
needles, is about 125 m2/g. Several appl i cat i ons of at t apul gi t e depend on t hi s
i nt er nal st r uct ur e of t he aggr egat e and i t s st abi l i t y. I t is r emar kabl e t ha t
t her e is l i t t l e change in t hese pr oper t i es over an enor mous r ange of t emper a-
t ur e up t o about 1300~ al t hough t her e are ma r ke d changes i n t he cryst al
st r uct ur e as bound wat er and hydr oxyl s are r emoved (McCarter, Kr i cger and
Hei nemann, 1950).
Colloidal Characteristics
The colloidal nat ur e of at t apul gi t e does not usual l y become appar ent unt i l
t he part i cl es are separ at ed i nt o i ndi vi dual needles. Thi s separ at i on becomes
pr ogr essi vel y mor e difficult as t he heat t r e a t me nt of t he r aw cl ay is made
mor e vi gorous, and when mos t of t he bound wat er has been r emoved, t he
possi bi l i t y of obt ai ni ng a colloidal dispersion is al mos t nil. Processi ng t he
colloidal gr ades of at t apul gi t e t her ef or e includes a dr yi ng st ep mi l d enough
t o i nsure t ha t l i t t l e or no bound wat er is lost.
I n cont r ast t o t he swelling bent oni t es, which par t i al l y di sperse t hemsel ves
spont aneousl y i n wat er owing t o t he swelling caused by penet r at i on of wat er
bet ween t he uni t l ayers, t he t hr ee- di mensi onal st r uct ur e of at t apul gi t e
pr ohi bi t s a ny such i nt er nal swelling act i on. The a t t r a c t i ve forces bet ween t he
needles in a part i cl e are appr eci abl e, and mechani cal act i on is necessary t o
t ear a pa r t t hese needles ( Gabr ysh et al., 1961). I n t he l abor at or y, a hi gh-speed
mi xer l i ke t he War i ng Bl endor or Osterizer, or a mi l k- shake mi xer, is hi ghl y
effective. I n commer ci al appl i cat i ons colloid mills, homogeni zers, and ot her
hi gh- shear mi xer s are commonl y used.
Ef f ect i ve di spersi on resul t s when i ndi vi dual needles, or at l east smal l
bundl es, are capabl e of movi ng r el at i ve t o one anot her under shear. Such a
di spersi on in wat er at say 3 per cent solids is hi ghl y t hi xot r opi c, havi ng hi gh
appar ent vi scosi t y at low shear but becomi ng near l y wat er - t hi n under hi gh
shear. Recover y of hi gh vi scosi t y upon r emoval of hi gh shear is al most
i nst ant aneous in pur e wat er, and at rest a definite yi el d poi nt is observed.
These phenomena are i ndi cat i ve of a hi gh degree of i nt er act i on bet ween
needles, so t ha t a t hree-di mensi onal net wor k is bui l t up wi t hi n t he fluid.
However , t he i nt er act i on is not so st r ong t hat i t resists hi gh shear. Addi t i on
of a defl occul at i ng agent t o t he suspensi on resul t s in a decrease in appar ent
vi scosi t y. A considerable r ange of flow behavi or ma y result, dependi ng on
solids cont ent and quant i t y of defl occul ant . I t is possi bl e t o pr epar e a non-
ATTABULGITE: PRO]?ERTIES AI~D USES 287
pour abl e gel whi ch becomes al most wat er - t hi n on shaki ng, but whi ch set s
up agai n t o a gel in a few mi nut es.
A charact eri st i c of at t apul gi t c t ha t makes i t sui t abl e for ma n y appl i cat i ons
where clays such as bent oni t e ar e unsui t abl e is its di spersi bi l i t y in t he
presence of hi gh el ect rol yt e concent rat i ons, gi vi ng dispersions l i t t l e di fferent
f r om t hose in pur e wat er . Since el ect rol yt es pr event t he swelling of bent oni t e,
sat i sf act or y di spersi ons cannot be made under t hese condi t i ons.
At t apul gi t e is also dispersible in ma n y organic liquids, especi al l y i f a
surface act i ve agent is added t o reduce t he ol eophobi c nat ur e of t he surface.
Such dispersions r esembl e t hose made in wat er, rangi ng f r om t hi n t hi xot r opi c
liquids t o stiff gels.
A P P L I C A T I O N S
A n u m b e r o f r e p r e s e n t a t i v e a p p l i c a t i o n s o f a t t a p u l g i t e a r e l i s t e d i n T a b l e l ,
c l a s s i f i e d a s t o t h e p r i m a r y f u n c t i o n o f t h e a t t a p u l g i t e . I t i s n o t p o s s i b l e i n a
s h o r t a r t i c l e t o g i v e d e t a i l s o f a l l t h e m a n y u s e s o f a t t a p u l g i t e , s o o n l y a
f e w t y p i c a l a p p l i c a t i o n s c a n b e d i s c u s s e d h e r e . A m o r e e x t e n s i v e s u r v e y i s
g i v e n b y G r i m ( 1 9 6 2 ) a n d s o m e a p p l i c a t i o n s a r e d e s c r i b e d i n d e t a i l i n
t e c h n i c a l b u l l e t i n s p u b l i s h e d b y t h e p r o c e s s o r s o f a t t a p u l g i t e .
Colloidal Applications
Oil well drillingfluids.--The drilling mud ci rcul at ed t hr ough a well serves
t he pr i ma r y f unct i on of r emovi ng bi t cut t i ngs f r om t he hole. I n addi t i on, i t
l ubri cat es t he bi t , pr event s hole sloughing, and f or ms an i mper vi ous filter
cake on t he walls of t he hole, t hus pr event i ng loss of t he fluid t o por ous
f or mat i ons. Of ut mos t i mpor t ance among t he charact eri st i cs of a cl ay for a
drilling mud is t he abi l i t y of t he cl ay t o bui l d up a sui t abl e vi scosi t y at a
r el at i vel y low solids level, and t o mai nt ai n t he desired vi scosi t y t hr oughout
t he drilling of t he well.
Bent oni t e has been wi del y used for t hi s purpose, but i t can be used onl y
wi t h t he hel p of expensi ve chemi cal t r eat ment s i n areas where cont ami nant s
such as salt, cal ci um suffate, or magnesi um sul fat e are encount ered. Since
t hese cont ami nant s pr event t he swelling of bent oni t e, bent oni t e is qui t e
i neffect i ve in yi el di ng or mai nt ai ni ng vi scosi t y in t hei r presence.
At t apul gi t e, on t he ot her hand, does not depend on swelling in order t o
yi el d vi scosi t y and is qui t e st abl e in t he presence of t hese cont ami nant s; i t
also shows excel l ent st abi l i t y under t he hi gh t emper at ur e condi t i ons
encount er ed in deep drilling in cert ai n areas.
Adhesives.--In t he pr oduct i on of cor r ugat ed boar d t he st ar ch adhesi ves
empl oyed lose vi scosi t y under shear, maki ng i t difficult t o appl y a const ant
amount of adhesi ve dur i ng a pr oduct i on run. As ment i oned earlier, at t apul -
gi t e devel ops vi scosi t y under shear, so t he i ncor por at i on of at t apul gi t e has
been an effective met hod of count er act i ng t he loss of vi scosi t y of t he st arch.
Liquid suspension fertilizers.--Liquid fertilizers are furni shi ng an i ncreas-
ing pr opor t i on of t he pl ant food consumed in t he Uni t ed St at es. Wi t hi n t he
288 T E N T H NATIONAL CONFERENCE ON CLAYS A N D CLAY MINERALS
TABLE 1.--SOME USES OF A'2TAI'ULGITE*
C O L L O I D A L
Actions: Viscosity building, gelling, thickening, protective colloid, suspending agent,
adsorbent, bonding agent.
t. Oil-base and water-base foundry sand binders
2. Adhesive viscosity control
3. Oil well drilling muds
4. Latex paint thickener and gelling agent
5. Pharmaceutical thickener and adsorbent
6. Liquid suspension fertilizers
7. Polishes--suspending agent for abrasives
8. Wax emulsion stabilizer
9. M e t a l drawing lubricants--suspending a g e n t
10. Laundry washing powders
11. Bonding agen~ for granulation of powders
I~OIW- C O L L O I D A L
Actions : Adsorption, absorption, catalyst, mild abrasive, parting agent.
1. Petroleum refining, decolorizing, neutralizing, brightening, desulfurization, deodor-
izing
2. Anti-caking agent for ammonium nitrate, etc.
3. Carrier for granular and powdered agricultural chemicals (insecticides, herbicides,
etc.)
4. Flatting agent in paints
5. Pharmaceutical intestinal absorbent
6. Floor absorbents
7. Animal bedding (cats, laboratory animals)
8. Polish ingredient for mild abrasive action
9. Flowability additive to dry fire extinguisher powders
10. Catalyst in NCR paper
11. Catalyst carrier
12. Olefin polymerization catalyst
13. Chromatographic adsorbent
14. Drying of oils
* Technical bulletins and additional information on many of these applications are
available from Minerals and Chemicals Philipp Corp., Menlo Park, N.J.
l ast t wo years, l i qui d suspensi on fertilizers have begun to come i nt o pro-
mi nence because of several l i mi t at i ons on t he t r ue l i qui d fertilizers, which
requi re compl et e sol ut i on of t he component s i n order t o be useful. The
r equi r ement of compl et e sol ubi l i t y is an obvi ous l i mi t at i on on t he amount of
pl ant food avai l abl e and furt her l i mi t s t he producer t o r at her hi gh- pur i t y
component s cont ai ni ng no i nsol ubl e const i t uent s. Secondary pl ant foods and
t race el ement s m~y also cause sol ubi l i t y probl ems.
The suspensi on fertilizers ci r cumvent these l i mi t at i ons of t he l i qui ds by t he
si mpl e expedi ent of usi ng t ypi cal l y 1 or 2 percent at t apul gi t e t o stabilize t he
suspensi on and pr event set t l i ng of i nsol ubl e component s. At t apul gi t e is t he
obvi ous choice for t hi s appl i cat i on because of its hi ghl y st abl e col l oi dal proper-
ties i n hi gh concent rat i ons of salts.
ATTAI~ULGITE: I)ROI)EI~TIES AND USES 289
Emulsion paints.---Although t her e are many ot her colloidal appl i cat i ons, as
i ndi cat ed in Tabl e 1, onl y one ot her appl i cat i on is ment i oned her e t o i l l ust rat e
addi t i onal charact eri st i cs of colloidal at t apul gi t e. At t apul gi t e has been used
t o repl ace organic t hi ckeners in emulsion pai nt s, resulting in a much mor e
wat er-i nsensi t i ve film, havi ng i mpr oved color r et ent i on on washing because of
t he i nsol ubi l i t y of t he at t apul gi t e t hi ckener.
Ot her advant ages of at t apul gi t e are its suspending charact eri st i cs for
pi gment s, and i t s t hi xot r opi c propert i es which reduce sag and pr ovi de easy
brushing. At t apul gi t e also acts as an emulsion stabilizer, serving as a pro-
t ect i ve colloid.
Non-Colloidal Applications
Percolation adsorptive processes.--The mechani cal and t her mal st abi l i t y and
high surface area resul t i ng from t he brush-heap st r uct ur e of granul ar at t apul -
gite lead t o its wide use as a percol at i on adsorbent . The rel at i vel y large pores
adapt i t t o t he r emoval of high mol ecul ar wei ght compounds, for exampl e,
t he sulfonatcs, resins, and asphal t i nes in pet r ol eum oils.
I n t he decol ori zat i on and neut ral i zi ng of a pet r ol eum oil, granul ar cl ay
(30/60 mesh, for example) is first heat - act i vat ed at 500-800~ and charged t o
t he filter shell. The oil is percol at ed t hr ough t he bed of cl ay unt i l t he adsorp-
t i ve capaci t y is r educed t o t he poi nt where t he efffluent oil reaches a pre-
det ermi ned qual i t y level. Aft er draining t he bed, washing wi t h napht ha, and
steaming, t he cl ay is sent t o a regenerat i ng kiln. The adsorbed organic ma t t e r
is bur nt off at 1000-1100~ and t he cl ay is re-used. Most refiners use at t apul -
gite for 10-20 cycles before discarding it.
Floor absorbents.--The hi gh por osi t y of at t apul gi t e lcads t o i t s wide use in
granul ar form for t he r emoval of oil, grease, and wat er f r om garage and
f act or y floors. The pores in at t apul gi t e are large enough t o per mi t r api d
sat ur at i on and, at t he same time, are small enough t o hol d t he liquid t ena-
ciously by capi l l ary act i on. The l ack of i nfl ammabi l i t y is an obvi ous reason
for selecting at t apul gi t e i n this application.
Carrier for agricultural chemicals. The absor bent propert i es which make
at t apul gi t e useful as a floor absor bent also find ext ensi ve use in convert i ng
pesticides and herbicides t o free-flowing granul es or dusts. Many of t hese
chemicals are liquids or st i cky pastes which woul d be difficult or impossible
t o use as produced. I mpr egnat ed and absorbed wi t hi n part i cl es of at t apul gi t e,
t he chemicals ma y be r eadi l y appl i ed i n t he field.
Pharmaceuticals.--Lack of t oxi ci t y and high adsorpt i ve power have resul t ed
in t he i ncorporat i on of at t apul gi t e in phar maceut i cal preparat i ons, including
i nt est i nal adsorbent preparat i ons. Kaol i n had previ ousl y been used al most
exclusively in such preparat i ons. I t has been shown (Barr, 1957) t hat at t apul -
gite is far superior t o kaol i n in t he adsorpt i on of alkaloids, di pht heri a t oxi n,
and bact eri a. The superior characteristics were mai nt ai ned following gast ri c
juice washing. Also of i nt erest in t he phar maceut i cal field is t he capaci t y t o
neut ral i ze considerable amount s of st rong acid.
Catalysts.--The cat al yt i c propert i es of at t apul gi t e have not been expl oi t ed
19
290 TE~TI~ NATIONAL COI~FERE~NCE ON CLAYS AND CLAY MII~ERALS
t o t h e e x t e n t t h a t ot he r p r o p e r t i e s ha ve , a n d a d v a n c e s ma y be e x p e c t e d i n
t h i s f i el d. A r e c e n t d e v e l o p me n t ha s be e n t he us e of a s pe c i a l l y- pr oc e s s e d
a t t a p u l g i t e as a c oa t i ng on t h e p a p e r us e d i n NCR ( " n o c a r b o n r e q u i r e d " )
mu l t i c o p y bus i ne s s f or ms . I n t hi s case, t h e a t t a p u l g i t e act s as a c a t a l y s t t o
c o n v e r t t h e d y e i n t e r me d i a t e s t o t h e col or ed d y e s wh e n t h e e n c a p s u l a t e d
i n t e r me d i a t e s a r e r e l e a s e d b y p r e s s u r e ( Gr een a n d Sa n d b e r g , 1951).
S UMMAR Y AND C ONC L US I ON
The col l oi dal , a d s o r p t i v e , a b s o r p t i v e , a n d c a t a l y t i c p r o p e r t i e s of a t t a p u l -
gi t e h a v e ma d e i t wi d e l y us e d b y ma n y i ndus t r i e s . Th e r e ha s be e n a s t e a d y
d e v e l o p me n t i n knowl e dge of t h e f u n d a me n t a l p r o p e r t i e s of a t t a p u l g i t e a n d a
c o r r e s p o n d i n g l y s t e a d y g r o wt h i n i t s i n d u s t r i a l a p p l i c a t i o n s . At t h e s a me
t i me , t h e p r o d u c e r s of a t t a p u l g i t e h a v e been d e v i s i n g b e t t e r pr oc e s s i ng
me t h o d s , a n d i mp r o v e me n t s i n q u a l i t y h a v e be e n e x p e r i e n c e d wi t h r e s pe c t
t o each of t h e p r o p e r t i e s de s c r i be d. I f t h e p a s t i s a n y i ndi c a t i on, c u r r e n t
r e s e a r c h wi l l r e s ul t i n f u r t h e r i mp r o v e me n t s i n p r o p e r t i e s , a n d t h e n u mb e r of
i n d u s t r i e s e mp l o y i n g t hi s u n u s u a l c l a y mi n e r a l wi l l c ont i nue t o i ncr eas e.
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