Viscous carrier compositions, including gels, formed with an organic liquid carrier and a layered material:polymer complex

Intercalates formed by contacting the layer material, e.g., a phyllosilicate, with an intercalant polymer to sorb or intercalate the polymer between adjacent platelets of the layered material. Sufficient intercalant polymer is sorbed between adjacent platelets to expand the adjacent platelets to a spacing of at least about 50 .ANG. (as measured after water removal to a maximum of 5% by weight water), up to about 100 .ANG. and preferably in the range of about 10-45 .ANG., so that the intercalate easily can be exfoliated into individual platelets. The intercalated complex is combined with an organic liquid into an unexpectedly viscous carrier material, for delivery of the carrier material, or for delivery of an active compound, e.g., a pharmaceutical, or cosmetic, or lubricant, e.g., food guide lubricants dissolved or dispersed in the carrier material. Alternatively, the intercalated complex can be exfoliated prior to combination with the organic liquid.

FIELD OF THE INVENTION 
The present invention is directed to viscous carrier or viscous solvent 
compositions useful for carrying active organic compounds, such as 
glycols; glycerols; alcohols; ketones; and other organic liquids; 
pigments; drugs; skin moisturizers; hair care compounds, e.g., silicone 
oils and silicone fluids; permanent waving lotion and hair relaxer 
reducing agents, and other hair care compounds, such as moisturizers, 
shampoos, hair conditioners, and shampoos/conditioners; oven cleaners; car 
wash compositions; cosmetics; alcohols and other de-icers for airplane 
wings and the like; lotions, ointments and creams; drug carriers for 
various pharmaceuticals and drugs, particularly for topical administration 
of medications, such as topical wound and burn medicaments. The viscous 
carrier compositions are formed from intercalated layered materials, 
and/or exfoliates thereof, manufactured by sorption of one or more 
intercalant compounds, e.g., oligomers or polymers between planar layers 
of a swellable layered material, such as a phyllosilicate or other layered 
material, to expand the interlayer spacing of adjacent layers to at least 
about 5 .ANG., preferably at least about 10 .ANG.. The intercalates and/or 
exfoliates are combined with an organic liquid carrier to viscosify the 
carrier. The intercalates and exfoliates are described in our 
above-identified co-pending parent applications. The intercalated layered 
materials preferably have at least two layers of oligomer and/or polymer 
molecules sorbed on the internal surfaces between adjacent layers of the 
planar platelets of the layered material, such as a phyllosilicate, 
preferably a smectite clay, to expand the interlayer spacing to at least 
about 5 Angstroms, preferably at least about 10 Angstroms, more preferably 
to at least about 20 Angstroms, and most preferably to at least about 
30-45 Angstroms, up to about 100 .ANG., or disappearance of periodicity. 
The resulting intercalates are neither entirely organophilic nor entirely 
hydrophilic, but a combination of the two, and easily can be exfoliated 
for or during admixture with a carrier or solvent to provide a stable, 
thixotropic composition, preferably a stable gel, capable of carrying any 
liquid hydrophilic or hydrophobic compound, particularly organic liquid 
compounds, and combinations of hydrophilic and hydrophobic liquids. 
BACKGROUND OF THE INVENTION AND PRIOR ART 
It is well known that phyllosilicates, such as smectite clays, e.g., sodium 
montmorillonite and calcium montmorillonite, can be treated with organic 
molecules, such as organic ammonium ions, to intercalate the organic 
molecules between adjacent, planar silicate layers, thereby substantially 
increasing the interlayer (interlaminar) spacing between the adjacent 
silicate layers. The thus-treated, intercalated phyllosilicates, then can 
be exfoliated, e.g., the silicate layers are separated, e.g., 
mechanically, by high shear mixing. The individual silicate layers, when 
admixed with a matrix polymer, before, after or during the polymerization 
of the matrix polymer, e.g., a polyamide--see U.S. Pat. Nos. 4,739,007; 
4,810,734; and 5,385,776--have been found to substantially improve one or 
more properties of the polymer, such as mechanical strength and/or high 
temperature characteristics. 
Exemplary of such prior art composites, also called "nanocomposites", are 
disclosed in published PCT disclosure of Allied Signal, Inc. WO 93/04118 
and U.S. Pat. No. 5,385,776, disclosing the admixture of individual 
platelet particles derived from intercalated layered silicate materials, 
with a polymer to form a polymer matrix having one or more properties of 
the matrix polymer improved by the addition of the exfoliated intercalate. 
As disclosed in W0 93/04118, the intercalate is formed (the interlayer 
spacing between adjacent silicate platelets is increased) by adsorption of 
a silane coupling agent or an onium cation, such as a quaternary ammonium 
compound, having a reactive group which is compatible with the matrix 
polymer. Such quaternary ammonium cations are well known to convert a 
highly hydrophilic clay, such as sodium or calcium montmorillonite, into 
an organophilic clay capable of sorbing organic molecules. A publication 
that discloses direct intercalation (without solvent) of polystyrene and 
poly(ethylene oxide) in organically modified silicates is Synthesis and 
Properties of Two-Dimensional Nanostructures by Direct Intercalation of 
Polymer Melts in Layered Silicates, Richard A. Vaia, et al., Chem. Mater., 
5:1694-1696(1993). Also as disclosed in Adv. Materials, 7, No. 2: (1985), 
pp, 154-156, New Polymer Electrolyte Nanocomposites: Melt Intercalation of 
Poly(Ethylene Oxide) in Mica-Type Silicates, Richard A. Vaia, et al., 
poly(ethylene oxide) can be intercalated directly into Na-montmorillonite 
and Li-montmorillonite by heating to 80.degree. C. for 2-6 hours to 
achieve a d-spacing of 17.7 .ANG.. The intercalation is accompanied by 
displacing water molecules, disposed between the clay platelets with 
polymer molecules. Apparently, however, the intercalated material could 
not be exfoliated and was tested in pellet form. It was quite surprising 
to one of the authors of these articles that exfoliated material could be 
manufactured in accordance with the present invention. 
Previous attempts have been made to intercalate polyvinylpyrrolidone (PVP), 
polyvinyl alcohol (PVOH) and poly(ethylene oxide) (PEO) between 
montmorillonite clay platelets with little success. As described in Levy, 
et al., Interlayer Adsorption of Polyvinylpyrrolidone on Montmorillonite, 
Journal of Colloid and Interface Science, Vol. 50, No. 3, March 1975, 
pages 442-450, attempts were made to sorb PVP (40,000 average M.W.) 
between monoionic montmorillonite clay platelets (Na, K, Ca and Mg) by 
successive washes with absolute ethanol, and then attempting to sorb the 
PVP by contact with 1% PVP/ethanol/water solutions, with varying amounts 
of water, via replacing the ethanol solvent molecules that were sorbed in 
washing (to expand the platelets to about 17.7 .ANG.). Only the sodium 
montmorillonite had expanded beyond a 20 .ANG. basal spacing (e.g., 26 
.ANG. and 32 .ANG.), at 5.sup.+ % H.sub.2 O, after contact with the 
PVP/ethanol/H.sub.2 O solution. It was concluded that the ethanol was 
needed to initially increase the basal spacing for later sorption of PVP, 
and that water did not directly affect the sorption of PVP between the 
clay platelets (Table II, page 445), except for sodium montmorillonite. 
The sorption was time consuming and difficult and met with little success. 
Further, as described in Greenland, Adsorption of Polyvinyl Alcohols by 
Montmorillonite, Journal of Colloid Sciences, Vol. 18, pages 647-664 
(1963), polyvinyl alcohols containing 12% residual acetyl groups could 
increase the basal spacing by only about 10 .ANG. due to the sorbed 
polyvinyl alcohol (PVOH). As the concentration of polymer in the 
intercalant polymer-containing solution was increased from 0.25% to 4%, 
the amount of polymer sorbed was substantially reduced, indicating that 
sorption might only be effective at polymer concentrations in the 
intercalant polymer-containing composition on the order of 1% by weight 
polymer, or less. Such a dilute process for intercalation of polymer into 
layered materials would be exceptionally costly in drying the intercalated 
layered materials for separation of intercalate from the polymer carrier, 
e.g., water, and, therefore, apparently no further work was accomplished 
toward commercialization. 
In accordance with one embodiment of the present invention, intercalates 
are prepared by contacting a phyllosilicate with a PVP polymer, preferably 
essentially alcohol-free, or a PVOH intercalant polymer composition, 
wherein the PVOH preferably contains 5% or less residual acetyl groups, 
more preferably fully hydrolyzed, containing 1% or less acetyl groups. 
In accordance with an important feature of the present invention, best 
results are achieved using a water soluble oligomer (herein defined as a 
prepolymer having 2 to about 15 recurring monomeric units, which can be 
the same or different) or polymer (herein defined as having more than 
about 15 recurring monomeric units, which can be the same or different) 
composition for intercalation having at least about 2%, preferably at 
least about 5% by weight, more preferably at least about 10% by weight 
intercalant oligomer or intercalant polymer concentration, most preferably 
about 30% to about 80% by weight oligomer and/or polymer, based on the 
weight of oligomer and/or polymer and carrier (e.g., water with or without 
another solvent for the intercalant oligomer or intercalant polymer) to 
achieve better sorption of the intercalant polymers between phyllosilicate 
platelets. Regardless of the concentration of polymer in liquid solvent of 
the intercalating composition, the intercalating composition should have a 
polymer:layered material ratio of at least 1:20, preferably at least 1:10, 
more preferably at least 1:5, and most preferably about 1:4 to achieve 
efficient intercalation of the polymer between adjacent platelets of the 
layered material. The oligomer or polymer sorbed between and permanently 
bonded to the silicate platelets causes separation or added spacing 
between adjacent silicate platelets and, for simplicity of description, 
both the oligomers and polymers are hereinafter called the "intercalant" 
or "intercalant polymer" or "polymer intercalant". In this manner, the 
oligomers or polymers will be sorbed sufficiently to increase the 
interlayer spacing of the phyllosilicate in the range of about 5 .ANG. to 
about 100 .ANG., preferably at least about 10 .ANG., for easier and more 
complete exfoliation, in a commercially viable process, regardless of the 
particular phyllosilicate or intercalant polymer. 
A phyllosilicate, such as a smectite clay, can be intercalated sufficiently 
for subsequent exfoliation by sorption of polymers or oligomers that have 
carbonyl, hydroxyl, carboxyl, amine, amide, ether, ester, sulfate, 
sulfonate, sulfinate, sulfamate, phosphate, phosphonate, phosphinate 
functionalities, or aromatic rings to provide metal cation chelate-type 
bonding between two functional groups of one or two intercalant polymer 
molecules and the metal cations bonded to the inner surfaces of the 
phyllosilicate platelets. Sorption and metal cation electrostatic 
attraction or bonding of a platelet metal cation between two oxygen or 
nitrogen atoms of the molecules; or the electrostatic bonding between the 
interlayer cations in hexagonal or pseudohexagonal rings of the smectite 
layers and an intercalant polymer aromatic ring structure increases the 
interlayer spacing between adjacent silicate platelets or other layered 
material to at least about about 5 .ANG., preferably at least about 10 
.ANG., and more preferably at least about 20 .ANG., and most preferably in 
the range of about 30 .ANG. to about 45 .ANG.. Such intercalated 
phyllosilicates easily can be exfoliated into individual phyllosilicate 
platelets before or during admixture with a liquid carrier or solvent, for 
example, one or more monohydric alcohols, such as methanol, ethanol, 
propanol, and/or butanol; polyhydric alcohols, such as glycerols and 
glycols, e.g., ethylene glycol, propylene glycol, butylene glycol, 
glycerine and mixtures thereof; aldehydes, ketones, carboxylic acids; 
amines; amides; and other solvents, for delivery of the solvent in a 
thixotropic composition, or for delivery of any active hydrophobic or 
hydrophilic organic compound, such as a typically active pharmaceutical, 
dissolved or dispersed in the carrier or solvent, in a thixotropic 
composition. 
Depending upon the conditions that the composition is subjected to during 
intercalation and exfoliation, particularly temperature; pH; and amount of 
water contained in the intercalating composition, the intercalate and/or 
exfoliate/carrier composition can be formed to any desired viscosity, 
e.g., at least about 100 centipoises, preferably at least about 500-1000 
centipoises, whether or not gelled, and particularly to extremely high 
viscosities of about 5,000 to about 5,000,000 centipoises. The 
compositions are thixotropic so that shearing will lower viscosity for 
easier delivery, and then by reducing shear or eliminating shear, the 
compositions will increase in viscosity. The intercalant polymer 
intercalates between the spaces of adjacent platelets of the layered 
material for easy exfoliation, and complexes with the metal cations on the 
platelet surfaces where the polymer remains after the intercalant, or 
exfoliate thereof, is combined with the carrier/solvent. It is theorized 
that the polymer coating on the surfaces of the clay platelets is 
ionically complexed with interlayer cations and participates (aids) in the 
viscosification and thixotropy of the carrier/solvent composition. 
However, other forms of bonding such as hydrogen bonding or Van Der Waals 
forces or molecular complexing also may be responsible for the adherence 
of the polymer to the surfaces of the layered material, either entirely, 
or in part. 
DEFINITIONS 
Whenever used in this Specification, the terms set forth shall have the 
following meanings: 
"Layered Material" shall mean an inorganic material, such as a smectite 
clay mineral, that is in the form of a plurality of adjacent, bound layers 
and has a thickness, for each layer, of about 3 .ANG. to about 50 .ANG., 
preferably about 10 .ANG.. 
"Platelets" shall mean individual layers of the Layered Material. 
"Intercalate" or "Intercalated" shall mean a Layered Material that includes 
oligomer and/or polymer molecules disposed between adjacent platelets of 
the Layered Material to increase the interlayer spacing between the 
adjacent platelets to at least about 5 .ANG., preferably at least about 10 
.ANG.. 
"Intercalation" shall mean a process for forming an Intercalate. 
"Intercalant Polymer" or "Intercalant" shall mean an oligomer or polymer 
that is sorbed between Platelets of the Layered Material and complexes 
with the platelet surfaces to form an Intercalate. 
"Intercalating Carrier" shall mean a carrier comprising water with or 
without an organic solvent used together with an Intercalant Polymer to 
form an Intercalating Composition capable of achieving Intercalation of 
the Layered Material. 
"Intercalating Composition" shall mean a composition comprising an 
Intercalant Polymer, an Intercalating Carrier for the Intercalant Polymer, 
and a Layered Material. 
"Exfoliate" or "Exfoliated" shall mean individual platelets of an 
Intercalated Layered Material so that adjacent platelets of the 
Intercalated Layered Material can be dispersed individually throughout a 
carrier material, such as water, an alcohol or glycol, or any other 
organic solvent. 
"Exfoliation" shall mean a process for forming an Exfoliate from an 
Intercalate. 
SUMMARY OF THE INVENTION 
In brief, the present invention is directed to viscous, thixotropic carrier 
compositions comprising a liquid carrier or solvent composition containing 
intercalated and/or exfoliated platelets of a layered material. The 
intercalated layered material is formed by contacting a layered material, 
such as a phyllosilicate, with an oligomer and/or polymer to sorb or 
intercalate the intercalant polymer or mixtures of intercalant polymers 
between adjacent phyllosilicate platelets. Sufficient intercalant polymer 
is sorbed between adjacent phyllosilicate platelets to expand the spacing 
between adjacent platelets (interlayer spacing) to a distance of at least 
about 5 .ANG., preferably at least about 10 .ANG. (as measured after water 
removal to a maximum water content of 5% by weight) and preferably in the 
range of about 30-45 .ANG., so that the intercalate easily can be 
exfoliated, sometimes naturally, without shearing being necessary. At 
times, the intercalate requires shearing for exfoliation that easily can 
be accomplished, e.g., when mixing the intercalate with the carrier or 
solvent, to provide a composition of carrier or solvent and exfoliated 
platelets of the layered material having a desired viscosity of about 20 
centipoises to about 5,000,000 centiposes, preferably at least about 500 
centipoises. 
The viscous compositions can be in the form of a stable thixotropic gel 
that is not subject to phase separation and can be used to deliver any 
active materials, such as in the cosmetic, hair care and pharmaceutical 
industries. The layered material is intercalated and optionally exfoliated 
by contact with an intercalant polymer and water and then mixed and/or 
extruded to intercalate the polymer between adjacent phyllosilicate 
platelets and optionally separate (exfoliate) the layered material into 
individual platelets. The amount of water varies, depending upon the 
amount of shear imparted to the layered material in contact with the 
polymer and water. In one method, the intercalating composition is pug 
milled or extruded. At a water content of about 25% by weight to about 50% 
by weight water, preferably about 35% to about 40% by weight water, based 
on the dry weight of the layered material, e.g., clay. In another method, 
the clay and water are slurried, with at least about 25% by weight water, 
based on the dry weight of the layered material, e.g., preferably less 
than about 20% by weight clay in water, based on the total weight of 
layered material and water, more preferably less than about 10% layered 
material in water, with the addition of about 2% by weight to about 90% by 
weight polymer, based on the dry weight of the layered material. 
In accordance with a preferred embodiment of the present invention, the 
intercalant polymer should be water-soluble (herein defined as 
sufficiently soluble such that at least 0.1 gram of the polymer will 
dissolve per 100 grams of distilled water at 25.degree. C.). In accordance 
with a preferred embodiment of the present invention, the intercalant 
polymer should include an aromatic ring and/or have a functionality 
selected from the group consisting of a carbonyl; carboxyl; hydroxyl; 
amine; amide; ether; ester, sulfate, solfonate, sulfinate, sulfamate, 
phosphate, phosphonate, phosphinate functionality, or an aromatic ring to 
be sufficiently complexed or bound to the platelet surfaces of the layered 
material. It is hereby theorized that polymer binding to the platelet 
surfaces is by metal cation electrostatic bonding or complexing, e.g., 
chelation, of the metal cations of the phyllosilicate sharing electrons 
with two carbonyl, two carboxyl, two hydroxyl, two oxygen, two amine, two 
SO.sub.x, two PO.sub.x (wherein x=2, 3, or 4) and/or two amide 
functionalities of one intercalant polymer molecule, or of two adjacent 
intercalant polymer molecules to an inner surface of the phyllosilicate 
platelets. Such intercalant polymers have sufficient affinity for the 
phyllosilicate platelets to provide sufficient interlayer spacing for 
exfoliation, e.g., about 5 .ANG.-100 .ANG., preferably about 10 .ANG.-50 
.ANG., and to maintain attachment to the surfaces of the platelets, 
without the need for coupling agents or spacing agents, such as the onium 
ion or silane coupling agents disclosed in the above-mentioned prior art. 
Sorption of the intercalant polymer should be sufficient to achieve 
expansion of adjacent platelets of the layered material (when measured 
dry--having a maximum of about 5% by weight water) to an interlayer 
spacing of at least about 5 .ANG., preferably a spacing of at least about 
10 .ANG., more preferably a spacing of at least about 20 .ANG., and most 
preferably a spacing of about 30-45 .ANG.. To achieve intercalates that 
can be exfoliated easily using the preferred water-soluble polymer 
intercalants disclosed herein, such as polyvinylpyrrolidone, polyvinyl 
alcohol, and mixtures thereof, the weight ratio of intercalant polymer to 
layered material, preferably a water-swellable smectite clay such as 
sodium bentonite, in the intercalating composition contacting the 
phyllosilicate should be at least about 1:20, preferably at least about 
1:12 to 1:10, more preferably at least about 1:5, and most preferably 
about 1:5 to about 1:3. It is preferred that the concentration of polymer 
in the intercalating composition, based on the total weight of polymer 
plus intercalant carrier (water plus any organic liquid solvent) in the 
intercalating composition is at least about 15% by weight, more preferably 
at least about 20% by weight polymer, for example about 20%-30% to about 
90% by weight polymer, based on the weight of polymer plus intercalant 
carrier (water plus any organic solvent) in the intercalant composition 
during intercalation. 
It has been found that the intercalates of the present invention are 
increased in interlayer spacing step-wise. If the phyllosilicate is 
contacted with an intercalating composition containing less than about 16% 
by weight intercalant polymer, e.g., 10% to about 15% by weight polymer, 
based on the dry weight of the phyllosilicate, a monolayer width of 
intercalant polymer is sorbed (intercalated) between the adjacent 
platelets of the layered material. A monolayer of polymer intercalated 
between platelets increases the interlayer spacing to about 5 .ANG. to 
less than about 10 .ANG.. When the amount of intercalant polymer is in the 
range of about 16% to less than about 35% by weight, based on the weight 
of the dry layered material, the intercalant polymer is sorbed in a 
bilayer, and each layer complexes separately with one of two adjacent 
platelet surfaces, thereby increasing the interlayer spacing to about 10 
.ANG. to about 16 .ANG., as shown in FIGS. 1 and 2. At an intercalant 
polymer loading in the intercalating composition of about 35% to less than 
about 55% intercalant polymer, based on the dry weight of the layered 
material in the intercalating composition, the interlayer spacing is 
increased to about 20 .ANG. to about 25 .ANG., corresponding to three 
layers of intercalant polymer sorbed between adjacent platelets of the 
layered material, as shown in FIGS. 1 and 2. At an intercalant polymer 
loading of about 55% to about 80% intercalant polymer, based on the dry 
weight of the layered material in the intercalating composition, the 
interlayer spacing will be increased to about 30 .ANG. to about 35 .ANG., 
corresponding to 4 and 5 layers of intercalant polymer sorbed 
(intercalated) between and complexed to adjacent platelets of the layered 
material, as shown in FIGS. 1 and 2. 
Such interlayer spacings have never been achieved by direct intercalation 
of an oligomer or polymer molecule, without prior sorption of a coupling 
agent, such as an onium or silane coupling agent, and provides easier and 
more complete exfoliation for or during incorporation of the platelets 
into a carrier or solvent to provide unexpectedly viscous carrier 
compositions, for delivery of the carrier, or for administration of an 
active compound that is dissolved or dispersed in the carrier or solvent. 
Such compositions, especially the high viscosity gels, are particularly 
useful for delivery of active compounds, such as oxidizing agents for hair 
waving lotions, and drugs for topical administration, since extremely high 
viscosities are obtainable; and for admixtures of the platelets with polar 
solvents in modifying rheology, e.g., of cosmetics, oil-well drilling 
fluids, paints, lubricants, especially food grade lubricants in the 
manufacture of oil and grease, and the like. 
Once exfoliated, the platelets of the intercalate are predominantly 
completely separated into individual platelets having intercalant polymer 
molecules complexed with the platelet surfaces, and the originally 
adjacent platelets no longer are retained in a parallel, spaced 
disposition, but are free to move as predominantly individual, polymer 
coated (continuously or discontinuously) platelets throughout a carrier or 
solvent material to maintain viscosity and thixotropy of the carrier 
material. The predominantly individual phyllosilicate platelets, having 
their platelet surfaces complexed with polymer molecules, are randomly, 
homogeneously and uniformly dispersed, predominantly as individual 
platelets, throughout the carrier or solvent to achieve new and unexpected 
viscosities in the carrier/platelet compositions even after addition of an 
active organic compound, such as a cosmetic component or a medicament, for 
administration of the active organic compound(s) from the composition. 
As recognized, the thickness of exfoliated, individual clay platelets 
(about 10 .ANG.) is relatively small compared to the size of the flat 
opposite polymer-complexed platelet faces. The clay platelets have an 
aspect ratio in the range of about 200 to about 2,000. Dispersing such 
finely divided platelet particles into an organic liquid carrier or 
solvent provides a very large area of contact between carrier and platelet 
particles, for a given volume of particles in the composition, and 
provides a high degree of platelet homogeneity and unexpectedly high 
viscosity to the composition. 
The polymer intercalants used to form the intercalates and/or exfoliates 
used in the compositions of the present invention need not have any (but 
can include) reactivity with the carrier or solvent in which the inventive 
intercalates and/or exfoliates are dispersed, while improving one or more 
properties, particularly viscosity, of the carrier or solvent material.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
To form the intercalated materials useful in admixture with the carriers or 
solvents in accordance with the present invention, the phyllosilicate 
should be swelled or intercalated by sorption of an oligomer or polymer 
that includes an aromatic ring and/or a functionality selected from the 
group consisting of carbonyl; carboxyl; hydroxyl; amine; amide; ether; 
ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, phosphonate, 
phosphinate, or combinations thereof. In accordance with a preferred 
embodiment of the present invention, the intercalating composition should 
include at least about 4% by weight water, up to about 5000% by weight 
water, based on the dry weight of the phyllosilicate, preferably about 7% 
to about 100% water, more preferably about 25% to about 50% by weight 
water, prior to or during contact with the intercalant polymer to achieve 
sufficient intercalation for exfoliation. Preferably, the phyllosilicate 
should include at least about 4% by weight water before contact with the 
intercalating carrier for efficient intercalation. The amount of 
intercalant polymer in contact with the phyllosilicate from the 
intercalating composition, for efficient exfoliation, should provide an 
intercalant polymer/phyllosilicate weight ratio (based on the dry weight 
of the phyllosilicate) of at least about 1:20, preferably at least about 
3.2:20, and more preferably about 4-14:20, to provide efficient sorption 
and complexing (intercalation) of the polymer between the platelets of the 
layered material, e.g., phyllosilicate, (preferably about 16 to about 70 
percent by weight intercalant polymer, based on the dry weight of the 
layered silicate material). 
The preferred polymer intercalants are water-soluble and are added to the 
intercalating composition in the form of a solid or liquid (neat or 
aqueous solution or dispersion, with or without a liquid organic solvent, 
e.g., alcohol) having an intercalant polymer concentration of at least 
about 2%, preferably at least about 5% by weight polymer, more preferably 
at least about 50% to about 100% by weight intercalant polymer in the 
intercalating composition, based on the dry weight of the layered 
material, for intercalant polymer sorption. The polymer can be added as a 
solid with the addition to the layered material/polymer blend of at least 
about 20% water, preferably at least about 30% water to about 5000% water 
or more, based on the dry weight of the layered material, with or without 
another solvent for the intercalant polymer. Preferably about 30% to about 
50% water, more preferably about 30% to about 40% by weight water, based 
on the dry weight of the layered material, is included in the 
intercalating composition, when extruding or pug milling, so that less 
water or solvent is sorbed by the intercalate, thereby necessitating less 
drying energy after intercalation. The intercalant polymer may be 
introduced into the spaces between every layer, nearly every layer, or at 
least a predominance of the layers of the layered material such that the 
subsequently exfoliated platelet particles are preferably, predominantly 
less than about 5 layers in thickness; more preferably, predominantly 
about 1 or 2 layers in thickness; and most preferably, predominantly 
single platelets. 
Any swellable layered material that sufficiently sorbs the intercalant 
polymer to increase the interlayer spacing between adjacent phyllosilicate 
platelets to at least about 5 .ANG., preferably at least about 10 .ANG. 
(when the phyllosilicate spacing is measured dry--having a maximum of 
about 5% by weight water) may be used in the practice of this invention. 
Useful swellable layered materials include phyllosilicates, such as 
smectite clay minerals, e.g., montmorillonite, particularly sodium 
montmorillonite; magnesium montmorillonite and/or calcium montmorillonite; 
nontronite; beidellite; volkonskoite; hectorite; saponite; sauconite; 
sobockite; stevensite; svinfordite; vermiculite; and the like. Other 
useful layered materials include micaceous minerals, such as illite and 
mixed layered illite/smectite minerals, such as rectorite, tarosovite, 
ledikite and admixtures of illites with the clay minerals named above. 
Other layered materials having little or no charge on the layers may be 
useful in this invention provided they can be intercalated with the 
intercalant polymers to expand their interlayer spacing to at least about 
5 .ANG., preferably to at least about 10 .ANG.. Preferred swellable 
layered materials are phyllosilicates of the 2:1 type having a negative 
charge on the layers ranging from about 0.15 to about 0.9 charges per 
formula unit and a commensurate number of exchangeable metal cations in 
the interlayer spaces. Most preferred layered materials are smectite clay 
minerals such as montmorillonite, nontronite, beidellite, volkonskoite, 
hectorite, saponite, sauconite, sobockite, stevensite, and svinfordite. 
As used herein the "interlayer spacing" refers to the distance between the 
internal faces of the adjacent dry layers as they are assembled in the 
layered material before any delamination (exfoliation) takes place. The 
interlayer spacing is measured when the layered material is "air dry", 
e.g., contains about 3-10% water, preferably about 3-6% by weight water, 
based on the dry weight of the layered material. The preferred clay 
materials generally include interlayer cations such as Na.sup.+, 
Ca.sup.+2, K.sup.+, Mg.sup.+2, NH.sub.4.sup.+ and the like, including 
mixtures thereof. 
The amount of intercalant polymer intercalated into the swellable layered 
materials useful in this invention, in order that the intercalated layered 
material platelet surfaces sufficiently complex with the polymer 
molecules, such that the layered material may be easily exfoliated or 
delaminated into individual platelets, may vary substantially between 
about 10% and about 80%, based on the dry weight of the layered silicate 
material. In the preferred embodiments of the invention, amounts of 
polymer intercalants employed, with respect to the dry weight of layered 
material being intercalated, will preferably range from about 8 grams of 
intercalant polymer/100 grams of layered material (dry basis), preferably 
at least about 10 grams of polymer/100 grams of layered material to about 
80-90 grams intercalant polymer/100 grams of layered material. More 
preferred amounts are from about 20 grams intercalant polymer/100 grams of 
layered material to about 60 grams intercalant polymer/100 grams of 
layered material (dry basis). 
The polymer intercalants are introduced into (sorbed within) the interlayer 
spaces of the layered material in one of two ways. In a preferred method 
of intercalating, the layered material is intimately mixed, e.g., by 
extrusion or pug milling, to form an intercalating composition comprising 
the layered material, in an intercalant polymer or intercalant 
polymer/water solution, or intercalant polymer, water and an organic 
solvent. To achieve sufficient intercalation for exfoliation, the layered 
material/intercalant polymer blend contains at least about 8% by weight, 
preferably at least about 10% by weight intercalant polymer, based on the 
dry weight of the layered material. The intercalating carrier (preferably 
water, with or without an organic solvent) can be added by first 
solubilizing or dispersing the intercalant polymer in the carrier; or the 
dry intercalant polymer and relatively dry phyllosilicate (preferably 
containing at least about 4% by weight water) can be blended and the 
intercalating carrier added to the blend, or to the phyllosilicate prior 
to adding the dry intercalant polymer. In every case, it has been found 
that surprising sorption and complexing of intercalant polymer between 
platelets is achieved at relatively low loadings of intercalating carrier, 
especially H.sub.2 O, e.g., at least about 4% by weight water, based on 
the dry weight of the phyllosilicate. When intercalating the 
phyllosilicate in slurry form (e.g. 900 pounds water, 100 pounds 
phyllosillicate, 25 pounds polymer) the amount of water can vary from a 
preferred minimum of at least about 30% by weight water, with no upper 
limit to the amount of water in intercalating composition (the 
phyllosilicate intercalate is easily separated from the intercalating 
composition). 
Alternatively, the intercalating carrier, e.g., water, with or without an 
organic solvent, can be added directly to the phyllosilicate prior to 
adding the intercalant polymer, either dry or in solution. Sorption of the 
polymer intercalant molecules may be performed by exposing the layered 
material to dry or liquid polymer intercalant compositions containing at 
least about 2% by weight, preferably at least about 5% by weight 
intercalant polymer, more preferably at least about 50% intercalant 
polymer, based on the dry weight of the layered material. Sorption may be 
aided by exposure of the intercalating composition to heat, pressure, 
ultrasonic cavitation, or microwaves. 
In accordance with another method of intercalating the intercalant polymer 
between the platelets of the layered material and exfoliating the 
intercalate, the layered material, containing at least about 4% by weight 
water, preferably about 10% to about 15% by weight water, is blended with 
an aqueous solution of a water-soluble intercalant polymer in a ratio 
sufficient to provide at least about 8% by weight, preferably at least 
about 10% by weight intercalant polymer, based on the dry weight of the 
layered material. The blend then preferably is extruded for faster 
intercation of the polymer with the layered material. 
The preferred polymer intercalants are water-soluble, such as 
polyvinylpyrrolidone (PVP) having a monomeric structure (I) as follows: 
##STR1## 
The water-solubility of PVP can be adjusted according to (1) the degree of 
hydrolysis of the polyvinylpyrrolidone, and (2) by forming a metal salt of 
PVP, such as sodium or potassium. PVP can be hydrolyzed to the structure 
(II): 
##STR2## 
and the PVP, or copolymers of vinylpyrrolidone and a vinyl amide of 
.gamma.-amine butyric acid, can be intercalated in the salt form, e.g., 
sodium or potassium polyvinylpyrrolidone polymers. Preferred PVP 
intercalants, and the following PVP derivatives, should have a weight 
average molecular weight in the range of about 100 to about 100,000 or 
more, more preferably about 1,000 to about 40,000. 
Other suitable water-soluble vinyl polymers include poly(vinyl alcohol) 
##STR3## 
The polyvinyl alcohols function best when they are essentially fully 
hydrolyzed, e.g., 5% or less acetyl groups, preferably 1% or less residual 
acetyl groups. The lower molecular weight PVA's function best, e.g., a 
weight average molecular weight of about 2,000 to about 10,000, but higher 
molecular weights also function, e.g., up to about 100,000. 
The polyacrylic acid polymers and copolymers and partially or fully 
neutralized salts, e.g., metal salts, are also suitable, having monomer 
units: 
##STR4## 
and are commercially available as CARBOPOL resins from B. F. Goodrich and 
PRIMAL resins from Rohm & Haas. Light cross-linking is acceptable, so long 
as water-solubility is retained. Weight average molecular weights, for the 
polyacrylic polymers and copolymers described above and below, of about 
10,000 or less, e.g., 200-10,000, intercalate more easily, but higher 
molecular weights up to about 100,000 or more also function. 
Other water-soluble derivatives of, and substituted, polyacrylic acids also 
are useful as intercalant polymers in accordance with the present 
invention, such as poly(methacrylic acid), (PMAA), having a monomeric 
structure: 
##STR5## 
Similar water-soluble polymers and copolymers that are suitable in 
accordance with the present invention include poly(methacrylamide), or 
PMAAm, having a general monomeric structure: 
##STR6## 
Poly(N,N-Dimethylacrylamide) having the general monomeric structure: 
##STR7## 
Poly(N-Isopropylacrylamide), or PIPAAm, having the monomeric structure: 
##STR8## 
Poly(N-acetamidoacrylamide), having a monomeric structure: 
##STR9## 
and Poly(N-acetmidomethacrylamide), having a monomeric structure: 
##STR10## 
Water-soluble copolymers including any one or more of the above-described 
acrylic polymers also are useful in accordance with the principles of the 
present invention, including the acrylic interpolymers of polyacrylic acid 
and poly(methacrylic acid); polyacrylic acid with poly(methacrylamide); 
and polyacrylic acid with methacrylic acid. 
Other suitable water-soluble polymers include polyvinyloxazolidone (PVO) 
and polyvinylmethyloxazolidone (PVMO), having the monomeric structures: 
##STR11## 
Also suitable are polyoxypropylene, polyoxyethylene block polymers that 
conform to the formulas: 
##STR12## 
wherein x and z are each an integer in the range of about 4 to about 30; 
and y is an integer in the range of about 4 to about 100, for example 
Meroxapol 105; Meroxapol 108; Meroxapol 171; Meroxapol 172; Meroxapol 174; 
Meroxapol 178; Meroxapol 251; Meroxapol 252; Meroxapol 254; Meroxapol 255; 
Meroxapol 258; Meroxapol 311; Meroxapol 312; and Meroxapol 314. 
Other suitable water-soluble/water-dispersible intercalant polymers include 
polyacrylamide and copolymers of acrylamide; acrylamide/sodium acrylate 
copolymer; acrylate/acrylamide copolymer; acrylate/ammonium methacrylate 
copolymer; acrylate/diacetoneacrylamide copolymers; acrylic/acrylate 
copolymers; adipic acid/dimethylaminohydroxypropyl diethylenetriamine 
copolymer; ammonium acrylate copolymers; ammonium styrene/acrylate 
copolymers; ammonium vinyl acetate/acrylate copolymers; 
aminomethanepropanol (AMP) acrylate/diacetoneacrylamide copolymers; 
aminomethylpropanediol (AMPD) acrylate/diacetoneacrylamide copolymers; 
butyl benzoic acid/phthalic anhydride/trimethylolethane copolymer; 
cornstarch/acrylamide/sodium acrylate copolymer; diethylene 
glycolamine/epichlorohydrin/piperazine copolymer; dodecanedioic 
acid/cetearyl alcohol/glycol copolymers; ethylene/vinyl alcohol copolymer; 
ethyl ester of polyethyleneimines, such as hydroxyethyl/PEI-1000 and 
hydroxyethyl PEI-1500; isopropyl ester of, polyvinyl 
methacrylate/methacrylic acid (PVM/MA) copolymer; melamine/formaldehyde 
resin; methacryloyl ethyl betaine/methacrylate copolymers; methoxy 
PEG-22/dodecyl glycol copolymer; octadecene/maleic anhydride copolymer; 
octylacrylamide/acrylate/butylaminoethyl methacrylate copolymers; 
octylacrylamide/acrylate copolymers; polyethylene glycol (PEG)/dodecyl 
glycol copolymers; polyvinylimines, such as, PEI-7; PEI-15; PEI-30; 
PEI-45; PEI-275; PEI-700; PEI-1000; PEI-1500; and PEI-2500; phthalic 
anhydride/glycerin/glycidyl decanoate copolymer; metal salts of acrylic 
and polyacrylic acid; polyaminopropyl biguanide; polymeric quaternary 
ammonium salts, such as polyquaternium-1; polyquaternium-2; 
polyquaternium-4; polyquaternium-5; polyquaternium-6; polyquaternium-7; 
polyquaternium-8; polyquaternium-9; polyquaternium-10; polyquaternium-11; 
polyquaternium-12; polyquaternium-13; polyquaternium-14; and 
polyquaternium-15; polyvinyl imidazolinium acetate; potassium 
polyacrylate; sodium polyacrylate; metal salts of PVM/MA copolymers, e.g. 
Li, K, Na, Ru, Ce salts; polyvinylpyrrolidone (PVP)/eicosene copolymers; 
PVP/ethyl methacrylate/methacrylic acid copolymer; PVP/hexadecene 
copolymer; polyvinylpyrrolidone/vinyl acetate (PVP/VA) copolymer; 
PVP/vinyl acetate/itaconic acid copolymer; sodium acrylate/vinyl alcohol 
copolymers; sodium C.sub.4 -C.sub.12, and other metal salts of 
olefin/maleic acid copolymers; sodium polymethacrylate; sodium polystyrene 
sulfonate; sodium styrene/acrylate/PEG-10 dimaleate copolymer; 
water-soluble esters and ethers of cellulose; sodium styrene/PEG-10 
maleate/nonoxynol-10 maleate/acrylate copolymer; 
starch/acrylate/acrylamide copolymers; styrene/acrylamide copolymer; 
styrene/acrylate/ammonium methacrylate copolymer; styrene/maleic anhydride 
copolymer; styrene/PVO copolymer; sucrose benzoate/sucrose acetate 
isobutyrate/butyl benzyl phthalate copolymer; sucrose benzoate/sucrose 
acetate isobutyrate/butyl benzylphthalate/methyl methacrylate copolymer; 
urea/formaldehyde prepolymers; urea/melamine/formaldehyde prepolymers; 
vinyl acetate/crotonic acid copolymers; and vinyl alcohol copolymers. 
Other water-soluble polymeric polyols and polyhydric alcohols, such as 
polysaccharides, also are suitable as polymer intercalants. 
The amount of intercalated and/or exfoliated layered material included in 
the liquid carrier or solvent compositions to form the viscous 
compositions suitable to deliver the carrier or some carrier-dissolved or 
carrier-dispersed active material, such as a pharmaceutical, may vary 
widely depending on the intended use and desired viscosity of the 
composition. For example, relatively higher amounts of intercalates, i.e., 
from about 10% to about 30% by weight of the total composition, are used 
in forming solvent gels having extremely high viscosities, e.g., 5,000 to 
5,000,000 centipoises. Extremely high viscosities, however, also can be 
achieved with a relatively small concentration of intercalates and/or 
exfoliates thereof, e.g., 0.1% to 5% by weight, by adjusting the pH of the 
composition in the range of about 0-6 or about 10-14 and/or by heating the 
composition above room temperature, e.g., in the range of about 25.degree. 
C. to about 200.degree. C., preferably about 75.degree. C. to about 
100.degree. C. It is preferred that the intercalate or platelet loading be 
less than about 10% by weight of the composition. Intercalate or platelet 
particle loadings within the range of about 0.01% to about 40% by weight, 
preferably about 0.05% to about 20%, more preferably about 0.5% to about 
10% of the total weight of the composition significantly increases the 
viscosity of the composition. In general, the amount of intercalate and/or 
platelet particles incorporated into the carrier/solvent is less than 
about 20% by weight of the total composition, and preferably from about 
0.05% to about 20% by weight of the composition, more preferably from 
about 0.01% to about 10% by weight of the composition, and most preferably 
from about 0.01% to about 5%, based on the total weight of the 
composition. 
In accordance with an important feature of the present invention, the 
intercalate and/or platelet/carrier compositions of the present invention 
can be manufactured in a concentrated form, e.g., as a master gel, e.g., 
having about 10-90%, preferably about 20-80% intercalate and/or exfoliated 
platelets of layered material and about 10-90%, preferably about 20-80% 
carrier/solvent. The master gel can be later diluted and mixed with 
additional carrier or solvent to reduce the viscosity of the composition 
to a desired level. 
The intercalates, and/or exfoliates thereof, are mixed with a carrier or 
solvent to produce viscous compositions of the carrier or solvent 
optionally including one or more active compounds, such as an 
antiperspirant compound, dissolved or dispersed in the carrier or solvent. 
In accordance with an important feature of the present invention, a wide 
variety of topically-active compounds can be incorporated into a stable 
composition of the present invention. Such topically active compositions 
include cosmetic, industrial, and medicinal compounds that act upon 
contact with the skin or hair, or are used to adjust rheology of 
industrial greases and the like. In accordance with another important 
feature of the present invention, a topically-active compound can be 
solubilized in the composition of the present invention or can be 
homogeneously dispersed throughout the composition as an insoluble, 
particulate material. In either case topically-effective compositions of 
the present invention are resistant to composition separation and 
effectively apply the topically-active compound to the skin or hair. If 
required for stability, a surfactant can be included in the composition, 
such as any disclosed in Laughlin, et al. U.S. Pat. No. 3,929,678, hereby 
incorporated by reference. In general, the topically-effective 
compositions of the present invention demonstrate essentially no phase 
separation if the topically-active compound is solubilized in the 
compositions. Furthermore, if the topically-active compound is insoluble 
in the composition, the composition demonstrates essentially no phase 
separation. 
The topically-active compounds can be a cosmetically-active compound, a 
medically-active compound or any other compound that is useful upon 
application to the skin or hair. Such topically-active compounds include, 
for example, antiperspirants, antidandruff agents, antibacterial 
compounds, antifungal compounds, anti-inflammatory compounds, topical 
anesthetics, sunscreens and other cosmetic and medical topically-effective 
compounds. 
Therefore, in accordance with an important feature of the present 
invention, the stable topically-effective composition can include any of 
the generally-known antiperspirant compounds such as finely-divided solid 
astringent salts, for example, aluminum chlorohydrate, aluminum 
chlorohydrox, zirconium chlorohydrate, and complexes of aluminum 
chlorohydrate with zirconyl chloride or zirconyl hydroxychloride. In 
general, the amount of the antiperspirant compound, such as aluminum 
zirconium tetrachlorohydrex glycine in the composition can range from 
about 0.01% to about 50%, and preferably from about 0.1% to about 30%, by 
weight of the total composition. 
Other topically-active compounds can be included in the compositions of the 
present invention in an amount sufficient to perform their intended 
function. For example, zinc oxide, titanium dioxide or similar compounds 
can be included if the composition is intended to be a sunscreen. 
Similarly, topically-active drugs, like antifungal compounds; 
antibacterial compounds; anti-inflammatory compounds; topical anesthetics; 
skin rash, skin disease and dermatitis medications; and anti-itch and 
irritation-reducing compounds can be included in the compositions of the 
present invention. For example, analgesics such as benzocaine, dyclonine 
hydrochloride, aloe vera and the like; anesthetics such as butamben 
picrate, lidocaine hydrochloride, zylocaine and the like; antibacterials 
and antiseptics, such as povidone-iodine, polymyxin b sulfate-bactracin, 
zinc-neomycin sulfate-hydrocortisone, chloramphenicol, methylbenzethonium 
chloride, and erythromycin and the like; antiparasitics, such as lindane; 
deodorants, such as chlorophyllin copper complex, aluminum chloride, 
aluminum chloride hexahydrate, and methylbenzethonium chloride; 
essentially all dermatologicals, like acne preparations, such as benzoyl 
peroxide, erythromycinbenzoyl peroxide, clindamycin phosphate, 
5,7-dichloro-8-hydroxyquinoline, and the like; anti-inflammatory agents, 
such as alclometasone dipropionate, betamethasone valerate, and the like; 
burn relief ointments, such as o-amino-p-toluenesulfonamide monoacetate 
and the like; depigmenting agents, such as monobenzone; dermatitis relief 
agents, such as the active steroids amcinonide, diflorasone diacetate, 
hydrocortisone, and the like; diaper rash relief agents, such as 
methylbenzethonium chloride and the like; emollients and moisturizers, 
such as mineral oil, PEG-4 dilaurate, lanolin oil, petrolatum, mineral wax 
and the like; fungicides, such as butocouazole nitrate, haloprogin, 
clotrimazole, and the like; herpes treatment drugs, such as 
9-(2-hydroxyethoxy)methyl!guanine; pruritic medications, such as 
alclometasone dipropionate, betamethasone valerate, isopropyl myristate 
MSD, and the like; psoriasis, seborrhea and scabicide agents, such as 
anthralin, methoxsalen, coal tar and the like; sunscreens, such as octyl 
p-(dimethylamino)benzoate, octyl methoxycinnamate, oxybenzone and the 
like; steroids, such as 
2-(acetyloxy)-9-fluoro-1',2',3',4'-tetrahydro-11-hydroxypregna-1,4-dieno1 
6,17-b!naphthalene-3,20-dione, and 
21-chloro-9-fluoro-1',2',3',4'-tetrahydro-11b-hydroxypregna-1,4-dieno16z, 
17-b!naphthalene-3,20-dione. Any other medication capable of topical 
administration also can be incorporated in composition of the present 
invention in an amount sufficient to perform its intended function. 
Eventual exfoliation of the intercalated layered material should provide 
delamination of at least about 90% by weight of the intercalated material 
to provide a more viscous composition comprising a carrier or solvent 
having polymer-complexed platelet particles substantially homogeneously 
dispersed therein. Some intercalates require a shear rate that is greater 
than about 10 sec.sup.-1 for such relatively thorough exfoliation. Other 
intercalates exfoliate naturally or by heating, or by applying low 
pressure, e.g., 0.5 to 60 atmospheres above ambient, with or without 
heating. The upper limit for the shear rate is not critical. In the 
particularly preferred embodiments of the invention, when shear is 
employed for exfoliation, the shear rate is from greater than about 10 
sec.sup.-1 to about 20,000 sec.sup.-1, and in the more preferred 
embodiments of the invention the shear rate is from about 100 sec.sup.-1 
to about 10,000 sec.sup.-1. 
When shear is employed for exfoliation, any method which can be used to 
apply a shear to the intercalant/carrier composition can be used. The 
shearing action can be provided by any appropriate method, as for example 
by mechanical means, by thermal shock, by pressure alteration, or by 
ultrasonics, all known in the art. In particularly useful procedures, the 
composition is sheared by mechanical methods in which the intercalate, 
with or without the carrier or solvent, is sheared by use of mechanical 
means, such as stirrers, Banbury.RTM. type mixers, Brabender.RTM. type 
mixers, long continuous mixers, and extruders. Another procedure employs 
thermal shock in which shearing is achieved by alternatively raising or 
lowering the temperature of the composition causing thermal expansions and 
resulting in internal stresses which cause the shear. In still other 
procedures, shear is achieved by sudden pressure changes in pressure 
alteration methods; by ultrasonic techniques in which cavitation or 
resonant vibrations which cause portions of the composition to vibrate or 
to be excited at different phases and thus subjected to shear. These 
methods of shearing are merely representative of useful methods, and any 
method known in the art for shearing intercalates may be used. 
Mechanical shearing methods may be employed such as by extrusion, injection 
molding machines, Banbury.RTM. type mixers, Brabender.RTM. type mixers and 
the like. Shearing also can be achieved by introducing the layered 
material and intercalant polymer at one end of an extruder (single or 
double screw) and receiving the sheared material at the other end of the 
extruder. The temperature of the layered material/intercalant polymer 
composition, the length of the extruder, residence time of the composition 
in the extruder and the design of the extruder (single screw, twin screw, 
number of flights per unit length, channel depth, flight clearance, mixing 
zone, etc.) are several variables which control the amount of shear to be 
applied for exfoliation. 
Exfoliation should be sufficiently thorough to provide at least about 80% 
by weight, preferably at least about 85% by weight, more preferably at 
least about 90% by weight, and most preferably at least about 95% by 
weight delamination of the layers to form individual platelet particles 
that can be substantially homogeneously dispersed in the carrier or 
solvent. As formed by this process, the platelet particles dispersed in 
the carrier or solvent have the thickness of the individual layers plus 
one to five monolayer thicknesses of complexed polymer, or small multiples 
less than about 10, preferably less than about 5 and more preferably less 
than about 3 of the layers, and still more preferably 1 or 2 layers. In 
the preferred embodiments of this invention, intercalation and 
delamination of every interlayer space is complete so that all or 
substantially all individual layers delaminate one from the other to form 
separate platelet particles for admixture with the carrier or solvent. The 
compositions can include the layered material as all intercalate, 
completely without exfoliation, initially to provide relatively low 
viscosities for transportation and pumping until it is desired to increase 
viscosity via easy exfoliation. In cases where intercalation is incomplete 
between some layers, those layers will not delaminate in the carrier or 
solvent, and will form platelet particles comprising those layers in a 
coplanar aggregate. 
The effect of adding into a carrier or solvent the nanoscale particulate 
dispersed platelet particles, derived from the intercalates formed in 
accordance with the present invention, typically is a substantial increase 
in viscosity of the carrier or solvent. 
The following specific clay:polymer complex preparations are presented to 
more particularly illustrate the invention and are not to be construed as 
limitations thereon. 
Preparation of Clay--PVP Complexes (Intercalates) 
Materials: 
Clay--sodium montmorillonite; 
PVP--molecular weights of 10,000 and 40,000. 
To prepare Clay (sodium montmorillonite)--PVP complexes (intercalates) we 
used three different processes for polymer intercalation: 
1. Mixture of the 2% PVP/water solution with the 2% clay/water suspension 
in a ratio sufficient to provide a polymer concentration of at least about 
8% by weight, preferably at least about 10% by weight, based on the dry 
weight of the clay. 
2. Dry clay powder (about 8% by weight moisture) was gradually added to the 
2% PVP/water solution in a ratio sufficient to provide a polymer 
concentration of at least about 8% by weight, preferably at least about 
10% by weight, based on the dry weight of the clay. 
3. Dry PVP was mixed with dry clay, the mixture was hydrated with 25-50%, 
preferably 35%-40% by weight water, based on the dry weight of the clay, 
and then extruded. 
Mixtures 1 and 2 were agitated at room temperature during 4 hours. 
The weight ratio Clay:PVP was changed from 90:10 to 20:80. 
These experiments show that all methods of preparation yielded the 
Clay--PVP complexes (intercalates), and the results of the intercalation 
do not depend on the method of preparation (1, 2, or 3) or molecular 
weight of the intercalant polymer (PVP), but do depend on the ratio of 
clay:PVP in the intercalating composition. In Table 1 the results of the 
X-ray diffraction for Clay--PVP complexes with different ratios of 
components are demonstrated. The plot of these data is shown in FIG. 1. 
From these data (Table 1, FIG. 1) one can see the step character of 
intercalation while the polymer is being sorbed in the interlayer space 
between adjacent platelets of the montmorillonite clay. There are 
increasing d(001) values from 12 .ANG. for clay with no PVP sorbed to 
24-25 .ANG. spacing between adjacent platelets with sorption of 20-30% 
PVP. The next step to 30-32 .ANG. spacing occurs when the sorbed PVP 
content is increased to 40-60%. Further increasing the sorbed PVP content 
to 70-80% increases the d(001) values to 40-42 .ANG.. There are d(002) 
reflexes together with d(001) reflexes in X-ray patterns of all complexes 
obtained (Table 1, FIG. 1). This indicates the regularity of Clay--PVP 
complex structures. 
TABLE 1 
______________________________________ 
PVP, %* d (001), .ANG. 
d (002), .ANG. 
______________________________________ 
1 0.0 12.4 6.2 
2 10.0 17.5 8.6 
3 20.0 24.0 11.4 
4 30.0 25.0 12.0 
5 40.0 30.0 15.2 
6 45.0 31.0 15.2 
7 50.0 30.0 15.5 
8 55.0 32.0 16.5 
9 60.0 34.0 17.0 
10 70.0 40.0 21.0 
11 80.0 42.0 21.0 
______________________________________ 
*Percent by weight, based on the dry weight of the clay plus polymer. 
Preparation of Clay--PVA Complexes (Intercalates) 
Materials: 
Clay--sodium montmorillonite; 
PVOH--degree of hydrolysis 75-99%, molecular weight of 10,000. 
To prepare Clay (sodium montmorillonite)--PVOH complexes (intercalates) we 
provided three different processes for polymer intercalation: 
1. Mixture of the 2% PVOH/water solution with the 2% clay/water suspension 
in a ratio sufficient to provide a polymer concentration of at least about 
8% by weight, preferably at least about 10% by weight, based on the dry 
weight of the clay. 
2. Dry clay powder was gradually added to the 2% PVOH/water solution in a 
ratio sufficient to provide a polymer concentration of at least about 8% 
by weight, preferably at least about 10% by weight, based on the weight of 
the clay. 
3. Dry clay was moisturized with PVOH/water solution to a moisture content 
of 25%-80%, preferably about 35%-40% water, and then extruded. 
The mixtures 1 and 2 were agitated at room temperature during 4 hours. 
The weight ratio Clay:PVOH was changed from 80:20 to 20:80. 
Some of the exfoliates were studied by X-ray diffraction. These experiments 
show that all methods of preparation yielded the composite Clay--PVOH 
complexes (intercalates), and the results of the intercalation do not 
depend on the method of preparation (1, 2, or 3), or molecular weight of 
the intercalant polymer (PVOH), or degree of hydrolysis, but do depend on 
the ratio of clay:PVOH in the intercalating composition. In Table 2 the 
results of the X-ray diffraction for Clay--PVOH complexes with different 
ratios of components are demonstrated. The plot of these data is shown in 
FIG. 2. From these data (Table 2, FIG. 2) one can see the step character 
of increasing d(001) values from 12 .ANG. for clay with no sorbed PVOH to 
22-25 .ANG. spacing between adjacent platelets with sorption of 20-30% 
PVOH. The next step to 30-33 .ANG. occurs when the sorbed PVOH content 
increases to 35-50%. A further increase of the sorbed PVOH content to 
60-80% increases the d(001) values to 40-45 .ANG.. 
Heating of samples at 120.degree. C. during 4 hours insignificantly changed 
the d(001) values (Table 2, FIG. 2). 
TABLE 2 
______________________________________ 
PVOH %* d (001), .ANG. 
d (001), .ANG. 120.degree. C. 
______________________________________ 
1 0.0 12.4 9.6 
2 10.0 17.0 16.8 
3 20.0 23.0 22.0 
4 30.0 25.0 24.0 
5 35.0 32.0 32.0 
6 40.0 31.0 30.0 
7 45.0 33.0 32.0 
8 50.0 32.0 32.0 
9 60.0 42.0 42.0 
10 70.0 44.0 42.0 
11 80.0 45.0 44.0 
______________________________________ 
*Percent by weight, based on the dry weight of the clay plus PVOH. 
The graphs of FIGS. 3 to 5 are x-ray diffraction patterns of blends of 
different water-soluble polymers with sodium bentonite clay. The pattern 
of FIGS. 3 and 4 are taken from intercalated clay 20% by weight 
polyvinylpyrrolidone (weight average molecular weight=10,000 for FIG. 3; 
40,000 for FIG. 4) and 80% by weight sodium bentonite clay. The blends 
were formed by mixing the PVP and clay from a 2% solution of PVP and a 2% 
dispersion of sodium bentonite in a 1:4 ratio, respectively. As shown, the 
PVP:clay complexed since no d(001) smectite peak appears at about 12.4 
.ANG.. Similar results are shown for 20% polyvinyl alcohol, 80% sodium 
bentonite, as shown in FIG. 5, blended in the same way and in the same 
ratio. The d(001) peak of non-exfoliated (layered) sodium bentonite clay 
appears at about 12.4 .ANG., as shown in the x-ray diffraction pattern for 
sodium bentonite clay (containing about 10% by weight water) in the lower 
x-ray diffraction patterns of FIGS. 6 and 7. The graphs of FIG. 6 are 
x-ray diffraction patterns of sodium bentonite clay (montmorillonite) and 
a PVP:clay complex that was obtained by extrusion of a blend of 20% by 
weight polyvinylpyrrolidone (molecular weight 10,000) and 80% by weight 
sodium bentonite clay (containing a crystobalite impurity, having a 
d-spacing of about 4.05 .ANG.) with 35% water based on the weight of dry 
clay plus polymer. As shown in FIG. 6, the PVP clay complexed since no 
d(001) smectite peak appears at about 12.4 .ANG.. There are basal spacings 
with a d(001) peak of PVP:clay complex at about 24 .ANG. and d(002) peak 
of PVP:clay complex at about 12 .ANG., that shows close to regular 
structure of this intercalated composite with a PVP:clay ratio equal to 
1:4. The graphs of FIG. 7 are x-ray diffraction patterns of sodium 
bentonite clay (montmorillonite) and PVP:clay complex that was obtained by 
extrusion of blend of 50% by weight polyvinylpyrrolidone (molecular weight 
10,000) and 50% of sodium bentonite clay (containing a crystobalite 
impurity, having d-spacing of about 4.05 .ANG.) with 35% water based on 
the weight of dry clay plus polymer. As shown in FIG. 7, the PVP:clay 
complexed since no d(001) smectite peak appears at about 12.4 .ANG.. There 
are basil spacings with a d(001) peak of the PVP:clay complex at about 32 
.ANG. and a d(002) peak of PVP:clay complex at about 16 .ANG. that shows 
close to regular structure of this intercalated composite with a PVP:clay 
ratio equal to 1:1. When mechanical blends of powdered sodium bentonite 
clay (containing about 10% by weight water) and powdered 
polyvinylpyrrolidone (PVP) polymer were mixed with water (about 75% by 
weight water), the polymer was intercalated between the bentonite clay 
platelets, and an exothermic reaction occurred that, it is theorized, 
resulted from the polymer being bonded to the internal faces of the clay 
platelets sufficiently for exfoliation of the intercalated clay. 
It should be noted, also, that exfoliation did not occur unless the 
bentonite clay included water in an amount of at least about 4% by weight, 
based on the dry weight of the clay, preferably at least about 10% by 
weight water. The water can be included in the clay as received, or can be 
added to the clay prior to or during intercalant polymer contact. 
It should also be noted that the exfoliation occurred without shearing--the 
layered clay exfoliated naturally after sufficient intercalation of 
polymer between the platelets of the layered bentonite--whether the 
intercalate was achieved by using sufficient water, e.g., at least about 
20% by weight, preferably about 30% to about 100% by weight, or higher, 
based on the dry weight of the clay, for sufficient migration of the 
polymer into the interlayer spaces, and preferably also by extruding. When 
intercalating in a phyllosilicate slurry, it has been found that at least 
about 65% by weight water, based on the total weight of the intercalating 
composition, provides easier mixing and faster migration of the polymer 
into the spaces between platelets. 
The x-ray diffraction pattern of FIG. 8 shows that at a ratio of 80% PVP, 
20% clay, the periodicity of the intercalated composite, with a PVP clay 
ratio equal to 4:1, is increased to about 41 .ANG.. 
A number of compositions were prepared containing intercalates (complexes) 
formed by contacting sodium bentonite clay with an intercalating 
composition. The intercalating composition contained clay, water and a 
water-soluble polymer. Sufficient sodium bentonite clay was added to the 
intercalating composition to provide a preferred weight ratio of dry 
clay/polymer of 4:1 (80% by weight clay/20% by weight polymer) with 
sufficient water such that the intercalating composition and clay 
contained 35-40% by weight water for effective extrusion of the 
composition through die openings of an extruder. Similarly, the polymer 
and water can be mixed with clay to complex (intercalate) the polymer to 
the platelet surfaces between adjacent clay platelets. 
The complex (intercalate) was then combined with various organic liquids 
(with and without water) to determine the effect of intercalate loading as 
well as temperature, pH and water content of the intercalating composition 
on the viscosity of the liquid by the addition of the intercalate or 
exfoliate thereof. For the composition shown in FIGS. 9-14, every clay-PVP 
(polyvinylpyrrolidone) complex was an extruded blend having a weight ratio 
of clay:PVP of 4:1 containing 35-40% by weight water, based on the dry 
weight of the clay plus polymer. The complexes (intercalates and/or 
exfoliates) formed by extrusion were admixed, at various complex 
percentages, with the designated percentages of organic liquid (sometimes 
also with water) and the viscosity measured using a Brookfield viscometer, 
spindle #4, unless otherwise noted. 
As shown in the graph of FIG. 9, a composition consisting of 10% by weight 
of an extruded complex of 80% by weight sodium bentonite clay and 20% by 
weight polyvinylpyrrolidone (extruded using 38% water, based on the dry 
weight of the clay plus polymer, and then dried) was combined with 6% 
water and 84% glycerol. The composition was mixed to form a homegeneous 
composition and sometimes heated to form a more viscous gel before cooling 
to room temperature (24.degree. C.) to measure the viscosity. As shown in 
FIG. 9, mixing 10% by weight clay:PVP intercalate into 84% glycerol, and 
6% water resulted in a viscosity of 2,000-3,000 centipoises and heating 
the composition to gelation resulted in viscosities of about 3,500-4,000 
centipoises (80.degree. C.) and 7,000-8,000 centipoises (100.degree. 
C.)--all viscosities being measured at 24.degree. C. 
As shown in FIG. 10, when the intercalate/water/glycerol compositions of 
FIG. 9 were heated to 145.degree. C. and then cooled to room temperature, 
the viscosity of the 10% intercalate/6% H.sub.2 O/84% glycerol composition 
was increased to about 200,000 to about 600,000 centipoises. 
FIG. 11 shows compositions similar to those of FIGS. 9 and 10 at two 
different loadings (5% by weight and 10% by weight) of the clay:PVP 
complex (again, a 4:1 weight ratio of sodium bentonite to 
polyvinylpyrrolidone extruded with 38% water and then dried to about 
3%-10% water, preferably about 4% to 6% water) with glycerol and water, 
with varied amounts of water. The compositions were gelled by heating to 
140.degree. C. and the compositions were cooled to room temperature 
(24.degree. C.) before the viscosity was measured. As shown in FIG. 11, 
for a 5% loading of the intercalate, an increase in water percentage up to 
about 5% by weight causes an increase in viscosity; for a 10% intercalate 
loading, an increase in water percentage up to about 8% by weight 
increases the viscosity of the intercalate/glycerol/water 
composition--with viscosities of about 500,000 centipoises to about 
3,000,000 centipoises being achieved. 
FIG. 12 is a graph showing viscosity measured at room temperature 
(24.degree. C.), of compositions containing 5% by weight of the sodium 
bentonite clay:PVP complex (intercalate) admixed with 0-6% by weight water 
and 89-95% by weight ethylene glycol, without heating. As shown in FIG. 
12, the addition of up to about 6% by weight water increases the viscosity 
of the intercalate/ethylene glycol composition-(without heating) from less 
than 1,000 centipoises to more than 9,000 centipoises. The same 
compositions were heated to 85.degree. C. and the viscosity measured 
(after cooling to room temperature). The effect of temperature (85.degree. 
C.) is quite dramatic, as shown in FIG. 13, increasing the viscosity to 
well over 100,000 centipoises, with the addition of about 2% by weight 
water, and increasing viscosity, substantially, without water as well. 
FIG. 14 is a graph showing viscosity, again measured at room temperature 
(24.degree. C.) of an unheated mixture of 10% by weight sodium bentonite 
clay:PVP complex (intercalate), with the remainder being varied 
percentages of ethanol and water. As shown in FIG. 14, for ethanol, the 
addition of up to about 20% by weight water (70% ethanol, 10% clay:PVP 
complex) increases the viscosity of the composition from well below 
400,000 centipoises to about 1,000,000 centipoises, even without heating. 
Various other organic liquids were admixed with clay:polymer intercalates 
at varied percentages of intercalate and varied percentages of water. All 
experiments used a 4:1 weight ratio of sodium bentonite clay to 
polyvinylpyrrolidone either mixed with a water slurry of the clay and 
polymer at 5-80% water--Technique #1) and then dried; or extruded with 
35-38% water and then dried (Technique #2). The results are shown in the 
following examples: 
EXAMPLE 1 
______________________________________ 
2-PROPANOL WITH 10%-4:1 COMPLEX (CLAY:PVP) 
10%-4:1 Complex (20 grams) 27%-Water (54 grams) 
63%-2-Propanol (126 grams) TECHNIQUE #1 
Spindle: #1 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
762 393 234 
______________________________________ 
EXAMPLE 2 
______________________________________ 
8% Water (16 grams) 5%-4:1 Complex (10 grams) 
87% Propylene Glycol (174 grams) TECHNIQUE #1 
Spindle: #4 Was heated to 160.degree. C. 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
23,800 11,700 7,700 
______________________________________ 
EXAMPLE 3 
______________________________________ 
8% Water (16 grams) 5%-4:1 Complex (10 grams) 
87% Propylene Glycol (174 grams) TECHNIQUE #2 
Spindle: #4 Was heated to 160.degree. C. 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
23,600 9,100 5,600 
______________________________________ 
EXAMPLE 4 
______________________________________ 
8% Water (16 grams) 10%-4:1 Complex (20 grams) 
82% Propylene Glycol (164 grams) TECHNIQUE #1 
Spindle: #4 Was heated to 115-120.degree. C. 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
21,400 11,700 7,350 
______________________________________ 
EXAMPLE 5 
______________________________________ 
8% Water (16 grams) 10%-4:1 Complex (20 grams) 
82% Propylene Glycol (164 grams) TECHNIQUE #2 
Spindle: #4 Was heated to 115-120.degree. C. 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
19,000 10,600 6,950 
______________________________________ 
Propylene glycol, glycerol, propanol, acetone, and anhydrous alcohol were 
mixed with varied percentages of sodium bentonite clay:PVP complexes, 
either slurried or extruded with water and then dried, and varied 
percentages of water, as shown in the following Examples. 
EXAMPLE 6 
______________________________________ 
Propylene Glycol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
20 8 None 
______________________________________ 
EXAMPLE 7 
______________________________________ 
Propylene Glycol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
15 8 None 
15 24 None 
______________________________________ 
EXAMPLE 8 
______________________________________ 
Propylene Glycol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
10 4 None 
10 6 None 
10 8 None 
10 16 None 
10 24 None 
______________________________________ 
EXAMPLE 9 
______________________________________ 
Propylene Glycol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
5 4 Very Little 
5 8 Very Little 
5 16 Very Little 
5 24 None 
5 30 None 
______________________________________ 
EXAMPLE 10 
______________________________________ 
Propylene Glycol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
2.5 4 Very Little 
2.5 8 None 
2.5 12 None 
2.5 16 None 
2.5 24 None 
______________________________________ 
EXAMPLE 11 
______________________________________ 
Glycerol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
10 0 None 
10 4 None 
10 8 None 
10 16 None 
______________________________________ 
EXAMPLE 12 
______________________________________ 
Glycerol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
5 0 None 
5 2 None 
5 4 None 
5 8 None 
______________________________________ 
EXAMPLE 13 
______________________________________ 
Ethylene Glycol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
10 8 None 
10 16 None 
______________________________________ 
EXAMPLE 14 
______________________________________ 
Ethylene Glycol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
5 0 Very Little 
5 2 None 
5 4 None 
5 6 None 
______________________________________ 
EXAMPLE 15 
______________________________________ 
Alcohol, Anydrous Reagent - 9401-03 
% of Complex % of Water 
Syneresis 
______________________________________ 
10 4 Very Much 
10 8 Yes 
10 16 None 
______________________________________ 
EXAMPLE 16 
______________________________________ 
1,4 Butane Diol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
10 4 None 
______________________________________ 
EXAMPLE 17 
______________________________________ 
1,4 Butane Diol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
5 4 Very Little 
5 8 None 
5 16 None 
______________________________________ 
EXAMPLE 18 
______________________________________ 
1-Propanol Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
10 8 Yes 
10 27 Yes 
10 45 Yes 
10 50 None 
______________________________________ 
EXAMPLE 19 
______________________________________ 
Acetone Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
20 40 None 
______________________________________ 
EXAMPLE 20 
______________________________________ 
Acetone Gel 
% of Complex % of Water 
Syneresis 
______________________________________ 
10 16 Yes 
10 45 None 
10 50 None 
______________________________________ 
EXAMPLE 21 
______________________________________ 
10% Complex, 8% Water, 72% Propylene Glycol (Master Gel) 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
464,000 306,000 162,800 
______________________________________ 
EXAMPLE 22 
______________________________________ 
27.5% Master Gel of Example 21 
65% Silicone Oil, 0.75% Abil*, 6.75% Water 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
1,630,000 EEE** EEE** 
______________________________________ 
* Abil: Amino silane surfactant from Huls America 
**EEE -- Exceeded capacity of viscometer 
EXAMPLE 23 
______________________________________ 
15% Complex, 24% Water, 61% Propylene Glycol (Master Gel) 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
456,000 278,000 142,400 
______________________________________ 
EXAMPLE 24 
______________________________________ 
27.5% Master Gell of Example 23 
65% Silicone Oil, 0.75% Abil, 6.75% Water 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
1,000,000 625,000 361,200 
______________________________________ 
EXAMPLE 25 
______________________________________ 
15% Complex, 8% Water, 77% Propylene Glycol (Master Gel) 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
168,000 63,000 40,800 
______________________________________ 
EXAMPLE 26 
______________________________________ 
27.5% Master Gel of Example 25 
65% Silicone Oil, 0.75% Abil, 6.75% Water 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
1,630,000 981,000 EEE* 
______________________________________ 
*EEE -- Exceeded capacity of ter 
EXAMPLE 27 
______________________________________ 
10% Complex, 0% Water, 90% Glycerol (Master Gel) 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
EEE* EEE* EEE* 
______________________________________ 
*EEE -- Exceeded Capacity of viscometer 
EXAMPLE 28 
______________________________________ 
10% Complex, 4% Water, 85% Glycerol (Master Gel) 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
240,000 137,000 114,000 
______________________________________ 
EXAMPLE 29 
______________________________________ 
37.5% - Master Gel of Example 27, 
51% Silicone Oil, 1.0% Abil, 11% Water 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
376,000 308,000 180,400 
______________________________________ 
EXAMPLE 30 
______________________________________ 
37.5% - Master Gel of Example 28, 
51% Silicone Oil, 1.0% Abil, 11% Water 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
512,000 371,000 201,600 
______________________________________ 
EXAMPLE 31 
______________________________________ 
37.5% - Master Gel of Example 28, 
55% Silicone Oil, 1% Abil, 6.5% Water 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
1,164,000 699,000 EEE* 
______________________________________ 
*EEE -- Exceeded capacity of viscometer 
EXAMPLE 32 
______________________________________ 
34% Master Gel of Example 28, 
60% Silicone Oil, 1.0% Abil, 5% Water 
Spindle: #4 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
EEE* EEE* EEE* 
______________________________________ 
*EEE -- Exceeded capacity of viscometer 
EXAMPLE 33 
______________________________________ 
10% Complex (20 grams), 4% Water (8 grams), 
91% Propylene Glycol (182 grams) 
Spindle: #4 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
16,200 10,500 7,550 
______________________________________ 
EXAMPLE 34 
______________________________________ 
10% Complex (20 grams), 6% Water (12 grams,) 
84% Propylene Glycol (168 grams) 
Spindle: #4 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
22,200 15,300 12,000 
______________________________________ 
EXAMPLE 35 
______________________________________ 
10% Complex (20 grams), 8% Water (16 grams), 
82% Propylene Glycol (164 grams) 
Spindle: #4 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
14,400 12,100 9,400 
______________________________________ 
EXAMPLE 36 
______________________________________ 
10% Complex (20 grams), 16% Water (32 grams), 
74% Propylene Glycol (148 grams) 
Spindle: #4 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
12,000 10,600 7,500 
______________________________________ 
EXAMPLE 37 
______________________________________ 
10% Complex (20 grams), 24% Water (48 grams), 
66% Propylene Glycol (132 grams) 
Spindle: #4 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
22,400 13,100 8,650 
______________________________________ 
EXAMPLE 38 
______________________________________ 
4% Water (8 grams), 1.25% Complex 4:1 (2.5 grams), 
94.75% Propylene Glycol (189.5 grams) - Was heated to 170.degree. C. 
Spindle: #2 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
290 285 227.5 
______________________________________ 
EXAMPLE 39 
______________________________________ 
8% Water (16 grams), 1.25% Complex 4:1 (2.5 grams), 
90.75% Propylene Glycol (181.5 grams) - Was heated to 160-165.degree. C. 
Spindle: #2 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
510 420 385 
______________________________________ 
EXAMPLE 40 
______________________________________ 
12% Water (24 grams), 1.25% Complex 4:1 (2.5 grams), 
86.75% Propylene Glycol (173.5 grams) - Was heated to 165-170.degree. C. 
Spindle: #2 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
4,500 3,135 1,897.5 
______________________________________ 
EXAMPLE 41 
______________________________________ 
16% Water (32 grams), 1.25% Complex 4:1 (2.5 grams), 
82.75% Propylene Glycol (165.5 grams) - Was geated to 170.degree. C. 
Spindle: #2 
______________________________________ 
RPM 3 6 12 
Viscosity (cps) 
5,370 3,350 1,970 
______________________________________ 
EXAMPLE 42 
______________________________________ 
4% Water (8 grams), 5% Complex (10 grams), 
91% Propylene Glycol (182 grams) - Heated to 110.degree. C. - From 
110 to 155.degree. C. took 15 min. - Max. temp. = 160.degree. C. 
Spindle: #2 
______________________________________ 
RPM 12 30 60 
Viscosity (cps) 
112.5 94.0 91.5 
______________________________________ 
EXAMPLE 43 
______________________________________ 
4% Water (8 grams), 5% Complex (10 grams), 
91% Propylene Glycol (182 grams) - Heated to 110.degree. C. - From 
110 to 155.degree. C. took 15 min. - Max. temp. = 160.degree. C. 
Spindle: #4 
______________________________________ 
RPM 1.5 3 6 12 
Viscosity (cps) 
78,000 36,600 21,200 
11,950 
______________________________________ 
EXAMPLE 44 
______________________________________ 
8% Water (16 grams), 5% Complex (10 grams), 
87% Propylene Glycol (174 grams) - Heated to 150.degree. C. - From 
110 to 150.degree. C. took 20 min. - Max. temp. = 150.degree. C. 
Spindle: #2 
______________________________________ 
RPM 12 30 60 
Viscosity (cps) 
145.0 130.0 120.5 
______________________________________ 
EXAMPLE 45 
______________________________________ 
16% Water (32 grams), 5% Complex (10 grams), 
79% Propylene Glycol (158 grams) - Heated to 145-150.degree. C. - From 
110 to 150.degree. C. took 19 min. - Max. temp. = 150.degree. C. 
Spindle: #2 
______________________________________ 
RPM 30 60 
Viscosity (cps) 98.0 102.5 
______________________________________ 
EXAMPLE 46 
______________________________________ 
16% Water (32 grams), 5% Complex (10 grams), 
79% Propylene Glycol (158 grams) - Heated to 145-150.degree. C. - From 
110 to 150.degree. C. took 19 min. - Max. temp. = 150.degree. C. 
Spindle: #4 
______________________________________ 
RPM 1.5 3 6 12 
Viscosity (cps) 
16,000 9,000 7,800 5,700 
______________________________________ 
EXAMPLE 47 
______________________________________ 
16% Water (32 grams), 5% Complex (10 grams), 
79% Propylene Glycol (158 grams) - Heated to 145-150.degree. C. - From 
110 to 150.degree. C. took 19 min. - Max. temp. = 150.degree. C. 
Spindle: #3 
______________________________________ 
RPM 6 12 30 
Viscosity (cps) 
7,220 5,110 3,040 
______________________________________ 
EXAMPLE 48 
______________________________________ 
24% Water (48 grams), 5% Complex (10 grams), 
71% Propylene Glycol (142 grams) - Heated to 120.degree. C. - From 
110 to 125.degree. C. took 19 min. - Max. temp. = 125.degree. C. 
Spindle: #2 
______________________________________ 
RPM 30 60 
Viscosity (cps) 118.0 108.0 
______________________________________ 
EXAMPLE 49 
______________________________________ 
24% Water (48 grams), 5% Complex (10 grams), 
71% Propylene Glycol (142 grams) - Heated to 120.degree. C. - From 
110 to 125.degree. C. took 19 min. - Max. temp. = 125.degree. C. 
Spindle: #4 
______________________________________ 
RPM 1.5 3 6 12 
Viscosity (cps) 
8,800 6,600 5,000 2,800 
______________________________________ 
EXAMPLE 50 
______________________________________ 
24% Water (48 grams), 5% Complex (10 grams), 
71% Propylene Glycol (142 grams) - Heated to 120.degree. C. - From 
110 to 125.degree. C. took 19 min. - Max. temp. = 125.degree. C. 
Spindle: #3 
______________________________________ 
RPM 6 12 30 
Viscosity (cps) 
3,820 2,470 1,100 
______________________________________ 
EXAMPLE 51 
______________________________________ 
30% Water (60 grams), 5% Complex (10 grams), 
65% Propylene Glycol (130 grams) - Heated to 120.degree. C. - From 
110 to 125.degree. C. 19 min. - Max. temp. = 125.degree. C. 
Spindle: #2 
______________________________________ 
RPM 12 30 60 
Viscosity (cps) 
692.5 389.0 258.0 
______________________________________ 
EXAMPLE 52 
______________________________________ 
30% Water (60 grams), 5% Complex (10 grams), 
65% Propylene Glycol (130 grams) - Heated to 120.degree. C. - From 
110 to 125.degree. C. 19 min. - Max. temp. = 125.degree. C. 
Spindle: #4 
______________________________________ 
RPM 1.5 3 6 12 
Viscosity (cps) 
23,600 11,200 5,400 2,800 
______________________________________ 
EXAMPLE 53 
______________________________________ 
30% Water (60 grams), 5% Complex (10 grams), 
65% Propylene Glycol (130 grams) - Heated to 120.degree. C. - From 
110 to 125.degree. C. 19 min. - Max. temp. = 125.degree. C. 
Spindle: #3 
______________________________________ 
RPM 6 12 30 
Viscosity (cps) 
6,100 3,550 2,112 
______________________________________ 
EXAMPLES 54 
______________________________________ 
8% Water (16 grams), 5% Complex (10 grams), 
87% Methanol (174 grams) 
Spindle: #1 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
1,160 960 588 
______________________________________ 
EXAMPLE 55 
______________________________________ 
4% Water (8 grams), 10% - 1:4 Complex (20 grams), 
86% Propylene Glycol (172 grams) 
Spindle: #3 
______________________________________ 
RPM 0.3 0.6 
Viscosity (cps) 19,600 18,400 
______________________________________ 
EXAMPLE 56 
______________________________________ 
6% Water (12 grams), 10% - 1:4 Complex (20 grams), 
84% Propylene Glycol (168 grams) 
Spindle: #3 
______________________________________ 
RPM 0.3 0.6 
Viscosity (cps) 128,000 67,200 
______________________________________ 
EXAMPLE 57 
______________________________________ 
8% Water (16 grams), 10% - 1:4 Complex (20 grams), 
82% Propylene Glycol (164 grams) 
Spindle: #3 
______________________________________ 
RPM 0.3 0.6 
Viscosity (cps) 61,200 56,600 
______________________________________ 
EXAMPLE 58 
______________________________________ 
16% Water (32 grams), 10% - 1:4 Complex (20 grams), 
74% Propylene Glycol (148 grams) 
Spindle: #3 
______________________________________ 
RPM 0.3 0.6 
Viscosity (cps) 79,200 49,200 
______________________________________ 
EXAMPLE 59 
______________________________________ 
24% Water (48 grams), 10% - 1:4 Complex (20 grams), 
66% Propylene Glycol (132 grams) 
Spindle: #3 
______________________________________ 
RPM 0.3 0.6 
Viscosity (cps) 168,400 89,000 
______________________________________ 
EXAMPLE 60 
______________________________________ 
8% Water (16 grams), 5% Complex (10 grams), 
87% Methanol (174 grams) 
Spindle: #2 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
1,160 960 588 
______________________________________ 
EXAMPLE 61 
______________________________________ 
8% Water (16 grams), 5% Complex (10 grams) 
87% Methanol (174 grams) 
Spindle: #2 
______________________________________ 
RPM 6 12 30 
Viscosity (cps) 
280 160 80 
______________________________________ 
EXAMPLE 62 
______________________________________ 
16% Water (32 grams), 5% Complex (10 grams), 
79% Methanol (158 grams) 
Spindle: #1 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
9,860 5,940 2,232 
______________________________________ 
EXAMPLE 63 
______________________________________ 
16% Water (32 grams), 5% Complex (10 grams), 
79% Methanol (158 grams) 
Spindle: #2 
______________________________________ 
RPM 6 12 30 
Viscosity (cps) 
665 403 204 
______________________________________ 
EXAMPLE 64 
______________________________________ 
20% Water (40 grams), 5% Complex (10 grams), 
75% Methanol (150 grams) 
Spindle: #1 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
13,880 7,460 3,228 
______________________________________ 
EXAMPLE 65 
______________________________________ 
20% Water (40 grams), 5% Complex (10 grams), 
75% Methanol (150 grams) 
Spindle: #2 
______________________________________ 
RPM 6 12 30 
Viscosity (cps) 
905 455 244 
______________________________________ 
EXAMPLE 66 
______________________________________ 
27% Water (54 grams), 5% Complex (10 grams), 
68% Methanol (136 grams) 
Spindle: #2 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
17,400 10,250 4,640 
______________________________________ 
EXAMPLE 67 
______________________________________ 
27% Water (54 grams), 5% Complex (10 grams) 
68% Methanol (136 grams) 
Spindle: #2 
______________________________________ 
RPM 6 12 30 
Viscosity (cps) 
1,170 533 271 
______________________________________ 
EXAMPLE 68 
______________________________________ 
35% Water (70 grams), 5% Complex (20 grams), 
60% Methanol (120 grams) 
Spindle: #2 
______________________________________ 
RPM 0.3 0.6 1.5 
Viscosity (cps) 
16,900 8,900 3,680 
______________________________________ 
EXAMPLE 69 
______________________________________ 
35% Water (70 grams), 5% Complex (20 grams), 
60% Methanol (120 grams) 
Spindle: #2 
______________________________________ 
RPM 6 12 30 
Viscosity (cps) 
1,175 525 251 
______________________________________ 
Propylene glycol and glycerol gels, prepared from a 4:1 weight ratio sodium 
bentonite clay:PVP intercalates at a 10% by weight intercalate loading, 
were tested to determine if the gels could hold substantial quantities of 
hydrophobic silicone oil material in a stable, viscous thixotropic gel 
(Examples 70-76). It was found that to avoid syneresis (liquid separation) 
when incorporating both very hydrophobic (silicone oil) and hydrophilic 
(glycol or glycerol) liquids, a small amount of surfactant, e.g., an amino 
silane, may be included. The following examples show that viscous gels (of 
both hydrophobic and hydrophilic liquids) can be prepared without 
syneresis. The compositions of Examples 70-76 have been stable for six 
months and remain stable. 
EXAMPLE 70 
______________________________________ 
27.5% 15% Propylene Glycol Gel w/8% Water 
65% Silicone Oil 
0.75% Abil Surfactant 
1.75% Water 
None Syneresis 
______________________________________ 
EXAMPLE 71 
______________________________________ 
27.5% 15% Propylene Glycol Gel w/24% Water 
65% Silicone Oil 
0.75% Abil Surfactant 
1.75% Water 
None Syneresis 
______________________________________ 
EXAMPLE 72 
______________________________________ 
27.5% 20% Propylene Glycol Gel w/8% Water 
65% Silicone Oil 
0.75% Abil Surfactant 
1.75% Water 
None Syneresis 
______________________________________ 
EXAMPLE 73 
______________________________________ 
37% 10% Glycerol Gel w/0% Water 
51% Silicone Oil 
1.0% Abil Surfactant 
11% Water 
None Syneresis 
______________________________________ 
EXAMPLE 74 
______________________________________ 
34% 10% Glycerol Gel w/4% Water 
60% Silicone Oil 
1.0% Abil Surfactant 
5% Water 
None Syneresis 
______________________________________ 
EXAMPLE 75 
______________________________________ 
37.5 10% Glycerol Gel w/4% Water 
55% Silicone Oil 
1.0% Abil Surfactant 
6.5% Water 
None Syneresis 
______________________________________ 
EXAMPLE 76 
______________________________________ 
37% 10% Glycerol Gel w/4% Water 
51% Silicone Oil 
1.0% Abil Surfactant 
11% Water 
None Syneresis 
______________________________________ 
The following compositions were prepared to show the viscosity increasing 
effect of a pH substantially outside of the 6-10, near-neutral range. A 
composition containing a Na bentonite:PVP complex (4:1 weight ratio 
clay:PVP) at 7-10% by weight; propylene glycol at 58-66% by weight, and 
water at 22-26% by weight, with the addition of 5-6% by weight of a 50% 
active aqueous solution of NaOH to pH 12-13 resulted in a thixotropic gel 
having a viscosity at 24.degree. C. of 1,500,000 centipoises, without 
heating. The compositions were prepared by shearing all components except 
the NaOH in a blender for 3 minutes, then adding the NaOH and shearing for 
an additional 1 minute. By changing the NaOH to H.sub.2 O ratio to get an 
optimum pH, an effective hair waving lotion/hair straightener can be 
obtained at high pH which can be maintained on the hair without running 
down auto the scalp. 
Numerous modifications and alternative embodiments of the invention will be 
apparent to those skilled in the art in view of the foregoing description. 
Accordingly, this description is to be construed as illustrative only and 
is for the purpose of teaching those skilled in the art the best mode of 
carrying out the invention. The details of the structure may be varied 
substantially without departing from the spirit of the invention, and the 
exclusive use of all modifications which come within the scope of the 
appended claims is reserved.