Electrorheological gels and method for preparation

Abstract: The present invention provides an electro-rheological gel comprising a curable silicone polymer, electrorheologically active particles and a metal catalyst. The composition may further comprise an organohydrogen-silicon crosslinking agent and/or an inhibitor. The dynamic mechanical properties of the filled gel can be tuned with an electric field such that large changes in storage modulus can be achieved.

Description: The present invention relates to an electrorheological gel formed from a curable silicone polymer, electrorheologically active solid particles and a metal catalyst which results in the formation of a filled gel. The invention further relates to a method for the preparation of such gels. When certain polarizable solid particles are dispersed in an electrically non-conducting hydrophobic liquid, the resulting suspensions exhibit peculiar rheological properties under the influence of an electrical field. These systems show a dramatic increase in viscosity and modulus with applied voltage. In some cases, they literally are transformed from a liquid to a solid upon the application of an electric field. This change is reversible and typically takes place in a matter of milliseconds. Materials which exhibit this phenomenon are called electrorheological (ER) or electroviscous (EV) fluids and have been known for the last fifty years. These fluids find utility in such areas as torque transfer and mechanical damping applications. The early ER fluids comprised such systems as starch dispersed in transformer oil or silica gel dispersed in kerosine or mineral oil. Since these early discoveries, only a relatively small number of new systems and improvements have emerged over the old ones. Generally, ER fluids are composed of a polarizable solid phase dispersed in a dielectric fluid phase. ER fluids are unique for their ability to change characteristics from liquid-like to solid-like media upon the application of an external voltage. This change is reversible and the liquid-like state returns upon removal of the voltage. Upon application of a voltage, the solid phase forms fibril-like networks which bridge the electrode gap. At this point, the material will not behave as a Newtonian fluid, but will exhibit a Bingham plastic behavior. Fluids exhibiting Bingham plastic behavior require application of a particular level of force (yield stress) before the material will flow again. ER fluids employing silicone oil as the fluid phase have been disclosed in U.S. Patents 4,645,614 and 4,668,417. ER fluid compositions having gel-like properties are described in JP-A 04/089893. Other such compositions are described in a journal article by Shiga et al. entitled "Electroviscoelastic effect of polymer gel containing fine particles" (Chemical Abstracts 114:103279z, 1991). The art of moisture curable silicones have been disclosed in US-A(s) 4,546,017; 4,824,924 and 5,162,460. US-A-4,725,648 discloses a polyorganosiloxane composition which cures to a rubber and which comprises curable silicone rubber and a polymer containing acrylic acid or an alkali metal salt of acrylic acid as a monomer unit. The present invention provides an electrorheological gel composition formed from: (A) a curable silicone polymer, (B) electrorheologically active solid particles, and (C) a metal catalyst. These compositions can further comprise (D) a crosslinking agent and/or (E) an inhibitor. The present invention further introduces a method for the preparation of electrorheological gels comprising the steps of (I) dispersing electrorheologically active solid particles in (A) a curable silicone polymer, and (II) adding (B) a metal catalyst to the mixture of (I). This method can further comprise adding a crosslinking agent and/or inhibitor after step (I). It is an object of this invention to provide an ER gel having dynamic mechanical properties which can be tuned with an electric field thus resulting in the ability to control the storage modulus and other properties of the composition. It is another object of this invention to produce an electrorheological gel, which prior to the application of an electric field has a storage modulus of between 500 and 500,000 pascals when measured at a frequency of 10 hertz at 25°C., a peak strain amplitude such that the gel resides in the linear region of viscoelasticity and has a dynamic mechanical loss tangent of at least 0.5, which gel is formed from a composition which comprises: (A) a curable silicone polymer having its formula selected from (i) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(OR) 3 ; (ii) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 ; (iii) (X) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 ; and (iv) mixtures thereof; wherein R is a monovalent hydrocarbon radical having from 1 to 20 carbon atoms, X is independently selected from R, acyloxy groups, hydroxy groups, alkoxy groups, oxime groups and olefinic hydrocarbon radicals having from 2 to 20 carbon atoms, m has an average value of from 0 to 100 and n has an average value of from 100 to 2,000; (B) electrorheologically active solid particles, and (C) a metal catalyst. The term "moisture curable", as applied to the compositions of this invention, generally denotes the ability of a composition to be cured to a gel at room temperature or higher in the presence of moisture. Also, the term "curable", as applied to this invention, generally denotes a chemical change which leads to a change in the state of the composition from a liquid to a solid. Storage modulus (G') for purposes of this invention denotes a measure of a materials' elastic properties within a defined strain range, at a given rate and temperature. The G' value is proportional to the amount of energy stored in a material when it is deformed in shear. The loss modulus (G") denotes a measure of a materials' viscous properties in shear with the same limits as G'. The G'' value is proportional to the energy lost when the material is deformed in shear with losses generally assumed to be in the form of heat. For our invention, Tan Delta (δ) is the ratio of the loss modulus to the storage modulus (G"/G') and is an indication of the materials' ability to damp energy. A Tan Delta greater than one indicates a material which has greater viscous contributions than elastic. Our curable silicone polymer (A) comprises an oligomeric silicone compound or composition containing reactive functional groups, by virtue of which it can be cured to a gel state. The term "gel state" as used herein describes a material which is crosslinked to exhibit a dynamic mechanical loss tangent (tan δ) of greater than 0.5 when measured at a frequency of 10 Hertz and 25°C. and wherein the peak strain amplitude is utilized such that the material resides in the linear region of viscoelasticity. Preferably, the gel also has a dynamic elastic storage modulus (G') of at least 500 Pascals under these measurement conditions. Gel state, as further defined herein, also denotes a crosslinked mass having an insoluble gel fraction of at least 10 weight percent when measured in a solvent for the liquid organopolysiloxane. Before component (A) is cured, it must have a loss tangent of 2.0 or more and a gel fraction of less than 10% under the aforementioned conditions. Since solid particles normally employed in electrorheological compositions are insoluble and can impart a significant elastic modulus when dispersed therein, the above mentioned loss tangent and gel fractions are determined on unfilled, neat component (A) for the purposes of our invention. Alternatively, the gel fraction can be obtained on the filled component (A) if the filler content is subtracted from this measurement. For this invention, the (unfilled) curable silicone polymer (A) must cure to a gelled state, having the above described rheological and solubility properties, within 12 hours at a temperature of 100°C. The above rheological characterization can be accomplished by standard methods known in the art. For example, the neat liquid curable silicone polymer (A), containing the proper amount of a metal catalyst, can be placed on the plates of a dynamic mechanical spectrometer and cured therebetween at the above mentioned conditions. Measurement of dynamic mechanical properties at 10 Hz can be carried out while cure is taking place at elevated temperature and thereafter at 25°C. Similarly, the gelled silicone can be extracted by conventional techniques using a solvent for the liquid organopolysiloxane to a point where no more material is dissolved, the gel fraction then being determined from the amount of the dried insoluble residue. In general form, the oligomeric component (A) is a curable organopolysiloxane. Thus, for example, component (A) may be selected from any of the filled or unfilled liquid organopolysiloxane room temperature vulcanizing (RTV) systems known in the art which fit within the rheological and solubility restrictions outlined above. One-part RTVs, wherein cure is accomplished by virtue of reactive groups being attached to organopolysiloxane chains, as well as two-part systems, wherein cure results from the reaction of a low molecular weight crosslinker with reactive groups on the organopolysiloxane, can be used. The scientific and patent literature is replete with examples of these systems and, since these compositions are well known in the art and are available commercially, a detailed description thereof is considered unnecessary. By way of illustration, an extensive bibliography of moisture-curable systems is provided in U.S. Patent 3,635,887. Component (A) in our compositions is a curable silicone polymer having a formula selected from (i) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(OR) 3 , (ii) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 , (iii) (X) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 , and (iv) mixtures thereof, wherein R is a monovalent hydrocarbon radical having from 1 to 20 carbon atoms, X is independently selected from R, acyloxy groups, hydroxy groups, alkoxy groups, oxime groups and olefinic hydrocarbon radicals having from 2 to 20 carbon atoms, m has an average value of from 0 to 100 and n has an average value of from 100 to 2,000. The monovalent radicals of R in Component (A) can contain up to 20 carbon atoms and include halohydrocarbon radicals free of aliphatic unsaturation and hydrocarbon radicals. Monovalent hydrocarbon radicals include alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl and octyl; cycloaliphatic radicals, such as cyclohexyl; aryl radicals, such as phenyl, tolyl and xylyl; aralkyl radicals, such as benzyl and phenylethyl. Highly preferred monovalent hydrocarbon radicals for the silicon-containing components of this invention are methyl or phenyl. Monovalent halohydrocarbon radicals include any monovalent hydrocarbon radical noted above which has at least one of its hydrogen atoms replaced with a halogen atom, such as fluorine, chlorine or bromine. Preferred monovalent halohydrocarbon radicals have the formula C n F 2n+1 CH 2 CH 2 - wherein the subscript n has a value of from 1 to 10, such as, for example, CF 3 CH 2 CH 2 - and C 4 F 9 CH 2 CH 2 -. The several R radicals can be identical or different, as desired, and preferably at least 50 percent of all R radicals are methyl. The functional group X is selected from the group consisting of R, acyloxy groups, hydroxy groups, alkoxy groups, oxime groups and mixtures thereof. R is as described above including preferred embodiments thereof. Acyloxy groups suitable as X in our compositions are exemplified by groups having the formula wherein R is a monovalent hydrocarbon radical having from 1 to 10 carbon atoms. Groups suitable as R in the gels of the invention include groups such as methyl, ethyl, propyl, butyl, phenyl, aryl, cycloalkyl groups and cycloaryl groups. Preferred as R groups are methyl, ethyl, propyl, butyl and phenyl. Preferred as the acyloxy group in our compositions are acetoxy groups such as acetoxy, acetoxyalkyl groups, acetoxyaryl groups, acetoxycycloalkyl groups and acetoxycycloaryl groups. Hydroxy groups suitable for use in the instant invention include hydroxyalkyl groups, hydroxyaryl groups, hydroxycycloalkyl groups and hydroxycycloaryl groups. Preferred hydroxy (OH) groups as X, herein, include groups such as hydroxy, hydroxypropyl, hydroxybutyl, hydroxyphenyl, hydroxymethylphenyl, hydroxyethylphenyl and hydroxycyclohexyl. Alkoxy groups suitable as X in component (A) include groups such as alkoxyalkyl groups, alkoxyaryl groups, alkoxycycloalkyl groups and alkoxycycloaryl groups. Preferred alkoxy groups for X are groups such as methoxy, ethoxy, butoxy, tertiary-butoxy, propoxy, isopropoxy, methoxyphenyl, ethoxyphenyl, methoxybutyl and methoxypropyl groups. Oxime groups suitable as X in component (A) preferably have the formula -ON=C(R 1 )(R 2 ), wherein R 1 and R 2 each represent a monovalent hydrocarbon radical having from 1 to 20 carbon atoms or a phenyl radical. Preferred as oxime groups in the our invention are dimethylketoxime, methylethylketoxime, diethylketoxime, methylpropylketoxime, methylbutylketoxime, methylhexylketoxime, ethylmethylketoxime, ethylpropylketoxime, ethylbutylketoxime, ethylhexylketoxime, methylphenylketoxime, ethylphenylketoxime, phenylmethylketoxime and diphenylketoxime. Oxime containing silanes such as methyltris(methylethylketoximo)silane, vinyltris(methylethylketoximo)silane, phenyltris(methylethylketoximo)silane, methyltris(diethylketoximo)silane, tetrakis(methylethylketoximo)silane and partial hydrolyzates thereof are also suitable as X in component (A). It is preferred that R 1 and R 2 are selected from methyl or ethyl. A highly preferred oxime group of the instant invention is -ON=C(Me)(Et) wherein Me denotes methyl and Et denotes ethyl. X can also be a mixture of any of the above described groups. The olefinic hydrocarbon radicals of X in our invention may have from 2 to 20 carbon atoms. The olefinic hydrocarbon radicals are preferably selected from the vinyl radical or higher alkenyl radicals represented by the formula -R 3 (CH 2 ) c CH=CH 2 wherein R 3 denotes -(CH 2 ) d - or -(CH 2 ) e CH=CH- and c has the value of 1, 2 or 3, d has the value of 3 or 6 and e has the value of 3, 4 or 5. The higher alkenyl radicals represented by the formula - R 3 (CH 2 ) c CH=CH 2 contain at least 6 carbon atoms. For example, when R 3 denotes -(CH 2 ) d -, the higher alkenyl radicals include 5-hexenyl, 6-heptenyl, 7-octenyl, 8-nonenyl, 9-decenyl and 10-undecenyl. When R 3 denotes -(CH 2 ) e CH=CH-, the higher alkenyl radicals include 4,7-octadienyl, 5,8-nonadienyl, 5,9-decadienyl, 6,11-dodecadienyl and 4,8-nonadienyl. Alkenyl radicals selected from 5-hexenyl, 7-octenyl, 9-decenyl and 5,9-decadienyl, are preferred. It is more preferred that R 3 denote -(CH 2 ) d - so that the radicals contain only terminal unsaturation and the most preferred radicals are the vinyl radical or the 5-hexenyl radical. Specific examples of preferred polydiorganosiloxanes for use as Component (A) in the compositions of this invention include ViMe 2 SiO(Me 2 SiO) n SiMe 2 Vi, HexMe 2 SiO(MeHexSiO) m (Me 2 SiO) n SiMe 2 Hex, ViMe 2 SiO(MeViSiO) m (Me 2 SiO) n SiMe 2 Vi, HexMe 2 SiO(MeHexSiO) 4 (Me 2 SiO) 196 SiMe 2 Hex, HexMe 2 SiO(MeHexSiO) 2 (Me 2 SiO) 198 SiMe 2 Hex, HexMe 2 SiO(MeHexSiO) 3 (Me 2 SiO) 151 SiMe 2 Hex, ViMe 2 SiO(MeViSiO) 2 (Me 2 SiO) 130 SiMe 2 Vi, HexMe 2 SiO(Me 2 SiO) n siMe 2 Hex, PhMeViSiO(Me 2 SiO) n SiPhMeVi, HexMe 2 SiO(Me 2 SiO) 130 SiMe 2 Hex, ViMePhSiO(Me 2 SiO) 145 SiPhMeVi, ViMe 2 SiO(Me 2 SiO) 130 SiMe 2 Vi, ViMe 2 SiO(Me 2 SiO) 800 SiMe 2 Vi, ViMe 2 SiO(Me 2 SiO) 300 SiMe 2 Vi and ViMe 2 SiO(Me 2 SiO) 900 SiMe 2 Vi, wherein Me, Vi, Hex and Ph hereafter denote methyl, vinyl, 5-hexenyl and phenyl, respectively and m and n are as defined above. Preferably the degree of polymerization (DP) of the curable silicone polymer (A) is such that the value of m in (i)-(iii) above is from 0 to 100 and the value of n is from 100 to 2000. It is preferred for this invention that the degree of polymerization of the curable silicone polymer is such that the value of m+n is from 300 to 2000. It is highly preferred that the value of n is from 500 to 1000. The amount of Component (A) employed in our compositions varies depending on the amount of solid particles or metal catalyst, and optionally, organohydrogensiloxane and/or inhibitor that is employed. It is preferred that from 40 to 95 weight percent of (A), the curable silicone polymer, be used and it is highly preferred that from 50 to 80 weight percent of (A) be employed, said weight percent being based on the total weight of the composition. Component (B) of our compositions comprises solid particles. The solid particles of component (B) are electrorheologically active particles, i.e., they exhibit rheological properties upon the application of an electrical field. A wide variety of solid particles may be used to form the dispersed phase in the ER gels of this invention. Examples are acid group-containing polymers, silica gel, starch, cellulose, electronic conductors, zeolite, silicone ionomers such as sulfate ionomers of aminofunctional siloxanes, organic polymers containing free salified acid groups, amino acid containing metal polyoxo-salts, organic polymers containing at least partially salified acid groups, homo-polymers of monosaccharides or other alcohols, copolymers of monosaccharides or other alcohols and copolymers of phenols and aldehydes or mixtures thereof. Salified for purposes of the present invention means to form or convert into a salt or mixed with a salt. Preferred as solid particles in the ER gels of this invention are corn starch, carboxy modified polyacrylamides, lithium salts of polymethacrylic acid, zeolite, amino acid containing metal polyoxo-salts and silicone ionomers. The successful development of electrorheological properties with substances conventionally used as the solid particles (B), such as starch and silica gel, requires the presence in the ER gel of a minimum amount of water. However, a new class of solid phase materials which function under anhydrous conditions has recently been taught in GB-A 2,170,510. The solid phase materials therein are electronic conductors, particularly organic semiconductors and may be used in the compositions of our invention to provide ER gels of particularly advantageous properties. The solid particles of this invention can also be amino acid containing metal polyoxo-salt such as those disclosed in U.S. Patent No. 5,320,770. These solid particles are compounds having the general formula: [(M) p (H 2 O) x (OH) y ] q c [A] r d · B z · n H 2 O wherein M is a metal cation or a mixture of metal cations at various ratios; p is the total valence of M and has a value of greater than zero; x is zero or has a value greater than zero, y is zero or has a value greater than zero, with the proviso that only one of x or y can be zero at any given time; q has a value of p minus y with the proviso that q has a value of at least one; c has a value of greater than zero; A is an anion or a mixture of anions at various ratios; r is the total valence of A with the proviso that r has a value of at least one; d has a value of greater than zero with the proviso that (q x c) is always equal to (r x d); B is an amino acid or a mixture of amino acids; z has a value of from 0.01 to 100; and n is a number from 0 to 15. Preferably, the solid particles (B) are silicone ionomers. Preferred are those which are a reaction product of (I) an amine functional diorganopolysiloxane having a DP of less than 10,000 in which at least 3 mole percent of the silicon atoms have attached thereto, through silicon-carbon bonds, an amine functional organic group bearing at least one -NHR" group, in which R'' is selected from hydrogen atom or an alkyl radical having from 1 to 6 carbon atoms, and (II) an acid such as those described in U.S. Patent 4,994,198. It is highly preferred that the solid particle (B) is a sulfate ionomer of an aminofunctional siloxane. The particle size of the solid particles in our compositions is not critical. However, the particle size successfully employed in the invention range from 1 micrometer to 200 micrometers, with a preferred range of 5-50 micrometers. Typically, 5 to 60 weight percent of the solid particles (B), by weight percent of the gel, are dispersed into the liquid siloxane phase of the present invention. Preferably, 20 to 50 weight percent of the solid particles are dispersed in this phase. However, the optimum amount used depends greatly on the specific type of solid particle that is employed, the type of organosiloxane selected, gel viscosity, intended application and other variables. Those skilled in the art will readily determine the proper proportions for any given system by routine experimentation. Component (C) in our compositions is a metal catalyst, preferably selected from organo compounds of tin, organo compounds of titanium, compounds of platinum and complexes thereof. Catalysts suitable as (C) are organotitanates such as tetraisopropyl titanate, tetrabutyl titanate, tetraethylhexyl titanate, tetraphenyltitanate and triethanolamine titanate; or organometallic compounds such as dibutyltin dilaurate, stannous acetate, stannous octoate, stannous benzoate, stannous sebacate, stannous succinate, tin octoate, dibutyltin diacetate, zinc octoate, cobalt octoate, stannous napthanate, cobalt naphthanate, titanium naphthanate and cerium naphthanate; siloxytitanates such as tetrakis(trimethylsiloxy)titanium and bis(trimethylsiloxy)-bis(isopropoxy)titanium; and betadicarbonyltitanium compounds such as bis(acetylacetonyl) diisopropyl titanate. Component (C) in our compositions can also be a Group VIII metal catalyst or a complex thereof. By Group VIII metal catalyst, it is meant iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. The metal catalyst of Component (C) can be a platinum-containing catalyst component since they are the most widely used and available. Platinum-containing catalysts can be platinum metal, optionally deposited on a carrier, such as silica gel or powdered charcoal; or a compound or complex of a platinum group metal. A preferred platinum-containing catalyst component for this invention is a form of chloroplatinic acid, either as the commonly available hexahydrate form or as the anhydrous form, as taught in U.S. Patent 2,823,218. A particularly useful form of chloroplatinic acid is that composition obtained when it is reacted with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane, as disclosed in U.S. Patent 3,419,593, because of its easy dispersibility in organosilicon systems. Other useful catalysts are those disclosed in U.S. Patents 3,159,601; 3,159,662; 3,220,972; 3,296,291; 3,516,946; 3,814,730 and 3,928,629. Other Group VIII metal catalysts suitable as Component (C) for the compositions of our invention include RhCl 3 , RhBr 3 , RhI 3 and complexes thereof, although it is preferred that platinum catalyst systems be employed such as ClRh(PPh 3 ) 3 and complexes thereof; H 2 PtCl 6 ; a complex of 1,3-divinyl tetramethyl disiloxane and H 2 PtCl 6 ; alkyne complexes of H 2 PtCl 6 or a form of chloroplatinic acid, either as the commonly available hexahydrate form or as the anhydrous form. It is preferred that catalyst (C) is selected from tetrabutyltitanate, stannous octoate, chloroplatinic acid, diisopropoxy-diethylacetoacetate titanate, 2,5-diisopropoxy-bis-ethylacetoacetate titanate and titanium bis(ethylaceto-acetate) diisopropoxy isopropyl alcohol. The amount of metal catalyst, Component (C), that is used in our compositions is not narrowly limited and can be readily determined by one skilled in the art by routine experimentation. Component (C), however, should be added in a quantity sufficient to effect curing of our composition. The most effective concentration of catalyst is from 0.001 to 10 parts by weight of the catalyst per 100 parts by weight of the curable silicone polymer Component (A). Preferably, it is added at 0.01 to 1 part by weight per 100 parts of Component (A). Our composition can further comprise (D) as a crosslinking agent. Preferably, Component (D) is at least one organohydrogensilicon compound which is free of aliphatic unsaturation and which contains two or more silicon atoms linked by divalent radicals, an average of from one to two silicon-bonded monovalent radicals per silicon atom and an average of at least one, and preferably three or more, silicon-bonded hydrogen atoms per molecule. Preferably, the organohydrogensiloxane crosslinker of the present invention contains an average of three or more silicon-bonded hydrogen atoms, such as 5, 10, 20, 40, 70, 100 or more. The organohydrogenpolysiloxane is preferably a compound having the average unit formula R a 4 H b SiO (4-a-b)/2 wherein R 4 denotes a monovalent radical free of aliphatic unsaturation, the subscript b has a value of from greater than 0 to 1, such as 0.001, 0.01, 0.1 and 1.0 and the sum of the subscripts a plus b has a value of from 1 to 3, such as 1.2, 1.9 and 2.5. Siloxane units in these organohydrogenpolysiloxanes have the formulae R 3 4 SiO 1/2 , R 2 4 HSiO 1/2 , R 2 4 SiO 2/2 , R 4 HSiO 2/2 , R 4 SiO 3/2 , HSiO 3/2 and SiO 4/2 . Said siloxane units can be combined in any molecular arrangement such as linear, branched, cyclic and combinations thereof, to provide organohydrogenpolysiloxanes that are useful as component (D) in our invention. A preferred organohydrogenpolysiloxane for these compositions is a substantially linear organohydrogenpolysiloxane having the formula ZR 2 SiO(ZRSiO) c SiR 2 Z wherein each R denotes a monovalent hydrocarbon or halohydrocarbon radical, free of aliphatic unsaturation and having from 1 to 20 carbon atoms. Representative monovalent hydrocarbon radicals include alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl and octyl; cycloaliphatic radicals, such as cyclohexyl; aryl radicals, such as phenyl, tolyl and xylyl; aralkyl radicals, such as benzyl or phenylethyl. Highly preferred monovalent hydrocarbon radicals for this invention are methyl or phenyl. Monovalent halohydrocarbon radicals free of aliphatic unsaturation include any monovalent hydrocarbon radical noted above, which is free of aliphatic unsaturation and which has at least one of its hydrogen atoms replaced with a halogen atom, such as fluorine, chlorine or bromine. Preferred monovalent halohydrocarbon radicals have the formula C n F 2n+1 CH 2 CH 2 -wherein the subscript n has a value of from 1 to 10, such as, for example, CF 3 CH 2 CH 2 - and C 4 F 9 CH 2 CH 2 -. The several R radicals can be identical or different, as desired. Additionally, each Z denotes a hydrogen atom or an R radical. Of course, at least two Z radicals must be hydrogen atoms. The exact value of y depends upon the number and identity of the R radicals; however, for organohydrogenpolysiloxanes containing only methyl radicals as R radicals c will also have a value of from 0 to 1000. In terms of preferred monovalent hydrocarbon radicals, examples of our organopolysiloxanes which are suitable include HMe 2 SiO(Me 2 SiO) c SiMe 2 H, (HMe 2 SiO) 4 Si, cyclo-(MeHSiO) c , (CF 3 CH 2 CH 2 )MeHSiO{Me(CF 3 CH 2 CH 2 )SiO} c- SiHMe(CH 2 CH 2 CF 3 ), Me 3 SiO(MeHSiO) c SiMe 3 , HMe 2 SiO(Me 2 SiO) 0.5c (MeHSiO) 0.5c SiMe 2 H, HMe 2 SiO(Me 2 SiO) 0.5c (MePhSiO) 0.1c (MeHSiO) 0.4c SiMe 2 H, Me 3 SiO(Me 2 SiO) 0.3c (MeHSiO) 0.7c SiMe 3 and MeSi(OSiMe 2 H) 3 . Highly preferred linear organohydrogenpolysiloxanes for our invention have the formula ZMe 2 SiO(Me 2 SiO) p (MeZSiO) q SiMe 2 Z wherein Z denotes a hydrogen atom or a methyl radical. An average of at least two Z radicals per molecule must be hydrogen atoms. The subscripts p and q can have average values of zero or more and the sum of p plus q has a value equal to c as noted above. The disclosure of U.S. Patent 4,154,714 shows highly-preferred organohydrogenpolysiloxanes for our invention. Especially preferred as Component (D) are methylhydrogensiloxanes selected from bis(trimethylsiloxy)-dimethyldihydrogendisiloxane, diphenyldimethyldisiloxane, diphenyltetrakis(dimethylsiloxy)disiloxane, heptamethyl-hydrogentrisiloxane, hexamethyldihydrogentrisiloxane, methylhydrogencyclosiloxanes, methyltris(dimethylhydrogen-siloxy)silane, pentamethylpentahydrogencyclopentasiloxane, pentamethylhydrogendisiloxane, phenyltris(dimethylhydrogensiloxy)silane, polymethylhydrogensiloxane, tetrakis-(dimethylhydrogensiloxy)silane, tetramethyltetrahydrogencyclotetrasiloxane, tetramethyldihydrogendisiloxane and methylhydrogendimethylsiloxane copolymers. The amount of Component (D), if employed, varies depending on the amount of curable silicone polymer (A), solid particles (B) and metal catalyst (C) that is employed. It is preferred for purposes of this invention that Component (D) comprise from 0 to 10 weight percent of the total composition. The compositions of our invention can also further comprise (E) as an inhibitor. The inhibitor (E) can be employed in combination with crosslinker (D) or can be used in the absence of crosslinker (D). Component (E) of our compositions of this invention is any material that is known to be, or can be, used as an inhibitor for the catalytic activity of catalysts. By the term "inhibitor", it is meant herein a material that retards the room temperature curing of a curable mixture of Components (A), (B), (C) and optionally (D) when incorporated therein in small amounts, such as less than 10 percent by weight of the composition, without preventing the elevated curing of the mixture. Inhibitors for the platinum group metal catalysts are well known in the organosilicon art. Examples of such metal catalyst inhibitors include unsaturated organic compounds such as ethylenically or aromatically unsaturated amides, U.S. Patent 4,337,332; acetylenic compounds, U.S. Patents 3,445,420 and 4,347,346; ethylenically unsaturated isocyanates, U.S. Patent 3,882,083; olefinic siloxanes, U.S. Patent 3,989,667; unsaturated hydrocarbon diesters, U.S. Patents 4,256,870; 4,476,166 and 4,562,096 and conjugated ene-ynes, U.S. Patent Nos. 4,465,818 and 4,472,563; other organic compounds such as hydroperoxides, U.S. Patent 4,061,609; ketones, sulfoxides, amines, phosphines and phosphites; nitriles such as U.S. Patent 3,344,111; diaziridines, U.S. Patent 4,043,977; and various salts, such as U.S. Patent 3,461,185. Organic inhibitor compounds which bear aliphatic unsaturation and one or more polar groups, such as carbonyl or alcohol groups, are preferred as (E) in the instant invention. Examples thereof include the acetylenic alcohols of U.S. Patent 3,445,420, such as ethynylcyclohexanol and methylbutynol; the unsaturated carboxylic esters of U.S. Patent 4,256,870, such as diallyl maleate and dimethyl maleate; and the maleates and fumarates of U.S. Patents 4,562,096 and 4,774,111, such as diethyl fumarate, diallyl fumarate and bis-(methoxyisopropyl) maleate. The half esters and amides of U.S. Patent 4,533,575; or the inhibitor mixtures of U.S. Patent 4,476,166, would also be acceptable. The above-mentioned patents teach how to prepare compounds which are suitable for use as Component (E) in our compositions for platinum catalysts. Maleates and fumarates are the preferred inhibitors for the compositions of this invention. The maleates and fumarates more preferred as Component (E) in our compositions have the formula R 5 (OQ) t O 2 CCH=CHCO 2 (QO) t R 5 , wherein R 5 denotes a monovalent hydrocarbon radical having from 1 to 10 carbon atoms and each Q denotes, independently, an alkylene radical having from 2 to 4 carbon atoms. R 5 can be an alkyl radical such as methyl, ethyl, propyl, isopropyl, butyl, pentyl or hexyl; an aryl radical such as phenyl or benzyl; an alkenyl radical such as vinyl or allyl; alkynyl radical; or a cyclohydrocarbon radical such as cyclohexyl. Q can be, for example, CH 2 CH 2 -, -CH 2 (CH 3 )CH-, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 , -CH 2 (CH 3 CH 2 )CH- and -CH 2 CH 2 (CH 3 )CH-. The individual R 5 and Q radicals of the maleates and fumarates can be identical or different, as desired. The value of subscript t can be a value equal to zero or 1. The individual values of t can be identical or different, as desired. Bis-methoxyisopropyl maleate and diethyl fumarate are preferred as inhibitors for this invention. The amount of Component (E) used in our compositions is not critical and can be any amount that will retard the catalyzed reaction at room temperature while not preventing said reaction at an elevated temperature. Thus, no specific amount of inhibitor can be suggested to obtain a suitable bath life at room temperature. Rather, the desired amount of any particular inhibitor will depend upon the concentration and type of the catalyst, the nature and amounts of Components (A), (B) and (C) and the presence or absence of optional ingredients. A practical range appears to be 0.5 to 1.05 percent of the total formulation for a maleate inhibitor and 0.8 to 2.0 percent of the total formulation for a fumarate inhibitor. Other preferred inhibitors are alcohols, for example, aromatic alcohols such as benzyl alcohol or n-octanol. Also preferred is a combination of diethyl fumarate as the inhibitor complexed with benzyl alcohol as (E). We have generally taught the broad and narrow limits for the optional inhibitor component concentration for this invention; however, one skilled in the art can readily determine the optimum level for each application as desired. The present invention further relates to a method for the preparation of an electrorheological gel which prior to the application of an electric field has a storage modulus of between 500 and 500,000 pascals when measured at a frequency of 10 hertz at 25°C., a peak strain amplitude such that the gel resides in the linear region of viscoelasticity and has a dynamic mechanical loss tangent of at least 0.5, which method comprises: (I) dispersing electrorheologically active solid particles in: (A) a curable silicone polymer having its formula selected from (i) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(OR) 3 ; (ii) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 ; (iii) (X) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 ; and (iv) mixtures thereof; wherein R is a monovalent hydrocarbon radical having from 1 to 20 carbon atoms, X is independently selected from R, acyloxy groups, hydroxy groups, alkoxy groups, oxime groups and olefinic hydrocarbon radicals having from 2 to 20 carbon atoms, m has an average value of from 0 to 100 and n has an average value of from 100 to 2000; and (II) adding (B) a metal catalyst to the mixture of (I). Components (A) and (B) are as delineated above for our compositions including preferred embodiments thereof. Our method can further comprise adding (D) a crosslinking agent after step (I) and/or adding (E) an inhibitor after step (I). The crosslinking agent (D) and inhibitor (E) are as delineated above for our compositions including preferred embodiments thereof. Furthermore, the electrorheological composition of our invention can be heated, preferably to a temperature of from 25 to 100°C., prior to its use. Dispersion of the solid particles in the gel phase of the present invention is accomplished by any of the commonly accepted methods, such as those employing a ball mill, paint mill and a high shear mixer. During this process, the solid particles and organosiloxane base gel are sheared at a high rate, thereby reducing the size of the particles. It has been found that a final particle size having an average diameter of 5 to 40 micrometers is preferred. If the diameter is 100 micrometers, the particles tend to settle out and limit the number of particles that can fit between the electrodes. If the diameter is too low, thermal Brownian Motion of the particles tends to reduce the ER effect. An equivalent dispersion of solid particles in the base gel in our compositions may also be effected by first grinding the particles to a suitable fineness or by spray drying the solid particles and subsequently mixing them into our uncured gel. The present invention further relates to a method of using the electrorheological gel composition of or prepared according to the present invention, which method comprises applying an electric field across the gel. If desired, a dispersant such as a hydrogenated castor oil, an organic solvent such as hexane, heptane, toluene, xylene, mineral spirits, ketones or acetates, cyclic or linear alkanes, aromatic hydrocarbons such as benzene and low molecular weight linear and cyclic polydimethylsiloxanes may be incorporated into our electrorheological compositions. However, it is a distinct advantage of our ER gels that they are physically stable and do not require the inclusion of a dispersant or solvent to maintain a sufficiently dispersed solid phase. Our ER gel compositions may further comprise antioxidants, stabilizers, colorants and dyes. When some of our compositions are exposed to moisture, they can cure resulting in a gelled silicone. The viscoelastic properties of materials are functions of chemical composition, structure, temperature, applied strain amplitude and applied strain rate. Generally, when all these variables are fixed the viscoelastic properties are fixed. However, electrorheological gels can alter the viscoelastic time-temperature-composition relationship by subjecting the gel to an electric field. A gel can be shifted from a predominantly viscous material (tan delta > 1) to a predominantly elastic material (tan delta < 1) by applying an electric field across the gel. Additionally, formulations can be made where the elastic contribution is always the dominant component and the dominance can be increased by the application of the electric field. The ability to control a cured gel's viscoelastic properties by applying electric fields will allow for novel methods of controlling implied stresses. Potential applications of these electrorheological gels may be found in constrained layer composite systems for the use of vibration damping and controlled stiffness applications. Multi-layered composites consisting of layers of electrorheological gel with alternating layers of electrodes (i.e. metal foils, conductive polymer films, etc.) can be fabricated and with our ER gels can be designed to dampen changes in mechanical or acoustical vibration. Further, the ability to alter the elastic modulus would permit a system which could alter the levels of energy transmittance by stiffening or relaxing the electrorheological gel material in the laminate by controlling the electric field applied across each gel layer. Our ER gel samples were evaluated in parallel disk geometry on a Rheometrics™ Dynamic Spectrometer (RDS2). Parallel disk geometry refers to a disk specimen which is placed between two parallel plates. The RDS2 shears the sample by oscillating the lower plate in a sinusoidal pattern. The amplitude of the oscillations is determined by the thickness of the sample and the desired level of strain. All of these values are input into a controlling computer. The test values shown in the tables are frequency sweeps at set strains. The frequency in the examples was set at 50 rad/s with the strain set at 0.5%. The parallel plates in the examples were about 50 millimeters in diameter. This data shows how the ER gel responds to applied strains. The values of G' increase when an electric field is applied which indicates the material is behaving as a stiffer spring than when no electric field is applied. Tan delta decreases when the electric field is applied which indicates the material's behavior is becoming more elastic. The following examples are presented to further illustrate the compositions of this invention. All parts and percentages in the examples are on a weight basis unless indicated to the contrary. Example I An electrorheological gel of the instant invention was prepared. First, 4.05 grams of an organopolysiloxane having the formula: ViMe 2 SiO(Me 2 SiO) 900 SiMe 2 Vi (Polymer B) was added to an aluminum weighing pan. Next, 0.45 grams of a silicone polymer having the formula: (MeO) 3 SiCH 2 CH 2 SiO(Me 2 SiO) 900 SiCH 2 CH 2 Si(OMe) 3 (polymer A) was added to the pan plus 2.0 grams of toluene. The items were mixed with a spatula and then 0.5 grams of 100 mole% amine hydrolyzate sulfate ionomer particles prepared from the disclosure of U.S. Patent 4,994,198, were mixed into the system. The amine hydrolyzate sulfate ionomer particles were prepared by combining an amine hydrolyzate which was a mixture of linear and cyclic organopolysiloxanes having the formula OCH 3 RCH 3 SiO(CH 3 RSiO) x SiCH 3 RCH 3 O having a viscosity of 1300 centistokes (mm 2 /s) and wherein R is CH 2 CH(CH 3 )CH 2 NHCH 2 CH 2 NH 2 with sulfuric acid in an aqueous solution. A ratio of one mole of H 2 SO 4 to one mole of R was used to prepare the particles. The water was then removed to produce the 100 mole percent amine hydrolyzate sulfate ionomer particles. A drop of diisopropoxy-diethylacetoacetate titanate (TDIDE) cataylst was added with stirring and the system allowed to remain exposed to the environment for 24 hours under ambient conditions. The samples were then placed in an oven at 50°C. for 24 hours followed by 5 hours at 120°C. The cured electrorheological gel was removed from the pan and evaluated for an electrorheological effect (i.e. increases in modulus upon the application of an electric field). The amount of electric field (voltage) applied to the electrorheological gel of our invention, the resulting Dynamic Storage Modulus and Tan Delta are presented in Table I. Applied Electric Field E(kV//m) Dynamic Storage Modulus G' (Pascals) Tangent Delta 0 4.7054 x 10 3 2.0805 1.0 4.9774 x 10 3 2.0701 2.0 6.7115 x 10 3 1.7393 Example II First, 1.50 grams of polymer B from Example 1 was mixed with 0.35 grams of polymer A (also from Example 1) plus 2.0 grams of toluene in an aluminum weighing pan. Next 1.50 grams of 100 mole% amine hydrolyzate sulfate ionomer particles were added and the mixture stirred until a uniform dispersion obtained. Next 1 drop of TDIDE catalyst was added, stirred and the mixture was left in ambient conditions for 24 hours. The samples were then placed in an oven at 50°C. for 24 hrs followed by 5 hrs at 120°C. The cured electrorheological gel was removed from the pan and similarly evaluated for an electrorheological effect. The amount of electric field (voltage) applied to our electrorheological gel, the resulting Dynamic Storage Modulus and Tan Delta are presented in Table II. Applied Field Potential E(kV/mm) Dynamic Storage Modulus G' (Pascals) Tangent Delta 0 4.2167 x 10 4 1.2506 1.0 8.6034 x 10 4 0.8977 2.0 1.5823 x 10 5 0.7165 Example III In this example, 2.80 grams of polymer B was mixed with 1.20 grams of polymer A, plus 2.0 grams of toluene in an aluminum weighing pan. Next 1.00 gram of 100 mole% amine hydrolyzate sulfate ionomer particles were added and the mixture stirred until a uniform dispersion obtained. Next 1 drop of TDIDE catalyst was added, stirred and the mixture was left in ambient conditions for 24 hours. The samples were then placed in an oven at 50°C. for 24 hours, followed by 5 hours at 120°C. The cured electrorheological gel was removed from the pan and evaluated for an electrorheological effect. The amount of electric field (voltage) applied to the electrorheological gel, the resulting Dynamic Storage Modulus and Tan Delta are presented in Table III. Applied Electric Field E(kV/mm) Dynamic Storage Modulus G' (Pascals) Tangent Delta 0 6.0689 x 10 4 0.6641 1.0 6.5309 x 10 4 0.6462 2.0 7.1080 x 10 4 0.6260 Example IV In a 100 ml beaker, 29.62 grams of an organopolysiloxane having the formula: ViMe 2 SiO(Me 2 SiO) 130 SiMe 2 Vi, 0.26 grams of an organohydrogensiloxane crosslinking agent having the formula Me 3 SiO(MeHSiO) 5 (Me 2 SiO) 3 SiMe 3 and 30 grams of corn starch were mixed together. Next, a catalytic amount (about 2 x 10 -5 parts per hundred of the organopolysiloxane polymer) of platinum was added and the mixture was stirred. Samples ranging from 3 to 10 grams were poured into aluminum weighing pans. The pans were placed in a vacuum oven set at 50°C. and the pressure was reduced to (5 inches Hg) 0.67 kPa to de-air the samples. The vacuum was removed after 5 minutes. The temperature was increased to 70°C. and the samples were cured for 12 hours prior to evaluation. The cured electrorheological gels were removed from the pan and evaluated for an electrorheological effect and values typical of the compositions of this invention are reported in Table IV. The amount of electric field (voltage) applied to our electrorheological gels, the resulting Dynamic Storage Modulus and Tan Delta are presented in Table IV. Applied Electric Field E(kV/mm) Dynamic Storage Modulus G' (Pascals) Tangent Delta 0 3.9824 x 10 3 0.5244 1.0 4.6115 x 10 3 0.5074 2.0 6.4610 x 10 3 0.4881 Example V In a 100 ml beaker, 29.62 grams of an organopolysiloxane having the formula: ViMe 2 SiO(Me 2 SiO) 130 SiMe 2 Vi, 0.26 grams of an organohydrogensiloxane crosslinking agent having the formula Me 3 SiO (MeHSiO) 5 (Me 2 SiO) 3 SiMe 3 and 30 grams of aluminum zirconium proline (AZP) were mixed together. Next, a catalytic amount (2 x 10 -5 parts per hundred of the organopolysiloxane polymer) of platinum was added and the mixture was stirred. Samples ranging from 3 to 10 grams were poured into aluminum weighing pans. The pans were placed in a vacuum oven set at 50°C. and the pressure was reduced to (5 inches Hg) 0.67 kPa to de-air the samples. The vacuum was removed after 5 minutes. The temperature was increased to 70°C. and the samples were cured for 12 hours prior to evaluation. The cured electrorheological gels were removed from the pan and evaluated for an electrorheological effect. Values typical of the compositions of our invention are reported in Table V. The amount of electric field (voltage) applied to our electrorheological gels, the resulting Dynamic Storage Modulus and Tan Delta are presented in Table V. Applied Electric Field E(kV/mm) Dynamic Storage Modulus G' (Pascals) Tangent Delta 0 1.4672 x 10 3 0.8189 2.0 1.5545 x 10 3 0.8420 3.0 2.5947 x 10 3 0.6680 4.0 7.3053 x 10 3 0.5393

Claims: An electrorheological gel, which prior to the application of an electric field has a storage modulus of between 500 and 500,000 pascals when measured at a frequency of 10 hertz at 25°C., a peak strain amplitude such that the gel resides in the linear region of viscoelasticity and has a dynamic mechanical loss tangent of at least 0.5, which gel is formed from a composition which comprises: (A) a curable silicone polymer having its formula selected from (i) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(OR) 3 ; (ii) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 ; (iii) (X) 3 SiO(RXSiO) m (R 2 SiO) n Si(X)3; and (iv) mixtures thereof; wherein R is a monovalent hydrocarbon radical having from 1 to 20 carbon atoms, X is independently selected from R, acyloxy groups, hydroxy groups, alkoxy groups, oxime groups and olefinic hydrocarbon radicals having from 2 to 20 carbon atoms, m has an average value of from 0 to 100 and n has an average value of from 100 to 2,000; (B) electrorheologically active solid particles; and (C) a metal catalyst. A gel according to claim 1 wherein (A) is selected from ViMe 2 SiO(Me 2 SiO) n SiMe 2 Vi, HexMe 2 SiO(MeHexSiO) m (Me 2 SiO) n SiMe 2 Hex, ViMe 2 SiO(MeViSiO) m (Me 2 SiO) n SiMe 2 Vi, HexMe 2 SiO (MeHexSiO) 4 (Me 2 SiO) 196 SiMe 2 Hex, HexMe 2 SiO (MeHexSiO) 2 (Me 2 SiO) 198 SiMe 2 Hex, HexMe 2 SiO (MeHexSiO) 3 (Me 2 SiO) 151 SiMe 2 Hex, ViMe 2 SiO (MeViSiO) 2 (Me 2 SiO) 130 SiMe 2 Vi, HexMe 2 SiO (Me 2 SiO) n SiMe 2 Hex, PhMeViSiO(Me 2 SiO) n SiPhMevi, HexMe 2 SiO (Me 2 SiO) 130 SiMe 2 Hex, ViMePhSiO(Me 2 SiO) 145 SiPhMeVi, ViMe 2 SiO (Me 2 SiO) 130 SiMe 2 Vi, ViMe 2 SiO (Me 2 SiO) 800 SiMe 2 Vi, ViMe 2 SiO (Me 2 SiO) 300 SiMe 2 Vi, ViMe 2 SiO (Me 2 SiO) 900 SiMe 2 Vi, wherein Me denotes methyl, Vi denotes vinyl, Hex denotes 5-hexenyl and Ph denotes phenyl. A gel according to claim 1 or 2 wherein (B) is selected from corn starch, carboxy modified polyacrylamides, lithium salts of polymethacrylic acid, zeolite, amino acid containing metal polyoxo-salts and silicone ionomers. A gel according to claim 1, 2 or 3 wherein (C) is selected from organo compounds of tin, organo compounds of titanium, platinum and complexes thereof. A gel according to any one of claims 1 to 4 wherein the composition further comprises a crosslinking agent (D). A gel according to claim 5 wherein (D) is an organohydrogensilicon compound is selected from bis (trimethylsiloxy)dimethyldihydrogendisiloxane, diphenyldimethyldisiloxane, diphenyltetrakis-(dimethylsiloxy)disiloxane, heptamethylhydrogentrisiloxane, hexamethyldihydrogentrisiloxane, methylhydrogencyclosiloxanes, methyltris (dimethylhydrogensiloxy)silane, pentamethylpentahydrogencyclopentasiloxane, pentamethylhydrogendisiloxane, phenyltris polymethylhydrogensiloxane,-silane, polymethylhydrogensiloxane, tetrakis(dimethylhydrogensiloxy)silane, tetramethyltetrahydrogencyclotetrasiloxane, tetramethyldihydrogendisiloxane and methylhydrogendimethylsiloxane copolymers. A gel according to any preceding claim wherein the composition further comprises an inhibitor (E) that retards the room temperature curing of a curable mixture of (A), (B) and (C) or (A), (B) and (C) plus (D). A gel according to claim 7 wherein the inhibitor (E) is selected from maleates, fumarates, aromatic alcohols and mixtures thereof. A method for the preparation of an electrorheological gel which prior to the application of an electric field has a storage modulus of between 500 and 500,000 pascals when measured at a frequency of 10 hertz at 25°C., a peak strain amplitude such that the gel resides in the linear region of viscoelasticity and has a dynamic mechanical loss tangent of at least 0.5, which method comprises: (I) dispersing electrorheologically active solid particles in: (A) a curable silicone polymer having its formula selected from (i) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(OR) 3 ; (ii) (RO) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 ; (iii) (X) 3 SiO(RXSiO) m (R 2 SiO) n Si(X) 3 ; and (iv) mixtures thereof; wherein R is a monovalent hydrocarbon radical having from 1 to 20 carbon atoms, X is independently selected from R, acyloxy groups, hydroxy groups, alkoxy groups, oxime groups and olefinic hydrocarbon radicals having from 2 to 20 carbon atoms, m has an average value of from 0 to 100 and n has an average value of from 100 to 2000; and (II) adding (B) a metal catalyst to the mixture of (I). A method of using an electrorheological gel according to any one of claims 1 to 8 or prepared according to claim 9, which method comprises applying an electric field across the gel.

Inventors: ECKSTEIN MARK HERMAN, FISHER MARK DAVID, SCHMIDT RANDAL GENE, ECKSTEIN, MARK HERMAN, FISHER, MARK DAVID, SCHMIDT, RANDAL GENE
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1995
Main classification: C10M171
IPC codes: C08G77, C10M171