clay water system

8/3/2019 Clay Water System

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Clays and Clay M inerals,1970,Vol. 18. pp. 357-362. Pergamon ress. Printed n Great Britain

I N T E R A C T I O N S O F C L A Y M I N E R A L S W I T HO R G A N I C P O L Y M E R S . S O M E P R A C T I C A L A P P L I C A T I O N S

B . K . G . TI-IENGDivision of Applied M ineralogy, C.S.1.R.O., M elbourne, Au stralia(Re c e i v e d 27 Ap r i l 1970)

A bs tra ct- A n acco unt is given of the interactions between clay minerals and organic polymers withparticular reference to their applications in agriculture, foundation engineering and industry.INTRODUCTION

T H E I N TE RA CT IO N of c l a y mi n e r a l s w i t h o r ga n i cp o l y m e r s h a v e r e c e iv e d a c o n s i d e r ab l e a m o u n t o fa t t e n t i o n b e c a u s e o f t h e i r g r e a t a g r ic u l t u r a l a n di n d u s t ri a l p o t e n t i a l . I t h a s n o t b e e n p o s s i b l e , n o rw a s i t d e e m e d d e s i r a b le , t o i n c l u d e all o f t h em e t h o d s o f f o r m a t i o n a n d t h e p r o p e r t ie s o f c l a y -p o l y m e r d e r iv a t i v e s . R a t h e r , i n th i s ar t ic l e , a na t t e m p t i s m a d e t o d r a w t o g e t h e r e x a m p l e s f r o mt h o s e a r e a s i n w h i c h t h e c l a y - p o l y m e r i n t e r a c t i o nh a s f o u n d p r a c t i c a l a p p l i c a ti o n s .T h e b e n e f ic i a l e ff e c t o f o r g a n i c m a t t e r o n s o i lp h y s i c a l c o n d i t i o n s h a s b e e n r e c o g n i z e d f o r a v e r yl o n g ti m e . I n r e c e n t y e a r s , i t h a s b e c o m e c l e a r t h a tt h e w a t e r - s t a b i li t y o f n a t u r a l s o i l / c la y a g g r e g a t e s i sr e la t e d t o t h e p r e s e n c e o f p o l y s a c c h a r i d e s i n t h es o i l ( G r e e n l a n d e t a l . , 1 9 6 2 ; H a r r i s e t a l . , 1 9 6 3 ;C l a p p a n d E m e r s o n , 1 9 6 5) . A i d e d b y t h e r a p ida d v a n c e s i n p o l y m e r te c h n o l o g y , t h is o b s e r v a t i o nh a s s t i m u l a t e d r e s e a r c h i n t o t h e u s e o f s y n t h e t i co r g a n i c p o l y m e r s a s c o n d i t i o n i n g a n d s t a b i l i z i n ga g e n t s i n a g r i c u l t u r a l a n d f o u n d a t i o n e n g i n e e r i n ga p p l i c a t i o n s ( H e d r i c k a n d M o w r y , 1 9 5 2 ; L a m ba n d M i c h a e l s , 1 9 5 4 ; E m e r s o n , 1 9 5 6 ; M u s s e l l a n dR o t h , 1 9 5 7 ) .O f t h e m a n y i n d u st ri a l p r o c e s s e s i n w h i c h r a w o rm o d i f i e d c l a y s h a v e b e e n u s e d ( J o r d a n , 1 9 6 1 ;M u r r a y , 1 9 6 1 ; N a h i n , 1 9 6 1 ; C o o k , 1 9 66 ), o n l yt hose r e l a t i ng t o t he i r f unc t i ons a s f i l l e r s o rr e i n f o r c i n g m a t e r i a ls i n e l a s t o m e r a n d p l a s ti c c o m -p o s i t i o n s a r e i n c l u d e d i n t h i s r e v i e w . T h e t e r m"f i l l e r" i s u se d he r e i n t he s e nse o f a fi ne l y d i v i de ds o l id w h i c h i s i n c o r p o r a t e d i n t o t h e p o l y m e r m a t r i xi n o r d e r t o m o d i f y i t s p r o p e r t i e s a n d t o m e e t s p e c i -f i c i n d u s t r i a l o r c o m m e r c i a l r e q u i r e m e n t s . B e c a u s eo f t h is a b u n d a n c e , a v a i la b i li t y , l o w c o s t . a n d s u r f a c ep r o p e r t i e s , t h e c l a y m i n e r a l s a r e a d m i r a b l y s u i t e df o r t h is p u r p o s e .

DISCUSSIONE f f e c t o f c l a y - p o l y m e r i n t e r a c t i o n s o n s o il ~ c la yp r o p e r t i e s

T h e a d d i t i o n o f s m a l l q u a n t it i e s o f c h a r g e d a n du n c h a r g e d l in e a r p o l y m e r s t o s o i l a n d c l a y s y s t e m s

h a s a p r o f o u n d e f f e c t o n t h e i r p h y s i c a l a n d c o l l o i d a lp r o p e r t i e s . T h e l i te r a t u re o n th i s s u b j e c t h a s b e e ns u m m a r i z e d b y v a n O l p h e n ( 1 9 6 3 ) a n d m o r er e c e n t ly b y G r e e n l a n d ( 1 9 6 5 ) w h i ls t I n g l e s (1 9 6 8 )h a s b r o u g h t t o g e t h e r i n f o r m a t io n o n t h e u s e o fs i m p l e a n d p o l y m e r i c o r g a n i c c o m p o u n d s a s s o i ls t a b i l i z i ng a ge n t s . O n l y t he s a l i e n t f e a t u r e s w i l lt h e r e f o r e b e d i s c u s s e d i n t h is i n s t a n c e .I m p r o v e m e n t s o b s e r v e d i n t h e s t r u c t u r e a n ds t a b i l i t y o f s o i l s a f t e r t r e a t m e n t w i t h s y n t h e t i co r g a n i c p o l y m e r s a r e b a s i c a l l y d u e t o i n c r e a s e s i na g g r e g a t i o n a n d w a t e r - s t a b i li t y o f t h e a g g r e g a t e sf o r m e d . O f a w i d e v a r i e t y o f o r g a n i c p o l y m e r se m p l o y e d , p o l y a n i o n s a n d u n c h a r g e d h y d r o x y l a t e dp o l y m e r s h a v e b e e n m o s t s u c c e s s f u l . A t f i r s t s i g h t ,i t m i g h t a p p e a r t h a t p o s i t i v e l y c h a r g e d p o l y m e r sw o u l d b e e f f e c t i v e a g g r e g a t e s t a b i l i z e r s b u t t h i sd o e s n o t a c c o r d w i t h p r a c t ic e . A p p a r e n t l y , t h e r a teo f c o l la p s e o f t h e p o l y c a t i o n o n t o t h e n e g a t i v e l yc h a r g e d c l a y s u r f a c e i s s o g r e a t t h a t o n l y v e r yl im i t e d in t e r p a r t ic l e b ri d g i n g b y th e p o l y c a t i o nc a n b e a c h i e v e d .P o l y a n i o n s a r e k n o w n t o b e e f fe c ti v e fl o c c u la n t sw h e n a d d e d t o d i l u t e c l a y s u s p e n s i o n s ( M i c h a e l s ,1 9 5 4 ; B e r g m a n n a n d F i e d le r , 1 9 5 5 ; B e u t e l s p r a c h e r ,1 9 5 5 ; M i c h a e l s a n d M o r e l o s , 1 9 5 5 ; P a c k t e r , 1 9 5 7 ;W a r k e n t i n a n d M i l le r , 1 9 5 8 ; L a M e r a n d S m e l l ie ,1 9 6 0 ; L a M e r a n d H e a l y , 1 9 6 3 ) . F l o c c u l a t i o ni n v o l v e s a d s o r p t i o n o f th e p o l y a n i o n a s w e l l a sf o r m a t i o n o f i n te r p a rt i cl e b o n d s . T h e m o d e o fa c t i o n o f t h e p o l y a n i o n s h a s t h e r ef o r e b e e nl ik e n e d t o t h e f o r m a t i o n o f a " s t r in g o f b e a d s "( G r e e n l a n d , 1 9 6 3 ). U n l i k e p o l y c a t i o n s a n du n c h a r g e d p o l y m e r s o f th e p o l y v i n y l a l co h o l t y p e ,p o l y a n i o n s d o n o t a p p e a r t o p e n e t r a t e t h e i n t e r -l a y e r s p a c e o f t h e e x p a n d i n g l a y e r - la t t ic e m i n e r a ls( R u e h r w e i n a n d W a r d , 1 9 5 2 ; H a g i n a n d B o d m a n ,1 9 5 4 ; H o l m e s a n d T o t h , 1 9 5 7 ; A h l r i c h s , 1 9 6 2 ) b u ta r e a t t a c h e d m a i n l y t o t h e e d g e s o f t h e c r y s t a l s t of o r m " p e r i p h e r a l " c o m p l e x e s ( E m e r s o n , 1 9 5 5 ).H o w e v e r , u n d e r c o n d i t io n s i n w h i c h t h e p o l y a n i o nm o l e c u l e i s p r e s e n t i n a n u n d i s s o c i a t e d o r s l i g h t l yd i s s o c i a t e d f o r m , s o m e i n t e r l a y e r a d s o r p t i o n m a yo c c u r . T h u s , a t a p H o f 2. 5, a c o n s i d e r a b le a m o u n t

357


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358 B . K .G . THENGof a low molecular weight soil fulvic acid is adsorbedin the interlayers o f montmorillonite (Schnitzer andKodama, 1967). Electrostatic attraction to positivecharges at crystal edges, precipitation and coordina-tion involving multivalent exchangeable cationsand hydrogen bonding between the carboxyl groupsof the polyanion and the oxygens of the claylattice, have been invoked as bonding mechanisms(Ruehrwein and Ward, 1952; Michaels, 1954;Emerson, 1956, 1960; Packter, 1957; Warkentinand Miller, 1958; van der Watt and Bodman,1960). Under the conditions of maximum chainextension and hence optimum flocculating effciency, however, the polyanion is largely repelledby the negatively charged clay surfaces unless thezeta potential is lowered by addition of electrolytes(Ruehrwein and Ward, 1952; Mortensen, 1960).The number of polyanion segments involved ininterparticle bonding is therefore not likely to belarge. Further, individual segment-to-clay bond isnot a strong one so that polyanions are generallynot very effective aggregate stabilizers.On the other hand, uncharged flexible linearpolymers such as the polyvinyl alcohols, have beenshown to be highly effective in increasing themechanical strength and water-stability of naturalsoil/clay aggregates (Emerson, 1963; Williams e ta l . , 1967, 1968). In aqueous solutions, the poly-vinyl alcohol molecule exists as a compact, rand-omly coiled chain seemingly unpromising as aflocculant for dilute clay suspensions. However,on contact with the clay the molecule rapidlyuncoils and spreads, in Greenland's phrase, like a"coat of paint". This mode of action explains whythe polymer is strongly and irreversibly adsorbedby clays (Greenland, 1963; Emerson and Raupach,1964). Although individual segments o f the polymerchain form only weak bonds with the clay surface(in the order of 4kT), the total energy of adsorptionis largely due to the numerous points cf contact(Silberberg, 1962). Furthermore, there will be asignificant gain in entropy since the adsorptionof one polymer molecule is accompanied by thedesorption of many water molecules which willfavor the adsorption process. The adsorption iso-therm for polyvinyl alcohol on clays is accordinglyof the "high-affinity" or H- type (Giles e t a l . , 1960).When polyvinyl alcohol is added to a system inwhich the clay crystals or domains are alreadyin close proximity, interparticle bonding may alsooccur. Thus, the addition of small amounts (


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INTERACTIONS OF CLAY MINERALS 359and shape, and the surface properties of the clayparticles.The efficiency of clays in the filling or reinforce-ment of polymer systems is dependent on theirdegree of dispersion in the organic medium sincethe more highly dispersed they are the greater isthe surface area available for interaction with thepolymer matrix. Apart f rom the use of conventionalnon-ionic dispersants to render the clay surfacehydrophobic and hence, more compatible with theorganic phase, dispersion may be greatly improvedby replacing part or all of the inorganic cationswith organic ions or polycations (Carter e t a l . ,1950; Gluesenkamp, 1957; Ruehrwein, 1957;Uskov, 1960 a; Nahin and Backlund, 1963; Carrettand Walker, 1967). Mechanical grinding or vibra-tion milling has also been used to achieve a gooddispersion and when carried out in the presence oforganic monomers, may give rise to graft polymersshowing substantial increases in hardness andflow temperature (Uskov, 1960 b; Uskov andKusnitsyna, 1960).The effect of clay particle size on the mechanicalproperties of rubber and amorphous polymers hasbeen investigated by Cook and Pickering (1968)and by Uskov e t a l . (1964), respectively. Ingeneral, the efficiency of clay fillers in upgradingthese properties may be considerably increasedby reducing their average particle size. Likewise,the mechanical strength and stability of crystal -line polymers, e.g. polycaproamide, can beincreased by adding kaolinite to the polymer melt.On crystallization, the clay particles tend to becomeconcentrated in the interspherulitic regions reduc-ing the mobility of the polymer in these areas andpreventing their regrouping in the crystalline phase.As a consequence, the average size of the spheru-lites is decreased, this reduction being greater asthe size of the filler particles is decreased (Solomkoe t a l . , 1966).The shape of the filler particle has also a markedeffect on its efficiency as a reinforcing agent ofpolymer systems. Thus, the plate-shaped kaolinitecrystals have a greater stiffening effect on rubberthan the spherical whiting particles of equivalentdiameter. This is evident in the viscosity of anunvulcanized rubber compound and in the modulusof a vulcanizate. The stiffening effect of clay in theunvulcanized system gives better dimensionalcontrol and stability during processing (Cook andPickering, 1968).Clays, especially kaolinites, enjoy a substantialapplication for the filling and reinforcement ofnatural and synthetic rubber (Cook and Pickering,1968; Smith, 1968). Infrared studies indicate thatthe interaction of kaolinite with rubber involveshydrogen bonding between the rubber molecule

and the hydroxyl groups on the clay surface, par-ticularly those located at crystal edges (Suito andArawaka, 1964; Tarasenko e t a l . , 1964). A similarbonding mechanism has been postulated by Kiseleye t a l . (1968) for the interaction o f polyvinyl acetateand polyalkyl methacrylates with silica surfaces.As was mentioned earlier, under certain conditionsa considerable amount (20 per cent by weight) ofpolymethyl methacrylate may be grafted onto ben-tonite from which it could not be extracted by pro-longed boiling in benzene (Uskov e t a l . , 1963).This observation was ascribed to hydrogen bondformation between the oxygens of the polymermolecule and the hydroxyls on the clay latticesince polystyrene which is incapable of beingbonded in this way, could not be grafted. Theirevidence, however , is not entirely convincing sinceonly very few hydroxyl groups exposed at the edgesof the montmorillonite lattice would be availablefor hydrogen bond formation. It seems moreprobable that the po lymethyl methacrylate moleculepenetrates the interlayer space of montmorillonitesince its monomer does so whilst styrene is notintercalated (Blumstein, 1965; Solomon and Rosser ,1965; Solomon and Loft, 1968).A highly effective method of reinforcing naturaland synthetic elastomers has recently been claimedby Libby e t a l . (1967). It involves grafting of aminosilane to kaolinite by attachment of the hydro lyzedsilanol group to the clay surface leaving the pendentamino group free to react with the polymer mole-cule during vulcanization. The resulting cross-linked polymer-clay network shows significantimprovements in modulus, abrasion resistance andcompression-set properties as compared with theunfilled material.Clay minerals have also been used in the fillingof polyvinyl chloride and related thermoplasticcompounds (Cook, 1966). As distinct from theirapplication in elastomer systems, however, claysconfer little or no reinforcement although they doincrease the hardness and the rigidity of the product(Furter, 1964). A notable exception and one whichmay be regarded as a major advance in this direc-tion has been reported by Fallick e t a l . (1968).Using a novel approach, they were able to developa family of mineral (kaolinite and asbestos)reinforced linear polyethylene to which they gavethe name of "Ceraplasts". Their method involvesdispersing the filler particles in the polymer melt,encapsulating them with a thin sheath of resin andfirmly binding this encapsulant to both the mineraland the polymer matrix. The substantial increasesin tensile and impact strengths of "Ceraplasts"over conventionally filled polyethylene, are asso-ciated with the presence of a gradient in modulusbetween that o f the mineral and the polymer matrix


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360 B . K . G . T H E N Gi n t h e e n c a p s u l a n t . A l a t e r v a r i a n t i s t h e c o m p o s i t eo b t a i n e d b y c o a t i n g t h e c l a y p a r t i c l e s w i t h a ne t h y l e n i c a l ly u n s a t u r a t e d c o m p o u n d a n d a f r eer a d i c a l g e n e r a t o r p r i o r t o b l e n d i n g t h e c o m p l e xw i t h p o l y e t h y l e n e ( B i x l e r a n d F a l l i c k , 1 9 69 ). As i m i l ar p r o c e s s h a s b e e n c l a i m e d b y B a u m ( 1 9 6 9)w h o c o a t e d h i s c l a y s w i t h h i g h b o i l i n g p o i n t ( > 1 4 0 ~C ) n o n - r e a c t i v e , n o n - a c i d i c , o x y g e n - c o n t a i n i n go r g a n i c s a n d a n o r g a n i c p e r o x i d e w h i c h s e r v e s a sa c r o s s - l i n k i n g a g e n t b e t w e e n t h e m o d i f i e d c l a ya n d t h e p o l y e t h y l e n e m o l e cu l e . A n i m p o r t a n ta d v a n t a g e o f c l a y - f i ll e d o v e r c a r b o n b l a c k - f i l le dp o l y e t h y l e n e i s t h a t t h e f o r m e r , b e s i d e s d i s p l a y i n ge q u a l o r s u p e r i o r m e c h a n i c a l p r o p e r t i e s t o t h el a t t e r m a t e r i a l, a r e w h i t e a n d m a y b e g i v e n a n yd e s i r e d c o l o r b y a d d i t i o n o f a n a p p r o p r i a t e c o l o r a n t .C r o s s - l i n k i n g o f p o l y e t h y l e n e a n d o t h e r t h e r m o -p l a s t i c s t o c l a y s u r f a c e s c a n a l s o b e a c h i e v e d b yi r r a d ia t i o n te c h n i q u e s ( N a h i n a n d B a c k l u n d , 1 9 63 ).T h e e x t e n t o f th i s c r o s s - l in k i n g m a y b e g r e a t l yi m p r o v e d b y p r i m i n g t h e c l a y s u r f a ce w i t h o rg a n i c sh a v i n g " p o l y e t h y l e n e - l i k e " c h a i n s , e .g ., p o l y v i n y la l c o h o l o r h e x a m e t h y l e n e d i a m i n e . W h e n s u c hm o d i f i e d c la y s a r e e x p o s e d t o g a m m a r a y s o r f a s te l e c t r o n s i n t h e p r e s e n c e o f p o l y e t h y l e n e , p r o d u c t so f g r e a t s t r e n g t h , e x c e l l e n t t h e r m a l s t a b i l i t y a n dr e s i s t an c e t o w a r d s o r g a n i c s o l v e n t s , a re o b t a i n e d( N a h i n , 1 9 6 4 ) .M o d i f ie d c l a y s h a v e a l so b e e n s u c c e s s f u l lyi n c o r p o r a t e d i n t o p o l y u r e t h a n e f o a m s w i t h t h ep r i n c i p a l o b j e c t i v e o f l o w e r i n g t h e c o s t o f t h ep r o d u c t . S i n c e a l o w d e n s i t y , o p e n - c e l l e d m a t e r i a li s d e s ir e d , c o n v e n t i o n a l i n o r g a n ic a d d i t i v e s s u c h a ss i li c a , a r e n o t s a t i s f a c t o r y i n t h a t t h e y a d v e r s e l ya f fe c t t h e d e n s i t y a n d c e l l s t ru c t u r e o f t h e f o a mw h e n u s e d i n a p p r e c i a b l e q u a n t i ti e s ( 1 0 p e r c e n t b yw e i g h t o r m o r e ) . O n t h e o t h e r h a n d , p a l y g o r s k i t e( " a t t a p u l g i t e " ) c o a t e d w i t h w a t e r - s o l u b l e p o l y -m e r s ( p o l y v i n y l p y r r o l id o n e , p o l y v i n y l a l c o h o l ,p o l y a c r y la m i d e ) d is p e r s e d i n t h e p o l y i s o c y a n a t e -p o l y o l s y s t e m p r i o r to i t s f o a m i n g , d o e s n o t a p p e a rt o c a u s e a n i n c r e a s e i n d e n s i t y o r a d e t e r i o r a t i o ni n t e x t u r e ( F e n ' i g n o , 1 9 6 2 ) . T h e p r i m e a d v a n t a g ei n u s in g c o a t e d c l a y s o f t h i s n a t u r e , h o w e v e r , l i e si n t h e a t t e n d a n t i n c r e a s e i n t h e v o l u m e o f th e f o a mp r o d u c e d b y a g i v e n w e i g h t o f r e a c ti o n m i x t u r e s ot h a t t h e p i g m e n t m a y b e c o n s i d e r e d a s a t r u ee x t e n d e r ,A n e x t e n s i o n a n d m o d i f i c a ti o n o f t h e a b o v ep r o c e s s t o i n c l u d e a w i d e r a n g e o f m o d i f i e d c l a y sa n d r e l a t e d a l u m i n o - s i l i c a t e m i n e r a l s , h a s b e e nc l a im e d b y S h o w a l t e r (1 9 6 6) .

CONCLUSIONI n h i s r e v i e w , N a h i n ( 1 9 6 1 ) h a s e m p h a s i z e dt h e i m p o r t a n c e o f d e v e l o p i n g o u r c o n c e p t s o f c l a y -o r g a n i c i n t e r a c t i o n s i n o r d e r f o r t h e s e t o b e c o m e

p r a c t i c a l. T o a l ar g e m e a s u r e , N a h i n ' s p e r s p e c t i v eh a s b e e n s u b s t a n t i a t e d in th a t w e h a v e s e e n c o n -s i d e r a b l e p r o g r e s s b e i n g m a d e i n t h is a r e a o v e r t h ep a s t f e w y e a r s . T h e d e v e l o p m e n t o f s y n t h e t i co r g a n i c p o l y m e r s f o r s oi l s t a b i l iz a t i o n p u r p o s e s h a s ,a d m i t t e d l y , n o t b e e n d r a m a t i c . T h i s i s d u e p a r t l y t ot h e h i g h c o s t o f o r g a n i c s o i l c o n d i t i o n e r s a s c o m -p a r e d w i t h t h a t o f c o n v e n t i o n a l i n o r g a n ic a d d i -t i v e s , a n d p a r t l y t o t h e d i v e r g e n t r e q u i r e m e n t sd e m a n d e d f r o m a s o i l s t a b i l i z i n g a g e n t b y t h e a g r i -c u l t u r i s t a n d b y t h e s o i l e n g i n e e r . O n t h e o t h e rh a n d , e v e n t h i s s h o r t a p p r a i s a l h a s m a d e i t a b u n d -a n t l y c l e a r t h a t c l a y m i n e r a l s p l a y a n i n d i s p e n s -a b l e p a r t i n e l a s t o m e r a n d p l a s t ic p r o c e s s i n g n o tt o m e n t i o n t h e a p p l i c a t i o n s t h e y e n j o y i n t h em a n u f a c t u r e o f p a in t s , p a p e r , i n s u la t i o n c o m p o u n d s ,p o l y e s t e r s a n d e p o x y r e s i n s.

O n e m a y , w i t h c o n f i d e n c e, e x p e c t t o s e e a ni n c r e a s i n g l y w i d e r f i e l d o f a p p l i c a t i o n o f c l a ym i n e r a l s in i n d u s t ry . A d v a n c e s i n c l a y - p o l y m e rt e c h n o l o g y w i ll c o m e a b o u t b y a b e t t e r u n d e r s t a n d -i n g o f t h e f a c t o r s d e t e r m i n i n g t h e i n t e r a c t i o n s o fo r g a n i c p o l y m e r s w i t h c l a y s u r f a ce s a n d b y t h ei n n o v a t i o n s a n d d e v e l o p m e n t s b a s e d o n t h i su n d e r s t a n d i n g .A c k n o w t e d g m e n t - I a m inde b te d to t he l a t e Dr . G . F .W a lke r who d r e w m y a t t e n tion to t he a pp l i e d a spe c t s o fc lay-p olym er in te rac t ions and encou raged me in wr i t ingthis ar tic le .

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362 B. K. G. TH EN GSuite, E. and Arakawa, M. (1964) Mechanism of rein-forcement of rubber with hard clay. Infrared studies ofrubber-filler systems:Bull. I n s t . C h e m . R e s . , K y o t oU n i v . 42, 105-114.Tarasenko, Yu. G., Uskov, I. A. and Solomko, V. P.(1964) The effect of kaolin on the proper ties of poly-methyl methacrylate and polystyrene: U k r . K h i m . Z h .30, 86-90.Theng, B. K. G., Greenland, D. J. and Quirk, J. P. (1967)The swelling in water of comple xes of montmorillonitewith polyvinyl alcohol :A u s t . J . S o i l R e s . 5, 69-75.Theng, B. K. G. and Walker, G. F. (1970) Inte ract ions ofclay minerals with organic monomer s : I s r a e l J . C h e m .In press.Theng, B. K. G., Walker, G. F. and Ingles, O. G. (1969)Unpublis hed results.Uskov, I. A. (1960a) Filled polymers. I. The filling ofpolymethyl methacrylate with aminated bentonite addeddirectly to the monomer: V y s o k o m o l e k u l . S o e d i n . 2,200-204.Uskov, I. A. (1960 b) Filled polymers. 111. Polymeriza-tion of polymethyl methacrylate during dispersionof sodium bentonite: V y s o k o m o l e k u l . S o e d i n . 2 . 926-930.Uskov, 1. A., Galinskaya, V. I. and Artyukh, L. V. (1966)Calorimetric method of determining the interactionenergy of polymers with fillers: V y s o k o m o l e k u l . S o e d i n .8, 1853.

Uskvo, I. A. and Kusnitsyna, T. A. (1960) Effect of dis-persing aminated bentonite in monomer medium onreinforce ment of polymethyl methacrylate : V y s o k o m o l .S o e d i n . 2, 728-730.Uskov, I. A., Tarasenko, Yu. G. and Solomko, V. P.(1964) Effect of the deg ree of dispersion of clay fillerson the properties of amorphous polymers: V y s o k o m o l -e k u l . S o e d i n . 6, 1768-1772.Uskov, I. A. Tarasenko, Yu. G., Surovtsev, V. I. andSolomko, V. P. (1963) Investigations of bentonite-filled polymethyl methacryla te and polyst yrene :V y s o k o m o l e k u l . S o e d i n . A d g e z i y a P o l y m e r o v S b .S t a t e i 31-34.Van der Watt, H. V. H. and Bodman, G. B. (1960)Viscosimetric constants of suspensions of clay-polymer c o m p l e x e s : C l a y s a n d C l a y M i n e r al s , 9 ,568-584.Van Olphen, H. (1963) A n I n t r o d u c t i o n t o C l a y C o l l o i dC h e m i s t r y , Interscience, New York.

Walker, G. F. and Garrett, W. G. (1967) Silicate layerminerals and products made therefrom:U.S. P a t .3,356,611.Williams, B. G., Greenland, D. J. and Quirk, J. P. (1967)The tensile strength of soil cores containing polyvinylalcohol : A u s t . J . S o i I R e s . 5 , 85-92.Williams, B. G., Greenland, D. J. and Quirk, J. P. (1968)The water-stability of natural clay aggregates containingpolyvinyl alcohol :A u s t . J . S o i l R e s . 6, 59-66.R6sam6-On donne un expos6 des inter-r6actions entre les min6raux argileux et les polym6resorganiques, en mentionnant en particulier leurs applications darts les domaines de l'agriculture, dela technique des fondations et de I'industrie.Kurzreferat-Es wird iiber die Wechselwirkungen zwischen Tonmineralen und organischen Poly-meren berichtet, und zwar unter besonde rem Hinweis auf ihre Verwendung sberei che in der Land-wirtschaft, dem Ingenieurbau und der Industrie.Pe310Me - - l-lo,apo6Ho paccMoTperlo B3aHMO,/Ie,~CTBHe FIIHHHCTblX MrlFlepa.rloB c opFaHHqeCKHMHI10.rlHMepaMH, oco~oe BHHMaHHe y/leJleHO fix IIpHMeHeHHtO B ceJlbCKOM XO3~I~CTBe, ,/IJI~l y~yqlLIeHH~lCBOI~CTB FpyHTOB H B FIpOMblHUleHHOCTH.

clay water system

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