DE2338066A1 - PROCESS FOR THE PRODUCTION OF AMORPHIC CARBON-CONTAINING SILICON DIOXIDE RUBBER, ELASTOMER AND PLASTOMER MATERIALS - Google Patents

Description

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Augu * te-Viktor) a-Strafle Λ «« Ul n> ^ LJl / L? u DA B TM PTTi Pienzenauerstraße 2

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hk £ PATENT LAWYERS ^{Hans E Ru8Chlte} 9eo3 ₂ 4

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Teplifaer Strasse «V ^ XRithR Dep.-Kassel Leopoldstrasse Account 5804723 AJvJUUUU Account: 4623757 Telegram address: Telegram address: Quadrature Berlin Quadrature Munich TELEX: 18378 «TELEX: 522767

19. GHt. 1973

R 1365

P 23 33 066.7

The Regents of the University of California 2200 University Avenue, Berkeley, California / USA

Process for the production of rubber, elastomer and amorphous carbonaceous silica

Plastomer fabrics

The invention relates to a process for the production of amorphous carbonaceous silicon dioxide containing Rubber, elastomer and plastomer substances, substance compounds that create a highly reactive, highly amorphous and anhydrous In the form of silicon oxide (silica, silica, silicic acid).

Certain agricultural organics are rich of biogenetic silica, i.e. silica that is contained within the cell structure occurs. Basically, rice husks, rice stalks, equisetum (a common weed, popularly called horsetail) unfi definite

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Palm leaves, especially the palmyra palm, changing Amount of silica or silicon dioxide in the cell structure. It is also known that certain bamboo sticks are relatively Contain large amounts of silica and wheat straw contains 2-3% silica in the cell structure. For example Most rice hulls generally contain approximately 20% silica, while rice straw is approximately approximately 18 1/2% silica may have. With certain Californian Horsetail weeds are known to have about 20-25% silica.

The use of rice husks and rice straw is for the rice growing industry It has become a major problem in that these parts of the plant appear to have only been burned or buried “Dump space for incinerating the material has become scarce in recent years, and incineration the silica-containing hulls and straw fragments to ashes in the open field generally create undesirable air pollution.

It is of course known that silica is used together with calcium oxides is a constituent of portland cement, mainly in the form of complex calcium silicates. However, the silica that is produced by combustion of silicic acid can organic, agricultural materials are turned into ashes, are only used as a cement component to the extent that when she replaced sand or slate because of the burning

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_ 3 -

the pods inevitably lead to the production of ashes, which contains crystalline forms of silicon dioxide.

The phase diagram of silica indicates that a Transition from the amorphous, non-crystalline form of the substance to those known as tridymite and cristobalite

en
crystalline form / takes place at very high temperatures when the silicon dioxide is in the pure state. Thus, in the case of pure silica in the amorphous form, it is theoretically necessary to raise the temperatures above 1093 ° O in order to effect the conversion. However, the incineration of rice hulls to ash, even at temperatures well below 1093 C, has always led to the formation of crystalline varieties of silica because the transition temperature from amorphous to crystalline form is substantially reduced by the presence of other components of the original rice hulls .

Previous attempts to use crystalline silica as the active component of To use Portland cement, always have heat-treated mixtures of limestone and silicon-containing ones Includes shale or clays at temperatures above 1427 ° C. The same goal can also be achieved by applying mechanical energy. It has been shown experimentally that Abrasive grinding or grinding of crystalline quartz can activate the silica by causing the chemical

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Tear bonds on the surface. In addition to attrition grinding Vibration-milled sand-lime mixtures that are abrasion-milled have been reported to be binding Have acquired properties and that so treated lime sand mixtures have been used as hydraulic cements.

These processes, with the exception of the commercial process of heating a silicon-containing raw material with limestone, have obviously been economically unattractive because of excessive mechanical energy in the vibration and Abrasion milling processes are required.

An object of the invention is to provide a new amorphous silica or silicon dioxide which is composed of an organic, agricultural product containing silica.

Another object of the invention is to provide a highly reactive form of silicon dioxide,

Another object of the invention is to provide a method of using organic agricultural Waste materials with a relatively high initial content of silica or silicon dioxide.

Another object of the invention is to provide new hydraulic cement compounds.

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Another object of the invention is to provide hydraulic cement compounds made from organic Waste derived, amorphous silica are made, this cement having high strength, acid-proof properties and can have a color range from white to black.

The figure of the drawing shows an enlargement of a photomicrograph from an electron microscope of the new silica according to the invention.

The above and other objects of the invention are achieved in part by serving as a novel composition of matter a highly reactive, highly amorphous, anhydrous material derived from organic agricultural matter is created, this agricultural substance having a high initial silica content of up to about 28% and the new compound has from about 49% to about 98% silicon dioxide, while the rest mainly Carbon residue and non-volatile inorganic constituents of organic plant material. The carbon residue and is generally removable by prolonged heating, so that a bond is formed by about 0.3% to no more than about 2% residual carbon (as determined by loss on ignition) and from about 1% to about 5% insignificant non-volatile impurities, too

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to which OaO does not belong.

A preferred embodiment of the invention comprises the above compound wherein the silica content of the fabric is from 75% to about 98%. It should also be noted that the novel silica compound according to the invention is characterized in that it retains the basic cell structure outline of the organic matter from which it is derived and that it generally has a large surface area in excess of 10 m / g. In one embodiment of the invention, it is believed that a novel silica compound according to the invention after its initial preparation contains approximately 2% carbon (as determined by loss on ignition studies) apparently entrapped in the amorphous silica structure of the fabric, or with amorphous silica is completely coated so that removal by thermal processes without further physical treatment is difficult, if not impossible .

As noted above, the new silica compound according to the invention frequently contains minor Verunreini conditions, mainly the non-volatile inorganic residue of the organic material from which it is put forth. In principle, it has been found that in addition to very small amounts of AIgO ,, Pe ₂ O ,, MnO, and some in

all

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trace elements present in natural organic substances, the silicon-containing substance according to the invention _{can contain from about 1% to about 2% potassium oxide (K 2} O), up to about 1.5% SO, and O and OaO.

As a result of the manner in which the substances are manufactured, the compound is generally completely anhydrous and retains an outline contributes to the basic cell structure of the organic material from which it is derived. Depending on the temperatures that it is subjected, the material can have surface sizes

2 2

of over 10 m / g and often of more than 100 m / g can be generated.

Further objects of the invention are achieved by a method of incinerating organic agricultural matter having an initial silica content of up to about 28%, which method involves heating the silica-containing organic matter to temperatures no greater than about 6770 for periods of time includes up to about 66 hours. In practice, it is sometimes desirable to first heat the silicic acid-containing substances, such as rice hulls, to about 204 G, at which temperature carbon-containing gas is produced in the form of dense, smelling vapors, accompanied by an exothermic reaction that gradually increases the temperature to approx 482 ⁰ O caused. The increase in temperature after the end of the

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exothermic reaction in an oxidizing atmosphere for Periods of up to about 66 hours depending on the temperature can result in a product that is still highly is amorphous and still contains only minor amounts of carbon residue.

Further objects of the invention are achieved by a new hydraulic Cement compound dissolved according to the invention, which from 5 to 50 wt .-% calcium oxide or slaked lime and from 90 to 50% by weight of the new silicon dioxide according to the Invention having.

Another aspect of the invention is an improved hydraulic cement that can be used in anhydrous form from about 5 to about 50% by weight of a portland cement and from about 50 to approx. 95% by weight silicon dioxide in the form of the new silicon dioxide substance according to the invention.

The noted portland cement is any portland cement containing from about 60 to about 69 weight percent bound and unbound Has calcium oxide.

A preferred embodiment from this point of view of the invention comprises a hydraulic cement of from about 20 to about 30 weight percent Portland cement and from about 80 to approx. 70% of the new silicon dioxide compound described above, Excellent cements have been found to work

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result in high strength from these compounds.

The various aspects of the invention are more fully illustrated with reference to the examples given later, in which percentages are expressed as percentages by weight are expressed unless otherwise specified.

The rubber and plastics aspects of the invention can be expressed as a novel composition of matter which comprises a material from the class consisting of rubber, elastomeric and plastomeric substances used as fillers 5 to 95% by weight of a carbon and silicon containing one Contain substance made from agricultural substance with a high initial content of silica by means of a Ashing process is obtained under conditions where the silicon-containing substance forms the base line structure of the retains agricultural substance and is amorphous in nature.

Compounds according to the invention can be made from natural rubber and its derivatives and from synthetic elastomers Manufactured as synthetic rubbers (substances that can be stretched or deformed by 100% and nearly fully return to the original state when the deforming force is removed) can. Other compounds of the invention can be made from materials commonly known as plastics

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or plastomers that are not rubber or rubbery in the sense that they do not vulcanize and which are polymeric in nature.

The different classes of elastic polymeric substances that are derived from agricultural plant matter Silica that can be reinforced include natural rubber and its derivatives and the synthetic ones rubbery elastomers (as defined by H.L. Fisher in Ind. Eng. Ohem., 31, 1W). These substances were generally classified according to Pisher's classification of elastic fabrics. Fisher's study shows that elastic fabrics differ within its broad definition, and it is not possible to accurately predict what effect the amorphous silica used in this invention has on physical properties every single class will have. However, it is generally true that the silica used in the invention can be used to produce a usable product in any formula formulation of elastic fabrics, whereby carbon black or silica-containing, reinforcing or expanding substances can be used and the effect have to give the elastic connection improved tensile strength.

Thus there are the following classes of elastic fabrics that

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be enhanced by the practical application of the invention:

(I) Natural rubber and its modifications including chemical, interpolymer and mixed polymer

Modifications.

(II) Rubbery, i.e. vulcanizable synthetic elastomers comprising:

(A) Non-polar dienic elastomers:

(1) homopolymers

(2) multipolymers

(B) Polar dienic elastomers:

(1) homopolymers

(2) multipolymers

(0) Non-serviceable elastomers,

The just given classification II of elastic fabrics
is intended to _{include all of the types of materials classified as synthetic rubber by H-} L. Fisher in the aforementioned reference. Fisher, in certain cases, uses the term "rubbery" imprecisely to mean "elastic", whereas
In the present description, the term is used in the more precise sense of vulcanizable as opposed to non-vulcanizable substances.

For the sake of simplicity, the special classi

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fications of elastic materials, which by the here disclosed silicon dioxide according to the practical application of the invention are designated as follows:

Class I - rubbers (natural rubber and modifications). Class IT - elastomers (synthetic, vulcanizable).

The term "serviceable" means any elastic or understood plastic material, at least partially of butadiene or a derivative of butadiene, i.e. from a polymerizable substance, is formed, the a plurality of polymerizable Contains ethylene bonds or linkages, at least two of which are conjugated.

The term “homopolymer” means the product of polymerization of a single polymerizable monomer. For example butadiene is homopolymerized to polybutadiene.

The term “copolymer” is understood to mean the polymerization product which is obtained when two or more polymerizable monomers copolymerized, i.e. simultaneously in mutual presence, are polymerized. For example, butadiene and styrene are polymerized together, to form a butadiene-styrene copolymer.

The term "interpolymer" denotes the polymerization product which is produced when two or more

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Monomers are polymerized sequentially ("referred to as" graft polymer "in the nomenclature report in Journal of Polymer Science, VIII, page 260, March 1952) or if one or more substances in the presence of a polymer polymerized (e.g. homo-, mixed- or condensation-polymerized). For example, natural rubber is used swollen with methyl methacrylate and the latter polymerized, whereby the product is an interpolymer seed. If the components of an interpolymer are inseparable from each other, the newly created polymer is called a "graft polymer" (cf. manual of T. Alfrey, Jr., J. Bohrer, and H. Mark, entitled "Oopolymerization," published 1952 by Interscience Publishers, Inc., New York, in particular Chapter VIII).

The term "mixed polymers" means a physical Understood mixture of two or more polymers. For example, if polybutadiene and the copolymer of Butadiene-styrene either by mixing their dispersions or latices, subsequent coagulation and drying or are intimately mixed with one another by mixing the dry polymers by means of milling, are the resulting Blends mixed polymers.

The numerous examples given above and below are tabulated to enable those skilled in the art to compare these so that a better understanding of the

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Advantages and the broad application of this principle invention achieved in the several areas concerned

Class I contains the natural rubbers and their derivatives and modifications including Haevea, Balata, Chicle and other naturally occurring types of rubber, and with natural rubber derivatives, are not only made of interpolymers Natural rubber and diene ,. Vinylene and allyl monomers, but also the chemical derivatives of these and of natural rubber, like the hydrogenated, hydroxylated, chlorinated, hydrochlorinated products and the like. As well as their plasticized products meant. The techniques for making the various Natural rubber derivatives are in the work of J. Le Bras, A. Delalande and J, Duclaux entitled "Les Derives Ohimiques de Caoutchouc Naturel", published 195O in Paris (France) by Dunod, well recorded. These different Natural rubber derivatives can be replaced by the silica substance disclosed herein according to practical use of the invention are reinforced.

The general purpose synthetic rubbers produced in large quantities are those known as GR-S Butadiene-styrene copolymers, both hot and cold GR-S types as well as oil-expanded GR-S copolymers and GR-S copolymers mixed with carbon black in batches, with or without the addition of oil, are all

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Tim dioxide according to the practice of the invention effectively reinforced.

Class IIA-1 elastomers contain the homopolymers of Dienes, such as butadiene, isoprene, piperylene, 1,3-pentadiene, Dimethylbutadiene, etc., and the class IIA-2 elastomers contain the copolymers, interpolymers and mixed polymers of the non-polar dienes mentioned or without vinyl compounds and other non-polar substances containing a polymerizable ethylenic group. Other important links of the elastomers of the class IIA-2 are the polymers, which two or more substances from the group which comprises the non-polar dienes and other non-polar polymerizable materials, at least of which one must be a diene for the polymer to be vulcanized «, examples of such class IIA-2 elastomers are:

(1) Two or more dienes, e.g. butadiene-isoprene mixed polymer rubber.

(2) One or more dienes with one or more vinyls, e.g. butadiene-styrene copolymer rubber, Ethylene-propylene-diene tripolymer rubber types in which the small amount of diene is usually not conjugated, such as cyclooctadiene, M-cyclopentadiene and divinylbenzene, and others Rubbers made from alpha olefins and polyolefins that contain residual unsaturated valences.

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"- 16 -

(3) One or more dienes with one or more compounds that do not contain vinyl and have a polymerizable ethylene bond, e.g. the isoprene-isobutylene copolymer, after emulsification in water to form a latex.

(4) Any of the compounds mentioned in (3) with the addition of one or more vinyls. In the ones just mentioned Vinyls are of course included styrene, vinyl toluene, and alpha methyl styrene when they are equimolar The content of a vinyl monomer which supports the polymerization, such as styrene or vinyl toluene, is copolymerized are. In the GR-S types of butadiene-styrene copolymers in this class there is also a member which contains a small proportion of a crosslinking agent, for which divinylbenzene is generally used to reduce polymer shrinkage while maintaining its elastomeric properties. It is not intended to exclude such a material because of the presence of the anti-shrink agent in the elastomer to be reinforced the reinforcement of the material by the silica disclosed herein in accordance with the practical application of FIG Invention not affected.

The isoprene-isobutylene copolymers (butyl rubbers), which, according to the classification, are elements of the elastomer group of class IIA-2, do not belong to type GR-S,

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since they (1) are not copolymers of a diene and a vinyl, but are copolymers of a diene and isobutylene, and (2) the meniscus in very low concentrations of the order of 5% compared to the 72% butadiene content of the GR-S 100 is present.

Butadiene acrylonitrile copolymer is an example of Subclass IIB-2.In this class of elastomers, homologues of butadiene can be used in conjunction with or instead of of butadiene can be used, and in addition, other polymerizable polar organic compounds can be used in place of or in addition to the acrylonitrile. Such other polar compounds include: vinyl aldehydes and ketones, e.g. acrolein, methakrolein, vinyl methyl ketone, methyl isopropenyl ketone, vinyl acids, e.g. acrylic acid, methacrylic acid, Cinnamic acid and its prepared from saturated and unsaturated alcohols, esters, phenols, etc., polar Derivatives of non-polar vinyls, such as the halogen derivatives of styrene and of vinyl toluenes, containing nitrogen Vinyl compounds, such as methacrylonitrile, vinyl pyridrine and the vinyl-substituted pyridines, and polymerizable halogenated hydrocarbons, z, B. Trichlorethylene, 1,1-difluoroethylene.

HO class elastomers include elastic and plastic materials that contain no butadiene or no substituted butadiene, however through hardening systems, even without sulfur,

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are vulcanizable, the polyalkene sulfide, Thiokol, an example of this class is that also includes ethylene propylene rubber and other rubbers made from alpha olefins, and also the halocarbon rubbers, in particular contains the types of fluorocarbon rubbers, die.durch peroxide or amine curing systems are curable, the lactoprene polymers not serving Include components and use an ester interchange or halogen replacement reaction for vulcanization purposes, further the elastoplasts, which include mixed glyptals as defined by H. Fisher and which are vulcanizable, the polyesters including those containing residual unsaturation and with an organic peroxide curing system are curable, and the polyesters terminated by carboxyl or hydroxyl groups, e.g., by reaction with vulcanized with a polyisocyanate, which forms the so-called isocyanate polyester elastomers of the Yulcollan type.

Another aspect of the invention is a resilient material that can be combined with that disclosed herein from agricultural, Licher plant substance derived silicon dioxide is reinforced. Plastic materials are polymeric substances understood as either plastomers or non-vulcanizing hairs Elastomers can be designated.

The term plastomers "refers to the H. Fishers class of plastomers, which are classified as subclasses (a) the

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genuine thermoplastics and (b) the thermosetting plastics. The term non-vulcanizable elastomers is in H. Fisher's subclassification of elastols and elastoplasts under his general classification of Contain elastomers, vulcanizable substances are excluded, which are more suitable in the class of rubber-like (vulcanizable) elastomers are housed.

Polyvinyl chloride and polyvinylidene chloride and their copolymers with and without plasticizers, in particular a copolymer of vinyl chloride-vinylidene chloride plastomers have become very important and are being used with the silica disclosed herein according to practical use the invention reinforced. No attempt is made to explain the numerous variations of vinyl chloride and Vinylidene chloride polymers and copolymers and the many different types of plasticizers that can be used to discuss.

An excellent overview of the polyvinyl chloride-type plastomers and a discussion of their similarities can be found in the literature sections Franz Kainer, "Polyvinylchlorid- and vinyl chloride copolymers ", published in 1951 by Springer-Verlag, Heidelberg, Germany.

Specifically, include the plastics and the non-vulcanizable Elastomers the following: Polymers from

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Monomers which contain polymerizable ethylenic bonds, but no vinyl polymers, with or without other polymerizable components, e.g. sulfur dioxide or vinyl components, such as polyethylene, polypropylene, polyisobutylene, polysulfones (e.g. isobutylene sulfur dioxide copolymers), isobutylene styrene Copolymers and the like., Polymers made from vinyl monomers or monomers such as styrene, vinyl toluene and alpha methyl styrene, from halogenated vinyl compounds such as chlorostyrene, vinyl chloride, vinylidene chloride, perfluoroethylene, trifluorochloroethylene, propylene, etc., polymers made from vinyl acids and their esters, e.g. Acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate, etc., polymers produced from vinyl ethers, eg vinyl ethyl ether, polymers produced from vinyl alcohols and their esters, eg vinyl alcohol, vinyl acetate, the acrylates and fluorinated acrylic esters and vinyl butyrate, polymers produced from vinyl ketones, eg methyl vinyl ketones on, methyl isopropenyl ketone, etc. and polymers produced from nitrogen-containing vinyl monomers, for example vinyl pyridine or acrylonitrile. Copolymers, mixed polymers and interpolymers of vinyl monomers aind included in this definition in combination with any other organic compounds that can connect to it. If a diene is used in the formation of such plastomers and non-vulcanizable elastomers, the plastomer must be hydrogenated, halogenated, hydrohalo-

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denatured, hydroxylated or otherwise "treated" to remove the unsaturated bonds because otherwise the unsaturated substances could be vulcanized and should therefore be classified as elastomers.

The cellulose derivatives that meet this definition are also used by the silicon dioxide disclosed here in accordance with FIG practical application of the invention, e.g. the cellulose ether derivatives, such as methyl cellulose, ethyl cellulose, Hydroxyethyl cellulose, carboxymethyl cellulose, etc., und'die Cellulose ester derivatives such as cellulose acetate and cellulose nitrate. The fortification of these cellulose derivatives is also effective when they are plasticized.

The plastomers and non-vulcanizable elastomers and their mixtures with elastomers of class I and II are all reinforced with the silica disclosed herein in accordance with the practice of the invention «

The examples given in this specification are typical and illustrate the principles of the invention however, it is not designed in any direction to show the maximum results attainable when the disclosed herein Silica used according to the practice of the invention is elastic and plastic Reinforce materials.

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Example I.

A sample (approximately 50-100 g) of hot sleeves from the Sacramento, California area was heated in an electric oven. The sample was placed on the cooling furnace and the temperature was gradually raised to about 149 ⁰ O, at which temperature the sample began to turn dark brown. Was defined as the temperature "to more than 149 ⁰ O increases, carbon-containing gases began to emerge, and the vapors were fairly close and odor noticeable at about 204 ° 0, without increasing the supplied to the furnace electric energy, the temperature of the sample rose gradually at approximately 482 ⁰ O as monitored by an Ohromel-Alumel thermocouple, indicating that the distillation or carbonation process was exothermic. When the temperature stabilized, the material samples were removed and subjected to further treatment and examination Ash material removed at this point was black and, highly amorphous and had a very large specific surface area and a weight loss on ignition of 45 to 50% (carbonized substance).

Example II

A small portion of the material from Example I (prior to performing the Glühverlusttests) was heated to temperatures between 482 and 510 ⁰ O O ⁰ for 48 hours. At the end of this

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Period, the black ash natte gray in color, but still had a porous, Skeletal structure with a large surface area and was highly amorphous ..

Example III

Another part of the black material produced at about 482 ⁰ O in Example I was heated for about an hour to a temperature between 566 and ⁰ O 59 3 ° C under oxidizing conditions. Again, the black ash turned gray, but retained the highly amorphous character of the original large surface area black ash. Even after heating to around 677 C, the gray ash retained its non-crystalline character. However, prolonged heating to a higher temperature caused the material to convert (at least partially) first to the crystobalitic and then the tridymic forms of crystalline silica.

Microscopic examination of those generated at 677 ° 0 and below Products of Examples I - III showed complete extinction under crossed nicoles, thus making the complete Lack of crystalline material was stated. It also shows the porous, skeletal structure of silicon dioxide according to the invention and a very large surface. The silica ash was also soft to the touch and became broken down into fine particles by light grinding.

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Example IV

Parts of the amorphous silica ash according to the invention, those at 677 ° C and below as in Examples I - III were prepared, were mixed with 20 wt .-% calcium oxide (CaO) in a mortar using a rubbing club at room temperature. The reactivity of the silicon dioxide was shown in that both the chemical analysis and the X-ray diagram showed a complete reaction between the calcium oxide and the silicon dioxide, a result that occurs naturally with Silica or rice hull ash known by Incineration processes established cannot be obtained.

Examples V - XIII

Individual quantities of rice hulls, rice straws and horsetail (Equisetum) were crushed so that they passed through a 6.35 mm mesh screen and were then treated in detail in an electric oven so that they were heated ^{to about 204 0 G,} to initiate the exothermic carbonation or distillation reaction as described in Example I above.

After the exothermic reaction was substantially complete, the samples were removed for analysis and examination. The remainder was exposed to an oxidizing atmosphere for half an hour at 53 ° G, at which time a second

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Sample was removed and warmed the rest of the material in the oxidizing atmosphere for a further 1 1/2 hours between 566 ⁰ C and 593 ° 0th

In the following table (Table I), Examples V-VIII represent in a corresponding manner the test results obtained from the incineration of rice hulls at the end of the exothermic reaction (Example “V), after half an hour at 538 ⁰ O (Example VI) and after are obtained further 1 1/2 hours at 566 to 593 ° ⁰ O O (example VII) Similarly, the examples provide VIII -. X represents the three samples are prepared by the same method of milled rice straw In Examples XI. - XIII, on the other hand, horsetail were used.

Each sample was divided into small pieces to determine (1) the total available silica, (2) the loss on ignition, (3) the surface area, (4) the silicon dioxide activity index and (5) of the X-ray diffraction diagram.

The total available silica was determined by determining the loss on ignition first, then the carbon-free sample has been bleached with perchloric acid to dissolve all remaining ingredients except silica, and that then ultimately determines the silica became.

The loss on ignition was determined by placing a weighed portion of the material in a platinum crucible at 1000 ⁰ in

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long an oxidizing atmosphere heated one hour _s then cooled and weighed again and then was I5 minutes was heated and so on, until a constant weight was obtained on cooling.

The surface area was determined by the standardized B.E.R.-nitrogen f absorption method determined.

The "silicon dioxide reactivity index" is an indication of the Reactivity of the silicon dioxide present in a material and is directly related to the amorphousness> 8 degrees of the Silicon dioxide. This figure has been developed to reflect the high degree of reactivity of the silicon dioxide according to the invention to show. The figure is obtained by experimentally determining the percentage of available silicon dioxide, which is in an excess of boiling 1/2 N. NaOH in a three-minute extraction in a stainless steel beaker dissolves in a sample of -325 meshes. If silicon dioxide is really amorphous »the characteristic ones are missing X-ray diffraction peaks of its crystalline forms. The degree of amorphousness, however, can be determined by the intensity or average height of the diffused band between 15 and 26 ° if x-rays are used, that of a copper electrode, with an ETickelfilter be generated. Those reported in Table I in conjunction with the relative X-ray diffraction intensity of the amorphous ribbon Data relies on a full 10 inch dial reading representing 200 counts per second.

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in total
velvet
available
cash
SiO ₂ (%) Table I. Upper
flat
small
- size Silicon-
dioxLdak-
activity
identification number 2338066 50
92 Annealing
desire
(%) 122
97 85
81 material 93 49.4
6.3 75 79 relative int
sity of cupid
phen tape through
Höntgenstrahl-
diffraction (count
gen / second Rice husk
senasche
example
V.
example
VI 4.5 74
54 example
VII 54 49 50 54 rice
straw
ash 44.0 example
VIII 85 22nd 61 46 example 90 12.0 11 43 IX 5.2 40 example
X 50 86 61 40 chess
telhalm
ash 75 43.3 81 63 example
XI 77 12.8 74 58 48 example
XII 9.8 32 example
XIII 30th

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The data in Table I indicate that all substances are highly reactive forms of silica in the non-crystalline or are amorphous. In contrast to the material that is made from rice hulls or rice straw, it contains from Horsetail produced silica ash a CaCO -, - residue. As the chemical analysis in Table II shows, this explains at least part of the greater loss on ignition for the ashes made from horsetail in Table I.

The analyzes shown in Table II are representative of the materials produced from rice straw and those Examples XI-XIII for the substances made from horsetail.

Table II.

material

Ash content of the unburned plant matter

Analysis of the ashes in % of the ashes

SiO ₂ CaO

residue not analyzed

O ₃ +

₂₅ Mn ₂ O ₃ )

Rice husk ash

Rice straw bag

Horsetail mesh

21.1

18.5 26.6

98.30 1.27 0.15

96.50 2.36 0.17

91.10 6.-41 1.7s 0.12

0.38

0.37 O.47

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Example XIV

A large amount of the amorphous silica compound after the invention was made from rice hulls from the Sacramento area, California in an inverted refractory oven, which has tangential feed devices on the ground for an air-transported rice hull flow, devices for initiating the above-mentioned exothermic reaction and devices for rapidly heating the ash and for Remove the ashes from the lower central part of the cylindrical Furnace. The material produced for this example was amorphous and exhibited from 12% -14% loss on ignition of organic Residue (essentially unburned carbon), had a specified surface area of 25 »5 m / gi a" silicon dioxide reactivity index " of 53 and black color.

Example XV

The procedure of Example XIV was repeated using a large quantity of rice hulls from Arkansas rather than Sacramento, California. The product contained 8.4% carbon, was gray-black, and the chemical composition of the loss-on-ignition-free product was similar to the ash made from the Sacramento material and was used to make a modified portland cement as noted below Establish strength parameters.

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Examples XVI - XIX

Parts of the amorphous silica ash from Examples XIV and XV "were individually for two hours in a ball mill with calcium oxide and various brands of portland cements of Type III milled according to ASTM, in each case a black or gray powder resulted which when mixed with water showed excellent hydraulic properties. To illustrate these properties, rice hull ash cement was used manufactured and according to the standardized mortar cube test method ASTM C IO9-7OT hardened. Then compressive strengths were determined, The standardized quantities of Ottawa sand proposed in the method C1O9-7OT "were used in all investigations are.

For the 50.8 mm grout squares there is that shown in Table III Compressive strength indicates that cements with extremely high strength values are produced.

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- 31 Table III

example

Cement composition
before the
additive
of sand

Water-cement ratio Compressive strength after the specified number of paint days of aging (psi)

28

XVI

XVII

XVIII

XIX

80% hot-sleeve ash from Example XIV + 20% Calcium oxide 0.57

70% Rice Husk Ash of Example XIV + 30% Portiand brand cement

Galaverous Type III 0.57

75% hot-sleeve ash of the example

XIV + 25% brand portland cement
Santa Cruz

Type III 0.53

70% rice hull ash of the sample

XV + "30%
Brand portland cement
Santa Cruz

Type III 0.54 1500

3500

513Ο

black

2390

3S8O

5140

black

2480

4180

5570

black

2580

6500

grey black

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comparison

Minimum ASTM requirements for general purpose portland cement (for reference purposes)

0.50

1200

2100

3500

Gray

example

A portion of the rice hull ash from Example XIV became a Temperature of 593 ° G for 66 hours under oxidizing conditions subjected in an electric furnace. The resulting material showed only 0.3O% weight loss by annealing and had a surface area of 6.5 m / g · The silica activity index was still 50%. This proportionately pure form of amorphous silica was further characterized by an index of refraction of 1.43 'and a density of about 2.0. This Re & shülsenki'eselsäureasche was in their physical properties compared to other forms of silica and the results are given in Table IV.

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Table IV

Density (g / cm3)

Breach number

Silicon dioxide reactivity index (%)

quartz 2.65 Gristobalite 2.32 Obsidian 2.25 Rice husks
ash
(0.3% Koh
fuel)
Example XX 2.0 Rice husks
ash
Example XIV

1.55 1.48

1.47

1.43

0.05 4 4

50

53

Example XXI

A small amount of non-white, low loss on ignition, amorphous silica ash prepared as in Example XX was ground in a laboratory mortar and mortar along with 25% calcium oxide. The resulting cement was white in color and showed hardening characteristics when mixed with water.

Hydraulic cements that show hardening characteristics can also be reused by using the new silicon-containing ashes of the invention using 5-50% by weight of lime and of

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90 - 50% by weight silicon dioxide as a new type of silicon-containing Ash maker of the invention (which, as mentioned, more than 4-9% to contain about 98% silicon oxide). The exact Amount of lime and siliceous ash that is used depends on the desired character of the cement and the amount of silica in the silica-containing ash. So can for ashes with a relatively large residual content Have carbon, cements are made with relatively low percentages of lime, and the amount of lime can be increased as the percentage of silica in the silica-containing ash increases.

In the same way, when using the silicon-containing Ash according to the invention can be produced with Portland cement cements which differ slightly from those in Table III The specified ratios differ and nevertheless have excellent compressive strengths.

Although the above examples show that the silicon-containing ash of the invention can be mixed with portland cement or calcium oxide is ground in order to produce the new hydraulic cements according to the invention, it should be noted that the grinding is not an absolute requirement for the manufacture of the cement. There is a difference in density between the portland cement or lime and the siliceous ash of the invention is present, it is difficult to mix evenly to achieve without the smallest effort, so that the smallest

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Milling effort to achieve the mixture is preferred. In addition, it should be noted that the new silicon-containing Ash according to the invention, if it is not intimately mixed with the lime or portland cement, tends to be proportionate to absorb large amounts of water. This water absorption is achieved through thorough intimate mixing of the cement components minimized before adding water, so milling is preferred for this reason. A The main purpose for minimal milling effort is to break the skeleton of the silicon-containing ash into relatively fine particles break up. Therefore, the new silicon-containing ash according to the invention can be ground separately and then with lime or portland cement be intimately mixed. In general, the meals of the lime or portland cement mixture can range from approx. 15 minutes to about 2 hours vary, with mortar using excellent compressive strength can be produced from the resulting cement.

As mentioned above, the new silicon-containing ashes of the invention are anhydrous when made are. This is due to certain, above-mentioned determinations of the loss on ignition under conditions of thermal-gravimetric Analysis has been demonstrated, that is, the studies on loss on ignition have been carried out while the Sample was weighed continuously. It was noted that any weight loss at temperatures, removal of the Carbon residue and not removal of any

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water-containing matter that remained after the initial production of the ash.

Example XXII

To illustrate the high acid resistance of the silicon-containing Ashes according to the invention produced cement and mortar were mortar cubes from Examples XVT, XVII and XVIII after seven days of curing in a 1% hydrochloric acid solution immersed. In addition, a typical ASTM Type I Portland cement mortar cube also became the same as a control Subject to test. After 30 days, the cubes from Examples XVT, XVII and XVIII showed no surface softening or etching, while the Type I mortar showed evidence of acid damage from softening and etching.

It vrlrä. notes that the compounds of the invention are applicable to the manufacture of both mortar and concrete. Generally speaking, mortar contains about two to six times as much sand by weight as the (anhydrous) hydraulic cement used, and when making mortar, sufficient water is added to the sand-cement mixture to make it workable and flowable. As a broad generalization, approximately half the amount by weight of the water, based on the amount of cement used, is added to the mixture, but about 0.5-0.6 times the amount of water, based on the cement weight, can be used.

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As is well known in the art, concrete is made from a hydraulic cement using sand and granite as filler material. Two to three times as much Sand weight and three to four times the weight of granite, based on the cement, can be used in the manufacture of concrete, using water to achieve the desired Consistency is used.

Example ΧΣΓΙΙ

A cement was made using the new silicon-containing ash produced according to Example XIV according to the invention Grind a measured portion of the ash with 25% by weight calcium hydroxide (slaked lime - CA (OH) p) over approximately two hours. Mortar cubes were made according to the ASTM method C1O9-7OT generated as described above. The standardized The amount of Ottawa sand required for the process and a water to cement ratio of 0.5 were used. the The resulting mortar cubes had the following compressive strengths after curing according to the ASTM method: After 3 days 1100 psi, after 7 days 2840 psi and after 28 days 4160 psi.

When using the new silicon-containing ashes according to the invention with calcium oxide or slaked lime to form hydraulic cement or mortar is preferred, between 20 and 40% by weight lime in the mixture of lime and silicic acid Use ashes as excellent results will be obtained in this area.

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Example XXIV

It will again be the silicon-containing ash from the XTV example was used, and a hydraulic cement was made by grinding the ash in a ball mill for 15 minutes and then the ground ash was mixed with 20 wt% calcium oxide for 15 minutes to make it homogeneous To achieve mixture. According to the ASTM C1O9-7OT procedure mortar cubes were made and cured. When making the mortar cubes, the water-cement ratio was 0.65. The seven-day compressive strength tests showed that the cubes had a compressive strength of 860 psi while the twenty-eight day compressive strength test of 1550 revealed

Example XXV

The procedure of Example XXIV was repeated using calcium oxide instead of 20% by weight calcium oxide. During the preparation of the mortar, the water-cement ratio was 0.70 and compressive strengths of 1210 psi and Reached 2170 psi for 7 and 28 days, respectively.

Except for the production of hydraulic cements, the new silicon-containing ashes according to the invention can be used as a basis used for catalysts and other active chemical substances there where a silicon-containing material with a relatively moderately large surface area is useful. Also find the

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siliceous ashes according to the invention useful as fillers for plastic materials and such materials as natural rubber and synthetic rubber, as well other uses that depend on a silica high reactivity and a relatively large surface area.

Examples XXVI and XXVII

To illustrate the usefulness and benefits of using the carbonaceous silica containing Material as a filler in a black-colored elastomer are batches of SB-R 1502 (a styrene-butadiene copolymer, which contains 23% bound styrene) for vulcanization manufactured in individual batches, one of which is a carbonaceous silica disclosed above and the other contained soot.

The .Batches were on a roller mill with full cooling Water mixed on the rollers. The batches were allowed to stand for 16 hours before mixing and were then pressed before the tray Test foils or plates ground again. The pressed test films were left idle for 24 hours before physical Investigations were fed. The pressing was carried out in a 50-ton press that was electrically heated Had press plates. The samples-x became 30 minutes long cured at 149 ° C. Pressure test disks were made and

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Cured for 35 minutes at 14-9 ° C.

The two formulations to be compared had the following Compositions:

Example XXVI Example XXVII SBR 1502 100 100 Aminox 2 2 zinc oxide 5 5 Stearic acid 5 Benzothiazyl disulfide 1.5 1.5 Tetramethylthiuram disulfide 0.25 0.25 sulfur 2 2 Light process oil 5 5 soot 75

Carboniferous

Silica 75

The carbonaceous material containing silicon dioxide in this example corresponded to the originally produced above in Examples XIV and XV described substance and was at a furnace • feemperatur of 732 ⁰ C. The material removed from the furnace was ground in a ball mill and then air-sifted. The material used in preparing the rubber composition of Example XXVII consisted of the finest fraction recovered from air sifting.

The carbonaceous silica-containing material had a carbon content of about 8% prior to grinding and classification.

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The proportion used after sifting had a specific one

ο Weight of 2.09 and a surface size 'of 29000 cm / g (determined by the Blaine method described below) and a calculated mean particle diameter of approximately one micron.

Aminox is a reaction product of acetone and diphenylamine that occurs at low temperatures and is manufactured by Uniroyal Chemical Company and is an antioxidant

The light process oil used was an aromatic petroleum oil, which was designated as Bearflex LPO and by the Golden Bear Oil Co. is manufactured.

The carbon black used in Example XXVI was Thermax. This is a Trade name for a medium thermal black produced by R.T. "Vanderbilt Company.

During batch mixing, it was noted that the carbonaceous silica of Example XXVII incorporated more easily into the dry polymer than the carbon black in Example XXVI, resulting in a shorter mixing time for the Example XXVII compound gave.

Separate small samples of the uncured (uncured) The fabric of Examples XXVI and XXVII were subjected to a cure determination subjected by use of a Monsanto rheometer model TM 100, with an oscillation arc of 1.5 ° "at

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the curing temperature of 149 ° C was used. The torque was measured continuously and recorded for 27 minutes. The data recorded indicated that cure in the fabric of Example XXVI was initiated in about 5 minutes while cure in the fabric of Example XXVTI was initiated in about 2 minutes. However, the fabric of Example XXVII achieved 90% cure in only 5 1/2 minutes while the fabric of Example XXVI took 25 minutes to achieve 90% cure. Thus, with the connection according to the invention, not only did hardening begin more quickly, but it also showed a very large reduction in the total hardening time required.

Unvulcanized elastomeric fabrics exhibit what is termed "nervous" Property when they are cut from the mold after being rolled into foils or sheets before hardening or pressed through a mold. "Nerves" refers to a change in size in the material after it is of the Influence of a deformation force is exempt. It was observed qualitatively that a marked reduction in the "nervous" Effect occurred, which was shown in the material of Example XXVII compared with the material of Example XXVI.

This was followed by curing, hardness, tensile strength, percentage elongation, modulus at 100% and at 300%, elongation, tensile strength and specific gravity of the substances produced in Examples XXVI and XXVII are determined.

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In addition, tensile strength, elongation, hardness and modulus were determined after 70 hours of heat aging in a circulating air oven

70 C determines "Then there was the set Compressibility after 22 hours of aging at 70 ⁰ G certain

The following results were obtained:

Original properties

Shore hardness A, (tips) (ASTM D-2240-64T) Tensile strength (psi) (ASTM D-412-66) Elongation (%) (ASTM D412-66) Modulus ^ 00% (psi) (ASTH D412-66) Modulus 100% (psi) (ASTM D412-66) Tensile Strength (pli) (ASTM D624, the G) Specific resistance (Waoser displacement)

Properties after heat aging

Singular compression

(/ ö of the original deflection)

(ASTM D-395-67) Shore A Hardness (Peak) Tensile Strength (psi) Elongation (%) module 100% (psi) riodul 3ΟΟ5έ (psi)

Example XXVl Example X 63 61 1050 575 430 450 • 800 435 300 225 145 95 121 126

7.5

64

1025

315

325

1000

10.8

63 575 440 250 45Ο

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The above data show that the compound of the invention (material of Example XXVII) had superior heat aging characteristics compared to the material of Example XXVI.

Example XXVIII

In general, the procedures used in Examples XXVI and XXVII were repeated and a procedure according to the Process used in Examples XIV and XV made of carbon and silicon containing 13 * 0% carbon contained. This substance had a specific weight

ο of 1.93 * a surface size of 24000 cm / g, determined by the Blaine method, and a mean particle diameter of 1.3 microns. The oven temperature during its manufacture was approximately 718 C. The material was after grinding to the above-mentioned surface size in ground in a ball mill.

The uncured rubber compound used in this example was based on the compound of the example XXVII with the exception of the special carbon and silicon-containing material used, the following data was obtained obtain:

309886/1120

Original properties

Shore hardness A (tips) '54-

Tensile Strength (psi) 900

Elongation (%) 710

Module 100% (psi) I50

Module 300% (psi) 350

Tensile strength (pli) 120

Properties after heat aging

Shore hardness A (tips) 59

Tensile Strength (psi) IO5O

Elongation (%) 650

Module 100% 225

Module 300% 500

Example ΣΧΙΣ

The procedure of Examples XXVI and XXVII was repeated with the exception that the carbon- and silicon-containing material used was prepared according to the method in Examples XIV and XV using a Ofentetnperatur of approximately 71S ⁰ C. The material flowing out of the furnace was ground in a ball mill to produce an upper

area size of 20,000 cm / g and an average particle diameter 1.5 microns. This material was used without air sifting and had a specific weight of 1.96 and a carbon content of 11.0%.

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The percentages of carbon, silicon and other constituents of the elastomeric batch

were identical to the percentages reported in Example XXVTI above. The following results of the physical Properties were obtained:

Original properties

Shore hardness A (tips) 55

Tensile Strength (psi) 875

Elongation (%) 710

Module 100% (psi) 160

Module 300% (psi) 250

Tensile strength (pli) 100

Properties after heat aging

Adjusted compression

(% of the original deflection) 27.4

Shore hardness A (tips) 58

Tensile Strength (psi) 375

Elongation (#) 620

Module 10050 (psi) 200 Module 300 ^: / o (psi)

As with the material in Examples XXVII and XXVIII, it was seen that the carbon and silicon containing Incorporated substance into the compound much more easily than carbon black

the
and that / resulting uncured material, a pronounced

303886/1120

Showed improvement in the extent of "nervous effect". Examples XXX and XXXI

Using the silicon-containing ones used in Example XXVII Ashes, another series of tests was carried out using an ethylene propylene diene terpolymer. Instead of however, using the finest carbon and silicon-containing material resulting from air sifting was recommended took a coarser fraction of this material «This material had a specific gravity of 2.09, an upper

surface area of 17,000 cm / g as determined by the Blaine method and an average particle diameter of approximately 1.7 microns.

The procedure followed was the same as in Examples XXVI and XXVII in that comparable batches of the Elastomers with and without the carbon and silicon-containing substance according to the invention were produced. The two too comparative approaches had the following compositions:

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Example XXX Example XXXI polymer 100.00 100.00 zinc oxide 5.00 5.00 Stearic acid 1.50 1.50 FEF soot 50.00 50.00 MT soot 150.00 Carboniferous.
Silica 150.00 Light process oil 40.00 40.00 Dipentamethylene tetrasulfide , 75 , 75 sulfur 2.00 2.00 Mercaptobenzothiazole 1.50 1.50 Benzothiazyl disulfide , 75 , 75

The particular ethylene propylene diene terpolymer used was the Nordel 1470 manufactured by DuPont. JFEF carbon black refers on high-speed extrusion furnace black, which is usually added to some elastomer compounds to improve tensile strength. MT black refers to a medium thermal black that is usually made from natural gas, has neutral pH and a relatively large particle size compared to furnace and carbon black.

The curing of the test films and print test disks was as disclosed above in Examples XXVI and XXVII. The following physical properties were observed.

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Original properties

Shore hardness A (peak) Tensile strength (psi)

Strain (%)

Load at 100% elongation (%) Load at 300% elongation (%).

Tensile strength (form 0) (pli)

Properties after heat aging

Set compression (%) of the original deflection) Shore hardness A (peak) Tensile strength (psi)
Strain (%)
100% elongation (psi)
300% elongation (psi)

2338066 Example'XXX Example XXXI 70 75 1300 1050 195 415 850 450 800 160 140

18.5 24.7 84 78 1300 1225 170 400 1125 575 ____ 975

Both the easier incorporation of the filler of the example XXXI as well as the degree of "nervous effect" of the resulting product showed a marked improvement over this the results obtained in Example XXX.

Example XXXII

To further illustrate the properties of the anhydrous, amorphous silica, which is in the compounds the invention was used, small amounts of rice hulls

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Ashes prepared as indicated above and used, for example, in the rubber compounds of Examples XXVII-XXIX and XXXI, were taken to make measurements of the water ionic composition (pH) of that part of the material which is soluble under certain circumstances. A method according to one part by weight of rice hull ash with 5 parts by weight of distilled and deionized water was mixed and approximately -five minutes at temperatures well below the boiling point of water (71 ⁰ C - 82 ⁰ C.). PH measurements were then made with a Beckman pH meter, and in all cases it was found that the solution had a pH of from about 10.5 to about 11.2.

Similar pH measurements were made on a precipitated, water-containing, amorphous silicon dioxide, known as Hi-SiI and manufactured by the Pittsburgh Plate Glass Company (Designation No. ' 215) »made. After heating with the water, the resulting solution had a pH of 6.9.

It is assumed that the facts that the alkali material, as described in the examples I to XV produced amorphous silica ash is responsible for the inclusion of this material in vulcanizable rubber compounds the same or shorter curing times are obtained than achievable with carbon black are. This is in direct contradiction to the teachings of the prior art. For example, in the one to O.E.Bertorelli

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issued U.S. Patent 3,110,606 stated that silica-containing materials when added to uncured rubber act as strong retarders of vulcanization.

In the above Examples XXVII-XXIX and XXXI, which include the generally according to Examples XIV and XV to illustrate the silica produced was the determination of the surface area and the particle size in accordance with ASTM Procedure 0-204 (which relates generally to determining the surface area of cementitious materials related to the Blaine Method) and parts of ASTM Method 0-402 which relate to the calculation the particle size from the data obtained in the Blaine method. In Examples I-XV the determinations were the particle size carried out according to the B.E.T. method. These Both methods are incompatible with very porous materials or materials with a very large surface area involved. The B.E.T. method of determining surface area has been found to be one by one to indicates two orders of magnitude larger surface area of the silicon dioxide. This seems to be related to the fact to have that the silicon dioxide produced according to Examples I to XV has a high degree of porosity in each individual Particle has. However, the particle size calculation given in Examples XXVII through XXXI was found to be Ue based data used when measuring surface area using

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2338069

the Blaine method.

It is preferred that the carbon and silicon containing material have a particle size of approximately less than 2 microns (determined from surface area measurements by the Blaine method) before being incorporated into the Rubber-plastomer and elastomer compounds according to the invention is milled.

In Examples I - XV and in particular in Examples I - XII it was indicated that prolonged exposure to the At temperatures above 677 ° C, silicon dioxide causes a significant loss of the amorphous properties of the substance caused. However, in Examples XIV and XV it has also been found that those for making the silica Device used in these examples slightly higher temperatures of the gas mass without any noticeable change in the can tolerate the amorphous nature of the substance. It is theoretically believed that in an oven in which the silica Agricultural matter containing it is exposed to high temperatures while it is in a highly turbulent State, and in which the dwelling time is short Particles of agricultural matter while the silica is subjected to incineration to ash, not exposed to the elevated temperatures for a sufficient period of time to cause the conversion of amorphous to occur to cause crystalline matter. Thus it is assumed

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that the conversion from amorphous to crystalline form is both a time and a temperature related phenomenon and also depends on the nature of the impurities present.

The silicon dioxide disclosed here can be used in rubber, Elastomers and plastomers in a wide range of percentages based on the total weight of the compound be used. In this way, from 5 ois to about 95% by weight of the silica disclosed herein is used as a filler or extender in the compounds of the invention will. In certain elastomeric and plastomeric compounds it can be used as the primary component with the elastomeric or plastomeric Material can be used simply acting as a binder. In other applications, the one disclosed here Silicon dioxide (as with other fillers and sprinklers, which belong to the state of the art) can be used to determine the physical properties of the elastomeric or plastomeric Change connection. In certain applications, from about 35 to about 95% by weight of the silicon dioxide disclosed here can be used be used.

In general, rubber and elastomer compounds contain a number of other components in addition to the latex or Polymer feedstock. These other components contain the necessary vulcanizing or crosslinking agents, vulcanizing activators, Vulcanization accelerators, antioxidants, antiozonants, fillers (both reinforcing

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as well as stretching agents), processing aids and plasticizers. There are many different types of all of these Fabrics that are all Jm. are well known in the art and the practice of the invention is intended to be used of the appropriate material of each included class depending on the nature of the plastomer (rubber) processing agent and the use that the product is to serve,

With reference to the data in Examples XXVI - XXXI can the advantages of the invention and the new compositions of matter resulting therefrom are summarized as follows will:

The rubber and plastomer compounds according to the invention have elongation properties which are comparable to and better than a compound containing only medium thermal carbon black as a filler, and has improved heat aging properties Strength values which are generally comparable with an equivalent compound containing carbon black.

In addition, the compounds according to the invention show a marked reduction in the "nervous effect" or the Shrinkage and are easier to manufacture because the carbon-containing silicon dioxide is more easily incorporated into the polymer

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incorporated and used to set the amount of the curing accelerator to reduce that is necessary to achieve an acceptable cure rate.

Because the amorphous silicon dioxide made from such organic materials as rice hulls is not completely free is of residual carbon, the material is black and thus has the advantage that it is in contrast to known Silica additions to rubber compounds in the manufacture of off-white rubber material without the need can be used to wash the paint with soot.

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Claims (1)

R 1365 - IS. Oct 1973 Claim 1. A method for the production of amorphous carbonaceous silicon dioxide containing rubber, elastomer and Plaetomeretoffen, characterized in that an organic plant _{substance which contains up to about 28 $ SiO 2 is} heated to a temperature which is sufficient to produce organic matter therefrom remove without converting a substantial amount of said SiOp into crystalline form. 2. The method according to claim 1, characterized in that said heating is achieved by keeping said organic agricultural substance for up to 66 hours Is subjected to temperatures not exceeding 677 ° C. 3. The method of claim 1, characterized in that said heating involves heating said substance to about 204 ⁰ O, thereby initiating an exothermic reaction and allowing this substance to reach a temperature of approximately 482 ° 0, and thereafter that Increasing the temperature of this substance under oxidizing conditions for periods of time up to about 66 hours at temperatures not exceeding 677 ° C. 4. The method according to claim 3, characterized in that the said substance is subjected to the said elevated temperature for up to 1 1/2 hours, which does not exceed 677 ° C lies. retroactively 309886 / 112Π 5. The method according to claim 4, characterized in that said temperature, which does not exceed ^{677 0 G, is between 566 0} C and 593 ° O. 6. Anhydrous substance, which is produced according to the method according to claim 1, characterized in that the substance has from about 49% to about 98% SiO ₂ and that the remaining portion has insignificant impurities and residual carbon, this carbon is removable upon prolonged heating to give a compound containing from about 0.3% to about 2% residual carbon and from 1.0% to about 5% insignificant impurities not including OaO. 7. Fabric according to claim 6, characterized in that the insignificant impurities up to approx. 2% KpO, up to around 1% NapO and up to approx. 1.5% SO, encompassed. 8. Fabric according to claim 6, characterized in that the content of said SiO ,, is from about 75% to about 98%, 9. Fabric according to claim 6, characterized in that it the basic cell structure outline of the organic substance from the it is derived, maintains. 10. Fabric according to claim 6, characterized in that it has a surface area that is greater than about 6 m / g « 309886/1120 11. The fabric of claim 6, characterized by a "silicon dioxide activity index" of at least about 40. 12. Fabric according to claim 6, characterized in that it contains up to about 6.5% OaO. 13. A fabric according to claim 6, characterized in that the content of said OaO is from 5% to 50% and the content of said SiO _{2 is} from 90% to 50%. 14. Fabric according to claim 6, characterized in that it has from 10% to 50% Portland cement, which has from about 60% to 69% of bound and unbound CaO, and that the content of SiO ₂ in said substance of about 52 up to 9o wt. of the SiQ ~. 15 · Substance compound, characterized by a polymeric substance from the class comprising rubber, elastomers and plastomers, containing from 5 to 95% by weight of a highly reactive, highly amorphous, anhydrous, silicon-containing substance, which is derived from organic, agricultural matter with a high Has initial content of silica or silicon dioxide of up to about 28%, and characterized in that the silicon-containing substance has from about 49% to about 98% silicon dioxide, ^ obei the remainder of the silicon-containing substance mainly Hesidual carbon and non-volatile inorganic components of the aforementioned or - 309886/1120 . 23380G6 agricultural agricultural substance, and that the aforesaid ingredient has at least about 0.3% residual carbon and from about 1% to about 5% minor non-volatile impurities, which do not include calcium oxide. 16. A compound according to claim 15 »characterized». that said polymeric material is rubber. 17. A compound according to claim 15 »characterized in that that the silicon-containing substance has a surface area that is greater than 10 m / g. 18. A compound according to claim 15 »characterized in that that the polymeric substance is an elastomer. 19 · Connection according to claim I5, characterized in that that the polymeric material is an elastomer. 20ο connection according to claim 18, characterized in that that the silicon-containing substance with 35 to about 95 wt .-% of the Connection is present. 309886/1120 -60 blank page