MXPA97004382A - Composition in gel containing a carbon compound - Google Patents

Abstract

The present invention relates to a gel composition comprising a metal oxide gel and a carbonaceous component selected from the group consisting of: carbon black, carbon fiber, activated carbon, graphitic carbon and mixtures thereof, wherein the Carbonaceous group has been linked to at least one organic group comprising: a) at least one aromatic group or at least one C1 to C12 alkyl group, and b) at least one ionic group, at least one ionizable group, or a mixture of an ionic group and an ionizable group, wherein at least one of said aromatic or alkyl groups of the organic group is directly attached to the carbonaceous component

Description

COMPOSITION IN GEL CONTAINING A CARBONACEOUS COMPOUND Field of the Invention The present invention relates to new gel compositions. Background The gels and processes for producing them are well known. As used herein the term "gel" embraces aerogels, xerogels, hydrogels and other gels known in the art. The term "airgel" was created by S.S. Kistler in U.S. Patent No. 2,188,007 and is generally used to refer to a gel that has been dried under supercritical temperature / pressure conditions. Gels, in particular aerogels, are used in a wide variety of applications, including thermal and acoustic insulation, catalyst carriers and carriers, molecular and electronic filters and screens. Gels having lower bulk densities are more advantageous for use in many applications. Due to their lower volume densities, aerogels have become the gel of choice for many applications. However, as stated above, aerogels are typically produced using supercritical drying, which requires the use of relatively expensive equipment and processing conditions. It is also advantageous for certain applications, such as adsorbents that use gels having higher volume densities. Summary of the Invention The present invention provides a new gel composition that has improved performance properties compared to gels known to date. The gel composition of the present invention comprises: a carbonaceous component attached to a gel component. The carbonaceous component can be selected from the group consisting of: natural gas carbon black, carbon fibers, activated carbons and graphitic carbons which can be attached to a gel component. If necessary, the carbonaceous component can be modified so that the carbonaceous component binds to the gel component of the gel composition of the present invention. Preferably, the carbonaceous component is chemically modified. The present invention also includes a novel gel composition comprising: a gel component and a natural gas carbon black product having at least one organic group, the organic group comprising: a) at least one aromatic group, and ) at least one ionic group, at least one ionizable group or a mixture of an ionic group and an ionizable group, wherein at least one aromatic group of the organic group is directly attached to the natural gas carbon black. The details regarding the process for preparing the natural gas carbon black product, and the preferred embodiments of the new gel composition, are set forth in the following Detailed Description of the Invention Section. The present invention further includes a novel gel composition comprising: a gel component and a natural gas carbon black product which • has at least one organic group, the organic group comprising: a) at least one alkyl group Ca-C? 2, and b) at least one ionic group, at least one ionizable group or a mixture of an ionic group and a group ionizable, wherein at least one alkyl group of the organic group is directly attached to the natural gas carbon black. The details regarding the process for preparing the natural gas carbon black product, and the preferred embodiments of the new gel composition, are set forth in the following Detailed Description of the Invention Section. Gel components suitable for use in the gel compositions of the present invention include metal oxide gels such as silica gels, titanium gels, aluminum gels and the like; and polymeric gels, such as resorcinol-formaldehyde gels (R-F), melamine formaldehyde gels (M-F), phenol-furfural gels (P-F) and the like. The preferred gel component is a metal oxide gel. The amount of carbonaceous component included in the gel compositions will depend on the proposed end use of the gel composition. UsuallyGW. , amounts of 1-99% by weight of the carbonaceous component can be used in the gel composition of the present invention. When it is desirable to produce a gel composition having a lower bulk density, amounts of 1-50% by weight, preferably 10-20% by weight, of the carbonaceous component in the gel composition of the present invention are used. Alternatively, when it is desirable to produce a gel composition having a higher bulk density, amounts of 50-99% by weight, preferably 75-85% by weight, of the carbonaceous component in the gel composition of the present invention. As used herein, "bulk density" refers to the mass of a gel particle divided by the total volume of the particle. The gel compositions of the present invention can be used advantageously in applications known to those of ordinary skill in the art for gel compositions. In particular, the gel compositions of the present invention can be used in applications that include the following: Insulation, including thermal, electrical and acoustic insulation. Particulate additives, including opacifying products, thickeners, fillers and reinforcing agents. Adsorbents Catalyst Supports Membranes Filters Radiation Detectors Coatings, including heat resistant coatings Dielectrics, including low K dielectrics. Additional details regarding the gel compositions of the present invention, their preparation and their uses are set forth in the following Detailed Description of the Invention Section. The advantages of the gel compositions of the present invention will become more apparent to those of ordinary skill in the art from the following more detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a photograph by electron microscope for detailed examination (SEM) of a fracture surface of the gel composition, dried from heptane, produced in Example 5. Figure 2 is a photograph by SEM of a fracture surface of the gel composition, dried from heptane, produced in Example 8. Figure 3 is a photograph by SEM of a fracture surface of the gel composition, dried from heptane, produced in Example 14. Figure 4 is a photograph by SEM of a fracture surface of the gel composition, dried from heptane, produced in Example 18. Figure 5 is a photograph by SEM of a fracture surface of the gel composition, dried from heptane, produced in Example 19. Figure 6 is a photograph by SEM of a fracture surface of the gel composition, dried from heptane, produced in Example 20. Figure 7 is a photograph by SEM of a fracture surface of the gel composition, dried from heptane, produced in Example 21. Figure 8 is a photograph by SEM of a fracture surface of the gel composition, dried from heptane, produced in Example 22. Detailed Description of the Invention As set forth above, the gel composition of the present invention comprises: a carbonaceous component attached to a gel component. The accompanying figures of photographs by electron microscope for detailed examination are provided to illustrate particular carbonaceous components attached to a gel component. Figure 1 is an SEM of a fracture surface of a gel composition that does not include a carbonaceous component. Figure 2 is an SEM of a fracture surface of a gel composition that includes a carbonaceous component that does not bind to the gel component. In contrast, Figure 3 is an SEM of a fracture surface of a gel composition that includes a carbonaceous component that binds to the gel component. A more detailed explanation of Figures 1-3 and an explanation of the remaining Figures 4-8 is set out below in the Examples section. In addition, the wear characteristics of the gel compositions of the present invention, wherein the carbonaceous component is attached to the gel component, are inferior to those of comparable gel compositions wherein the carbonaceous component does not bind to the gel component. . Additional details regarding wear are set forth in the following Examples section. The carbonaceous component of the gel composition of the present invention may be selected from the group consisting of: natural gas carbon blacks bondable to a gel component, carbon fibers bondable to a gel component, activated carbons bondable to a component in gel and graphitic carbons that can be attached to a gel component. Certain carbonaceous components will not bind to a gel component unless they are modified. Preferably, the carbonaceous component is chemically modified in the following manner. A unctable carbonaceous component can be prepared by reacting a carbonaceous component with a diazonium salt in a liquid reaction medium to attach at least one organic group to the surface of the carbonaceous component. The preferred reaction medium includes water, any medium containing water, and any medium containing alcohol. Water is the most preferred medium. The modified carbonaceous components and the various methods for their preparation are described in the U.S. patent application entitled "Natural Black Smoke Reaction with Diazonium Salts., Produced Natural Gas Smoke Black Products and Their Uses ", filed on December 15, 1994, the same day as the present application, and incorporated herein by reference, the modified carbonaceous components and the various methods for their preparation. they are also described in the U.S. patent application entitled "Reaction of Carbon Materials with Diazonium Salts and Resulting Carbon Products" filed on December 15, 1994, the same day as the present application, and also incorporated herein by reference A method for preparing bondable carbonaceous components for use in the gel compositions of the present invention is described in the following paragraph with reference to natural gas carbon black as the carbonaceous component. unbleable carbonates different from natural gas carbon black To prepare gas carbon black Unibody natural, the diazonium salt needs to be stable enough to allow reaction with the natural gas carbon black. In this way, the reaction can be carried out with some diazonium salts, considered otherwise unstable and bound to the decomposition. Some decomposition processes can compete with the reaction between natural gas carbon black and diazonium salt and can reduce the total number of organic groups bound to natural gas carbon black. In addition, the reaction can be carried out at elevated temperatures where many diazonium salts can be susceptible to decomposition. The elevated temperatures can also advantageously increase the solubility of the diazonium salt in the reaction medium and improve its handling during the process. However, elevated temperatures can result in some loss of the diazonium salt due to the other decomposition processes. The natural gas carbon black can be reacted with a diazonium salt when presented as an aqueous, easily stirred, diluted mixture, or in the presence of the appropriate amount of water for the formation of natural gas carbon black granule. . If desired, natural gas carbon black granules can be formed using conventional granulation technology. A preferred group of organic groups that can be attached to the natural gas carbon black are organic groups substituted with an ionic or ionizable group as a functional group. An ionizable group is one that is capable of forming an ionic group in the medium of use. The ionic group can be an anionic group or a cationic group and the ionizable group can form an anion or a cation. Ionizable functional groups that form anions include, for example, acidic groups or salts of acidic groups. Accordingly, the organic groups include groups derived from organic acids. Preferably, when it contains an ionizable group forming an anion, such an organic group has a) an aromatic group or a C1-C12 alkyl group and b) at least one acidic group having a pKa of less than 11, or at least one salt of an acidic group having a pKa of less than 11, or a mixture of at least one acidic group having a pKa of less than 11 and at least one salt of an acidic group having a pKa of less than 11. The pKa of the Acidic group refers to the pKa of the organic group as a whole, not just the acidic substituent. More preferably, the pKa is less than 10 and more preferably less than 9. Preferably, the aromatic group or the C 1 -C 12 alkyl group of the organic group is directly attached to the natural gas carbon black. The aromatic group may also be substituted or unsubstituted, for example, with alkyl groups. The C1-C12 alkyl group may be branched or unbranched and is preferably ethyl. More preferably, the organic group is a phenyl or naphthyl group and the acidic group is a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, or a carboxylic acid group. Examples include -COOH, -SO3H and -PO3H2, and their salts, for example -COONa, -COOK, -COO "NR4 +, -S03Na, -HP03Na, -S03" NR4 +, and P03Na2, where R is an alkyl group or phenyl. Particularly preferred ionizable substituents are -COOH and -S03H and their sodium and potassium salts. More preferably, the organic group is a substituted or unsubstituted sulfophenyl group or a salt thereof; a substituted or unsubstituted phenyl (polysulf) group or a salt thereof; a substituted or unsubstituted sulfonaphthyl group or a salt thereof; or a substituted or unsubstituted naphthyl (polysulf) group or a salt thereof. A preferred substituted sulfophenyl group is a hydroxysulfophenyl group or a salt thereof. Specific organic groups having an ionizable functional group that forms an anion are p-sulfophenyl, 4-hydroxy-3-sulfophenyl, and 2-sulfoethyl. The amines represent examples of ionizable functional groups which form cationic groups and which can be attached to the same organic groups as those discussed above for the ionizable groups which form anions. For example, amines can be protonated to form ammonia groups in an acidic medium. Preferably, an organic group having an amine substituent has a pKb of less than 5. The quaternary ammonia groups (-NR3 +) and the quaternary phosphonium groups (-PR3 +) also represent examples of cationic groups and can be attached thereto. organic groups above treated for the ionizable groups that form anions. Preferably, the organic group contains an aromatic group such as a phenyl or naphthyl group and a quaternary ammonia group or a quaternary phosphonium group. The aromatic group is preferably directly attached to the natural gas carbon black. Quaternized cyclic amines and quaternized aromatic amines can also be used as the organic group. In this manner, the N-substituted-firidinium compounds, such as pyridyl-methyl-N, can be used in this regard. An advantage of the natural gas carbon black products having a bonded organic group, substituted with an ionic or ionizable group is that the natural gas carbon black products can have an increased water dispersibility with respect to the carbon black of corresponding untreated natural gas. In general, the water dispersibility of natural gas carbon black products increases with the number of organic groups bonded to the natural gas carbon black having an ionizable group or the number of ionizable groups bound to a given organic group. . In this way, the increase in the number of ionizable groups associated with the natural gas carbon black products should increase their dispersibility in water and allow control of dispersibility in water to a desired level. It can be seen that the water dispersibility of the natural gas carbon black products containing an amine such as the organic group attached to the natural gas carbon black, can be increased by the acidification of the aqueous medium. When preparing water dispersible, natural gas carbon black products, it is preferred that the ionic or ionizable groups be ionized in the reaction medium. The resulting solution or mixture of product can be used as it is or diluted before being used. Alternatively, the natural gas carbon black products can be dried by techniques used for conventional natural gas carbon blacks. These techniques include, but are not limited to, drying in rotary ovens and stoves. However, overdrying may cause a loss in the degree of dispersibility in water. In the event that the above natural gas carbon black products are not dispersed in the aqueous vehicle as easily as desired, the natural gas carbon black products can be dispersed using conventionally known techniques such as milling or grinding. In contrast to conventional natural gas carbon black pigments, chemically modified, unbleivable natural gas carbon black products are not difficult to disperse in an aqueous medium. The chemically modified natural gas carbon black products do not necessarily require a conventional grinding process, nor are dispersants basically necessary to obtain a useful dispersion. Preferably, chemically modified, unbleivable natural gas carbon black products only require low shear stirring or mixing to easily disperse the pigment in water. The formation of granules from the unbondable natural gas carbon black products is preferably carried out using a conventional wet process needle granulation method. The resulting granules are easily dispersed in water with minimal agitation or shear mixing, reducing or avoiding the need for grinding or the use of a dispersant. The present invention also includes a novel gel composition comprising: a gel component and a natural gas carbon black product having at least one organic group, the organic group comprising a) at least one aromatic group, and b) at least one ionic group, at least one ionizable group or a mixture of an ionic group and an ionizable group, wherein at least one aromatic group of the organic group is directly attached to the natural gas carbon black. Preferably, the ionic or ionizable group is selected from the group consisting of: a carboxylic acid or a salt thereof; a sulfonic acid or a salt thereof; and a salt of quaternary ammonia. Preferably, the organic group is selected from the group consisting of: a sulfophenyl group or a salt thereof; • p-sulfophenyl or a salt thereof; and carboxyphenyl or a salt thereof. The natural gas carbon black products, suitable for use in the various embodiments of this gel composition of the present invention can be produced in the manner described above with reference to the creation of a unctable carbonaceous component. The present invention further includes a novel gel composition comprising: a gel component and a natural gas carbon black product having at least one organic group, the organic group comprising at least one C1-C12 alkyl group , and b) at least one ionic group, at least one ionizable group or a mixture of an ionic group and an ionizable group, wherein at least one alkyl group of the organic group is directly attached to the natural gas carbon black. Preferably, the ionic or ionizable group is selected from the group consisting of: a sulphonic acid of ethane or a salt thereof. The natural gas carbon black products, suitable for use in the various embodiments of this gel composition of the present invention may also be produced in the manner described above with reference to the creation of a unctable carbonaceous component. The gel compositions of the present invention can be produced by any process known in the art for the preparation of gel compositions. For example, a gel composition of the present invention can be produced by the following method which relates to an alkoxide system: 1) Dissolving a precursor of the desired gel component (an alkoxide in this example) in alcohol; 2) Add water to the solution so that the molar ratio of alkoxide and water is about 1; 3) Add an acid to the resulting solution so that the molar ratio of water and acid equals about 1: 0.0007 to produce a solution; 4) Add a carbonaceous component to the solution; ) Add a catalyst (usually an acid or a base) to the start gelation of the solution; 6) Ripen the resulting gel in a mold for approximately 24 hours at 50 ° C; 7) Rinse the resulting gel with water to replace the solvent component with water, and then ripen the gel in water at elevated temperature (up to 100 ° C, preferably about 70 ° C) for 24 hours; 8) Rinse the matured gel in solvent to drain the water and replace the water with solvent; 9) Dry the resulting gel to form a gel composition of the present invention. Gel precursors, suitable for use in the gel composition of the present invention include, but are not limited to, metal oxide gel precursors known in the art, such as: Metal Oxide Form (s) as Gel Precursor SÍO2 Alkoxide, Sodium Silicate, Colloidal Ti02 Alkoxide, Colloidal Al2? 3 Alkoxide, Colloidal, Sodium Aluminate, Salts The choice of a particular precursor is made based on the type of gel desired. Additional details with reference to the process for making a gel composition of the present invention and the exemplary processes are set forth below in the Examples section. As stated in the preceding section, the gel compositions of the present invention can be used for any known application for gel compositions. As will be recognized by those of ordinary skill in the art, whether a particular gel composition of the present invention is desirable for use in a particular application will depend on the characteristics of the gel composition, such as the amount of carbonaceous material incorporated in the composition. composition and volume density of the composition. Exemplary usages for the gel compositions of the present invention include, but are not limited to, the following: Isolation Applications The gel compositions of the present invention can be advantageously used in thermal, electrical and / or acoustic insulation applications as appropriate. set below. Thermal Insulation A gel composition of the present invention can be incorporated as a loose fill material in thermal insulation. In addition, a gel composition of the present invention can also be combined with a material selected from the group consisting of: calcium silicate, a mineral fiber, a metal oxide powder, a polymer foam, glass fiber, and the like and the combination incorporated in the thermal insulation. Alternatively, a gel composition of the present invention can be used under vacuum in thermal insulation. ELECTRICAL INSULATION A gel composition of the present invention can be incorporated into a proposed polymer composition for use as electrical insulation. Acoustic Isolation A gel composition of the present invention can be incorporated as a loose filler in acoustic insulation. Alternatively, a gel composition of the present invention can be combined with another material, such as cellulose, or polymer foam and the combination incorporated as a filler material in the acoustic insulation. Applications of Particulate Additive The gel compositions of the present invention can be used as particulate additives, such as thickeners, laminators, fillers or reinforcing agents. Examples of each include the following: Thickeners A gel composition of the present invention can be used as a thickener in pigment compositions and printing inks. The non-toxic gel compositions of the present invention can also be used as a thickener in food products. Laminators The term "laminator" or "product to opacify" refers to a composition that will opacify or laminate the finish of a paint, varnish or film. A gel composition of the present invention can be used as a laminator for lacquers, semi-satin varnishes, enamels or vinyl films. Filling Material A gel composition of the present invention can be used as a filling material in cements, adhesives and compositions of natural or synthetic rubber. Strengthening Agent A gel composition of the present invention can also be used as a reinforcing agent in polymer compositions, such as molded brake linings and in natural or synthetic rubber compositions. Adsorbent A gel composition of the present invention can be used as a material for adsorption of liquid, gas or vapor.

Catalyst Support A gel composition of the present invention can be used as a host support for powdered metal, or metal oxide catalytic materials. Membranes A gel composition of the present invention can be used as a material for selective separations of liquid, gas or vapor. Filters A gel composition of the present invention can be used as a filtration material for particulates. Radiation Detectors A gel composition of the present invention can be used to detect radiation in a radiation detector such as a Cherenkov radiation detector. Heat Resistant Coating A gel composition of the present invention can be used, as a thin film, as a thermal barrier coating. Low K Dielectric A gel composition of the present invention can be used in dielectric materials, for example as a low dielectric constant material. As will be recognized by those of ordinary skill in the art from the foregoing list of applications, the gel compositions of the present invention can be used in many, if not all, applications that have so far used the compositions. in conventional gel. You will also find that the above list is not an exhaustive list, but merely representative of the many potential uses for the gel compositions of the present invention. The effectiveness and advantages of various aspects and embodiments of the present invention will be further illustrated by the following examples wherein the following examination procedures were used. The area of the nitrogen surface (N2SA) of the natural gas carbon blacks used in the examples, expressed as square meters per gram (m2 / g) was determined according to Method A D3037 of the ASTM test procedure. The adsorption value of dibutyl phthalate (DBP) of the natural gas carbon blacks used in the examples, expressed as millimeters per 100 grams of natural gas carbon black (ml / 100 g), was determined according to the procedure established in ASTM D2414. The average basic particle size of the natural gas carbon blacks used in the examples, expressed as nanometers (nm), was determined according to the procedure set forth in ASTM D3849. The electron microscope photographs for detailed examination (SEM) were produced using an electronic microscope for Hitachi S570 thorough examination, produced and sold by Hitachi Corporation. Each of the photographs by SEM was taken at a setting of 20 kilovolts and an amplification of 25,000. The aqueous residue of the modified and unmodified natural gas carbon blacks was determined by the following procedure. The natural gas carbon black (5 g) was stirred with 45 g of water for 5 minutes.

The resulting dispersion was emptied through a screen and rinsed with water until the rinses were colorless. A 325 mesh screen was used unless otherwise indicated. After drying the screen, the weight of the residue in the screen was determined and expressed as a percentage of the natural gas carbon black used in the test. The volume density and wear of the gel compositions were determined by the following procedures: Volume Density The gels were melted and formed into cylindrical molds. In all cases the cylindrical shape of the gel was preserved after drying. The total gel volume was determined by physically measuring the dimensions of a dry gel. The volume density was determined by weighing the dry gel and dividing it by geometric volume. In the cases where a rod-like geometry was not maintained, or as a verification of the previous method, displacement by mercury was used. The volume density of the gel compositions measured by mercury displacement was carried out as follows. A glass cell, empty, clean, was filled with mercury at a specific height and the cell was weighed. The mercury was then removed and the cell was cleaned again. Next, a dry gel sample of known weight was placed in the glass cell and mercury was added to the cell at the same specific height as before. The weight of the cell containing the mercury and the sample was measured. The weight of the mercury in both cases was then converted to a volume based on the density of the mercury. The difference between the volume of mercury that fills an empty cell and the volume of mercury that fills the cell containing a sample is known as the volume displaced. Since mercury does not wet the sample, this volume is equal to the total volume of the sample. The density is then determined by dividing the weight of the sample between the displaced volume. Wear The wear of the gel compositions was measured in the following manner. A dry gel of specific size (approximately 6 mm in diameter and 25 mm high) slid several times for 2-3 inches along its 25 mm length against a white cloth, using hand pressure. The relative degree of carbon deposition was then compared to a gray scale generated by a calibrated computer. The computer generates several shades of gray and assigns them numbers that vary from 0 to 50 depending on the degree of gray. As the number increases from 0 to 50, so does the relative degree of gray. After the gel was applied to the fabric, a visual comparison was made between the deposited charcoal and the computer map and a gray scale number was assigned according to the above. The lower numbers corresponded to less wear. The wear values in combination with the photographs by SEM were used to determine if the carbonaceous material is attached to the gel component. The following examples illustrate methods for modifying carbonaceous materials and the production of gel compositions, including gel compositions of the present invention, from an alkoxide precursor and a sodium silicate precursor. EXAMPLES Three natural gas carbon blacks, CB-A, CB-B and CB-C were used in the following examples. The analytical properties of each of the natural gas carbon blacks, as determined by the procedures described above, were as shown in Table 1 below: Table 1 - Analytical Properties of Natural Gas Smoke Black Modifying Carbonaceous Materials Examples 1-4 illustrate methods for modifying carbonaceous materials, in particular natural gas carbon blacks. These examples establish the procedures used to produce the modified natural gas carbon blacks, the Modified CB-A, the Modified CB-B, the CB-B Phenolic and the Modified CB-C used in the remaining examples. Example 1 This example illustrates the preparation of a modified natural gas carbon black product using the natural gas carbon black designated CB-A in Table 1 above. Two hundred grams of CB-A were added to a solution of 10.1 g of sulphanilic acid and 6.23 g of concentrated nitric acid in 21 g of water. A solution of 4.87 g of NaN02 in 10 g of water was added to the rapid stirring mixture. An internal salt of 4-sulfobenzenediazonium hydroxide was formed in situ, which reacted with the natural gas carbon black. After 15 minutes, the dispersion was dried in an oven at 125 C. The resultant natural gas carbon black product was designated "CB-A Modified" and is a natural gas carbon black having 4-C6H4S03 groups United. Example 2 This example illustrates the preparation of a modified natural gas carbon black product using the natural gas carbon black designated CB-B in Table 1 above. A solution prepared from 36.2 g of sulphanilic acid, 8.76 g of NaOH and 162 g of water was cooled in ice. Twenty grams of N02 were added with stirring and the resulting suspension was heated to 75 C and added without delay to a granulator containing 300 g of CB-B. After the granulation for three minutes, 35 g of additional water was added. After the granulation for two additional minutes, the product was removed from the granulator and dried in an oven at about 125 ° C. The product had a 325 mesh residue of 0.14%, compared to 94% for the unreacted natural gas carbon black. The resultant natural gas carbon black product was designated "Modified CB-B" and is a natural gas carbon black having 4-C6H4S03 groups attached. Example 3 This example illustrates the preparation of a modified natural gas carbon black product other than Example 2, which uses the natural gas carbon black designated CB-B in Table 1 above. A 5-amino-2-hydroxybenzene sulfonic acid (1.89 g) was dissolved in 100 g of hot water, 10 g of CB-B were added and the mixture was cooled to room temperature. Concentrated HCl (1.18 g) was added and then a solution of 0.85 g of sodium nitrite in water was added, forming a diazonium salt in situ, which reacts with the natural gas carbon black. After stirring for 15 minutes, the resulting dispersion was dried in an oven at 125 C. The product had a 325 mesh residue of 0.06%, compared to 94% for the unreacted natural gas carbon black. The resultant natural gas carbon black product was designated "CB-B Phenolic" and is a natural gas carbon black having groups of 4,3-C 6 H 4 (OH) (S0 3 ~) attached. Example 4 This example illustrates the preparation of a modified natural gas carbon black product using the natural gas carbon black designated CB-C in Table 1 above. Two hundred grams of CB-C were mixed in 2.8 L of water. Sulfanilic acid (42.4 g) was dissolved in the stirring mixture, and then a cold solution of 25.5 g of N02 in 100 g of water was added with rapid stirring. An internal salt of 4-sulfobenzenediazonium hydroxide was formed in situ, which reacts with the natural gas carbon black. Bubbles were released. After stirring for one hour, 5 g of N02 was introduced directly into the mixture. The dispersion was stirred for 15 minutes, left overnight and dried in an oven at 130 ° C. The resultant natural gas carbon black product was designated "Modified CB-C" and is a natural gas carbon black having groups of 4-C6H4S03 attached. As illustrated in the following examples, modified natural gas carbon blacks, Modified CB-A, Modified CB-B, CB-B Phenolic and Modified CB-C are bondable to a gel component and are used to form the cfel compositions of the present invention. For comparison purposes, the gel compositions were also prepared using the unmodified natural gas carbon blacks, CB-A, CB-B and CB-C. Examples of Alkoxide Gel Precursor (Up to 50%, by Weight Load (solids)) Examples 5-22 are directed to gels produced from an alkoxide precursor only, and with an amount, less than or equal to 50% in weight (of solids), of a carbonaceous component. Example 5 A concentrated silica solution was prepared by mixing 61 ml (milliliters) of tetraethyl orthosilicate (98% pure), 61 ml of ethyl alcohol, 4.87 ml of deionized water, and 0.2 ml of 1M hydrochloric acid in a 500 ml round bottom flask with vigorous stirring. The flask was placed in a heating vat and the mixture flowed again with the aid of a condenser at 70 ° C for 2 hours. The resulting solution, which contained Si02 at 15% by weight, was cooled and stored at 5 ° C until use. Before gelation, the solution was warmed to room temperature and the concentration was adjusted by dilution with ethyl alcohol in such a way that the resulting mixture contained SiO2 at 11% by weight. This was carried out by combining 70% by volume of the original solution with 30% by volume ethyl alcohol. The gelation was initiated by the addition of 0.5 M NH40h at a volume ratio of 1:10 ammonia to the solution. After the ammonia was added, the mixture was allowed to stir for 2-5 minutes and then melted into cylindrical tubes. The gelation occurred within 7-10 minutes. The gels were then sealed inside the molds to prevent drying and maturing at 50 ° C for 24 hours. After the initial maturation the gels were removed from the mold, placed in sealed tubes containing deionized water and then matured at 70 ° C for an additional 24 hours. After removal from the oven, the gels were rinsed several times with deionized water. The gels were then placed in sealed tubes containing acetone and the porous fluid was allowed to exchange (basically a nona) for 10 hours at 50 ° C. At the end of a 10 hour interval the gels were rinsed with acetone. This process was repeated a total of 3 times. After such three intervals, a portion of the gels was dried directly from the acetone, first at 50 ° C for 12 hours thereafter at 140 ° C for an additional 12 hours. The resulting gels showed some shrinkage and each had a measured volume density of 0.5-0.6 g / cm3. The remaining gels were placed in sealed tubes containing heptane and the pore fluid was allowed to exchange for 10 hours at 50 ° C. At the end of a 10 hour interval the gels were rinsed with heptane.

This process was repeated three times. After these three intervals the gels were dried directly from the heptane, first at 70C'C for 12 hours thereafter at 140 ° C for an additional 12 hours. These gels retained their cylindrical shapes with the least amount of shrinkage and each had a volume density of 0.4-0.44 g / cm3. The volume density and wear of the representative samples of the gels dried in acetone and heptane was determined according to the methods described herein. The results are provided in Tables 2 and 3 below. EXAMPLE 6 This example illustrates the production of gel compositions containing an unmodified natural gas carbon black component, referred to herein as "CB-A", which has the analytical properties set forth in Table 1. In this example the steps of Example 5 were substantially repeated with one exception. Before starting gel formation, a specific amount of CB-A was added to the solution, which had been diluted with 70% by volume of the original solution and 30% by volume of ethyl alcohol. The amount of natural gas carbon black added was calculated in such a way that the total solids content remained the same, so that in effect the amount of natural gas carbon black added would replace an equivalent mass of silica. In this example, the desired solids content is 11% as in Example 5. Therefore, of that 11% solids, 95% consisted of silica and the remaining 5% solids was added as carbon black. free natural gas. In order to keep the solids content the same, the solution was diluted with an appropriate amount of ethyl alcohol to provide the adjusted silica content. Once the relative proportions were determined, the appropriate amount of natural gas carbon black was stirred in the solution for 5-10 minutes. The CB-A was dispersed in the solution in such a way that 5% of the total solids content was CB-A and the balance was silica. The gelation started as in the previous example. The volume ratio used to promote gelation was maintained at 1:10 and the concentration of the base remained at 0.5 M. As in the previous Example, the ammonia was added, the CB-A was dispersed with vigorous stirring for 2-5 minutes and then melted into cylindrical tubes. The gelation occurred within 8-12 minutes. The gels were then matured for 24 hours at 50 ° C, then removed from the smelters and matured for another 24 hours in deionized water at 70 ° C. The gels were then exchanged by solvent and dried as outlined in Example 5, from acetone and heptane. The volume density and wear of representative samples of the gels dried in acetone and heptane were determined according to the methods described herein. The results are provided in Tables 2 and 3 below. Examples 7-11 The steps of Example 6 were repeated with the exception that the amount of CB-A was increased from 10 to 50% of the total solids, silica being the balance. The particular amount of natural gas carbon black used in each example, as a percentage of total solids, is shown in the Table below: When the amount of CB-A varied from 10 to 20% the wet gels were noticeably stronger. For a given solvent, the dry gels demonstrated reduced shrinkage and lower bulk density as the CB-A content increased. One factor that was independent of the natural gas carbon black content was the wear characteristic of each of the dry gels. After handling a dry gel containing CB-A, a significant amount of residual natural gas carbon black was deposited from the material on the gloves with which it was handled and into the surrounding medium. In addition, the rate of wear of the fine carbon powders for the gels prepared with CB-A was substantial. The wear characteristics, and the substantial wear ratios, of the gels indicate the presence of natural gas carbon black that was not bonded to the gel component.

The volume density and wear of the representative samples of the acetone and heptane dried gels, of each example, were determined according to the methods described herein. The results are provided in Tables 2 and 3 below. Example 12 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. In this example substantially all of the procedures used in Examples 6-11 were repeated with the exception that the gel compositions incorporated the Modified CB-A of Example 1. As in Example 6, the Modified CB-A was dispersed in the partially hydrolyzed silica solution in such a way that 5% of the total solids content was CB-A Modified and the balance was silica. A set of gels were prepared with the addition of ammonia, matured in the same manner as described above, the solvent exchanged with acetone and heptane and dried as outlined in Examples 7-11. Modified CB-A dispersed more easily and remained dispersed longer in terms of sedimentation behavior than unmodified CB-A. In the wet state the gels appeared stronger than those without natural gas carbon black and slightly stronger than the gels containing unmodified CB-A. However, for a given solvent, the volume density was lower for the materials made by the use of Modified CB-A. More important was the observation that the wear behavior was significantly reduced by indicating that the natural gas carbon black was actively incorporated into the gel network, and bound to the gel component. The volume density and wear of the representative samples of the gels dried in acetone and heptane were determined according to the methods described herein. The results are provided in Tables 2 and 3 below. Examples 13-17 These examples illustrate the production of gel compositions of the present invention comprising a natural gas carbon black bonded to a gel component. The steps of Example 12 were repeated with the exception that the amount of CB-A Modified was increased from 10 to 50% of the total solids, silica being the balance. The particular amount of natural gas carbon black used in each example, as a percentage of total solids is shown in the Table below: When the gels produced with unmodified CB-A are compared, the dry gels of Examples 13-17 incorporating Modified CB-A demonstrate reduced shrinkage and lower bulk densities for a given solvent as the content of CB-A Modified. Further, for a solvent and a modified CB-A content given, the wet gels were physically stronger and the dry gels had lower bulk densities compared to the gels prepared with the unmodified CB-A. Another distinctive feature of the whole sets of CB-A Modified gel was a noticeable difference in wear behavior. After handling the dry gels, a substantial reduction in the residual carbon deposited on the gloves and the surrounding medium was observed in comparison with the gel compositions produced with unmodified CB-A. The wear rate of fine carbon powders for gels prepared with Modified CB-A also decreased greatly compared to gels produced with unmodified CB-A. These results indicate that the Modified CB-A was bound to the gel component. The volume density and wear of the representative samples of the acetone and heptane dried gels, of each example, were determined according to the methods described herein. The results are provided in Tables 2 and 3 below. EXAMPLE 18 In this Example, the procedures used in Examples 6-12 were substantially repeated using a different natural gas carbon black, designated herein as "CB-B", which has the analytical properties set forth in Table 1. in the previous Examples, CB-B was dispersed in the partially hydrolyzed silica solution such that 15% of the total solids content was CB-B and the balance was silica. A set of gels was then prepared with the addition of ammonia, matured, the solvent was exchanged and dried as outlined in Example 5.

The volume density and wear of the representative samples of the gels dried in acetone and heptane were determined according to the methods described herein. The results are provided in Tables 2 and 3 below. Example 19 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component.

In this example, the procedures used in Example 18 were substantially repeated with the exception that the gel compositions incorporated the Modified CB-B from Example 2. As in the previous Examples, the Modified CB-B was rinsed according to the established protocol and was then dispersed in the partially hydrolyzed silica solution in such a way that 15% of the total solids content was Modified CB-B and the balance was silica. A set of gels was then prepared, matured in the same manner as described above, the solvent was exchanged with acetone and heptane and dried as outlined in the previous Examples. The volume density and wear of the representative samples of the gels dried in acetone and heptane were determined according to the methods described herein. The results are provided in Tables 2 and 3 below. Example 20 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. In this example, the procedures used in Example 19 were substantially repeated with the exception that the gel compositions incorporated the CB-B Phenolic of Example 3. As in the previous Examples, the CB-B Phenolic was rinsed and then dispersed in the partially hydrolyzed silica solution in such a way that 15% of the total solids content was CB-B Phenolic and the balance was silica. A set of gels was then prepared with the addition of ammonia, the solvent was exchanged and dried as outlined in the previous Examples. The volume density and wear of the representative samples of the gels dried in acetone and heptane were determined according to the methods described herein. The results are provided in Tables 2 and 3 below. Example 21 In this example, the procedures used in the previous Examples 5-21 were substantially repeated using a different natural gas carbon black, designated herein as "CB-C", having the analytical properties set forth in Table 1. As in the previous Examples, CB-C was dispersed in the partially hydrolyzed silica solution in such a way that 15% of the total solids content was CB-C and the balance was silica. A set of gels was then prepared with the addition of ammonia, the solvent was exchanged and dried as outlined in the previous Examples. The volume density and wear of the representative samples of the gels dried in acetone and heptane were determined according to the methods described herein. The results are provided in Tables 2 and 3 below. Example 22 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. In this example, the procedures used in Example 21 were substantially repeated with the exception that the gel compositions incorporated the Modified CB-C of Example 4. As in the previous Examples, the Modified CB-C was rinsed and then dispersed in the partially hydrolysed silica solution in such a way that 15% of the total solids content was CB-C Modified and the balance was silica. A set of gels was then prepared with the addition of ammonia, the solvent was exchanged and dried as outlined in the previous Examples. The volume density and wear of the representative samples of the gels dried in acetone and heptane were determined according to the methods described herein. The results are provided in Tables 2 and 3 below.

Table 2 - Alkoxide Precursor Gels (< 50% Coal) Dried in Acetone Table 3 - Alkyl Precursor Gels «50% carbon) Heptane Dried # of SEM Fig. = Electron Microscope Figure Number for detailed examination As shown by the photographs by SEM, in particular Figure 3 of the gel composition of the present invention of Example 14, Figure 5 of the gel composition of the present invention of Example 19, Figure 6 of the gel composition of the present invention of Example 20 and Figure 8 of the gel composition of the present invention of Example 22, the modified natural gas carbon blacks are bonded to the silica gel component in the gel compositions of the present invention. As illustrated in Figures 3, 5, 6 and 8, the minimum or null amounts of the bonded carbonaceous component (modified natural gas carbon black) appear as a distinct aggregate in the SEM's of fracture surface of these compositions in gel. These results indicate that the modified natural gas carbon black binds to the silica gel component in several places and that the bond of silica to natural gas carbon black is stronger than silica bonds with silica in gel compositions. conventional ones that do not include a carbonaceous component attached to the gel component. In contrast, as illustrated in Figures 2, 4 and 7, the SEM 's of fracture surface of the gel compositions that include a carbonaceous component that does not bind to the gel component, show aggregates other than carbon black. natural gas. In these gel compositions, the natural gas carbon black does not bind to the silica gel component. Examples of Sodium Silicate Gel Precursor (Up to 50% by Weight Charge (solids)) Examples 23-28 are directed to gels produced from a sodium silicate precursor and less than or equal to 50% by weight. weight (of solids) of a carbonaceous component. Example 23 A silica stock solution was prepared by mixing commercially available sodium silicate (molar ratio of Si02 / Na0 of 3.22: 1) with deionized water in a volume ratio of 1.33: 1 of water with sodium silicate. The temperature of the mixture was maintained at 15 ° C, vigorously stirring in a beaker with an outer jacket. A separate solution comprising 2M H2S04 was prepared by diluting concentrated sulfuric acid (96%) with water. An aliquot of 104 ml of the sodium silicate stock solution was then slowly added to 50 ml of stirred 2M acid. The proportion of silicate addition was kept constant at 1 ml / minute and the acid solution was maintained at 15 ° C in an external jacketed beaker. The resulting silica solution contained approximately 10% by weight of silica in a saline solution.

The gelation was carried out by the controlled addition of 1M NaOH until the pH of the solution reached 5. At this point, the solution was stirred vigorously for 1 minute and then melted into cylindrical tubes. The gelation occurred in 5 minutes and the tubes were sealed to prevent drying. The gels were allowed to mature for 1-2 hours at 50 ° C in the molds after which they were placed in sealed tubes containing deionized water and kept at room temperature. Fresh water was added every 3 hours for a total of 12 hours at which time it was determined (by insertion of a sodium electrode) that the sodium sulfate salt was completely removed from the gel. The gels were then matured at 70 ° C in deionized water for 24 hours. After removal from the oven, the gels were rinsed several times with deionized water, placed in tubes sealed with acetone and allowed to exchange the porous fluid for 10 hours at 50 ° C. At the end of 10 hours the gels were rinsed with acetone and stored in fresh acetone at 50 ° C. This procedure was repeated three times. After such three intervals, the gels were placed in sealed tubes containing heptane and the porous fluid was allowed to exchange for 10 hours. At the end of 10 hours the gels were rinsed with heptane and stored in fresh heptane at 50 ° C. This procedure was repeated three times. After these three intervals the gels were dried directly from the heptane, first at 70 ° C for 12 hours thereafter at 140 ° C for an additional 12 hours. These resulting dry gels retained their cylindrical shapes and exhibited minimal shrinkage. The volume density and wear of a representative sample of the gel compositions were determined according to the methods described herein. The results are given in Table 4 below. Example 24 This example illustrates the production of gel compositions containing an unmodified natural gas carbon black component, referred to herein as "CB-A", which has the analytical properties set forth in Table 1. They were substantially repeated the steps of Example 23 with some processing changes. Before starting the formation of the gel, a specific amount of a particular natural gas carbon black was added, CB-A (as in Examples 6-11) to the solution. The amount of natural gas carbon black added was calculated such that the total solids content remained the same, so that in effect the amount of natural gas carbon black added would replace one silica mass equivalent. In this example, the desired solids content is 10% as in Example 23. Accordingly, of 10% solids, 90% consisted of silica and the remaining 10% solids was added as carbon black. free natural fas (CB-A). In order to keep the solids content the same, the solution was diluted with an appropriate amount of deionized water to provide the adjusted silica content. Once the relative proportions were determined, the appropriate amount of natural gas carbon black was stirred in the solution for 5-10 minutes. In this example, CB-A was dispersed in the solution containing sodium silicate combined with sulfuric acid in such a way that 10% of the total solids content was CB-A and the balance was silica. The gelation was started as in example 23, by increasing the pH with 1M NaOH to a final pH of 5. After gelation the materials were matured at 50 ° C for 1-2 hours, as in Example 23, they were removed from the molds and then rinsed free of salts for 12 hours at room temperature. The charged gels were then exchanged for solvent and dried as outlined in Example 23, from heptane. The volume density and wear of a representative sample of the gel compositions were determined according to the methods described herein. The results are given in Table 4 below. Example 25 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. In this Example, the procedures used in Example 24 were substantially repeated except that the gel compositions incorporated the Modified CB-A of Example 1. Modified CB-A was dispersed in an acetone beaker, vacuum filtered , and then repeatedly rinsed with deionized water until the pH of the rinse water was almost neutral. The Modified CB-A was then dried at 140 ° C for 12 hours. As in Example 24, Modified CB-A was dispersed in the solution containing sodium silicate combined with sulfuric acid in such a way that 10% of the total solids content was Modified CB-A and the balance was silica. In contrast to unmodified CB-A, the addition of Modified CB-A was limited due to the stability of the surface groups. Only at pH values higher than 3 could the Modified CB-A be introduced into the solution in such a way that the modification of the surface could be preserved. Accordingly, the pH was carefully raised to 3 with the controlled addition of 1M NaOH and the appropriate amount of Modified CB-A dispersed in the solution. The gelation was achieved, as before, by the controlled addition of 1M NaOH until the pH of the solution reached 5. After gelation the materials were matured at 50 ° C for 1-2 hours as before, removed from The molds were then rinsed free of salts for 12 hours at room temperature. The gel compositions were matured for 24 hours at 70 ° C in deionized water. A portion of the gels was then exchanged for solvent and dried from heptane as outlined in the above Examples. The volume density and wear of a representative sample of the gel compositions were determined according to the methods described herein. The results are given in Table 4 below. Example 26 In this Example, the procedures used in Example 24 were substantially repeated using a different natural gas carbon black, designated herein as "CB-B", which has the analytical properties set forth in Table 1. Before initiating gel formation, a specific amount of CB-B (as above) was added to the solution. The amount of CB-B added was calculated in such a way that the total solids content remained the same, so that in effect the amount of CB-B added replaced an equivalent mass of silica. In this example, the total solids content desired is 10% as in Example 23. Therefore, of that 10% solids, 90% consisted of silica and the remaining 10% solids was added as CB-B free. In order to keep the solids content the same, the solution was diluted with an appropriate amount of deionized water to provide the adjusted silica content. Once the relative proportions were determined, the appropriate amount of natural gas carbon black was stirred in the solution for 5-10 minutes. In this example, CB-B was dispersed in the solution containing sodium silicate combined with sulfuric acid in such a way that 10% of the total solids content was CB-B and the balance was silica. The gelation was initiated as in the previous examples, by increasing the pH with 1M NaOH to a final pH of 5. After gelation the materials were matured at 50 ° C for 1-2 hours as before, they were removed from the molds and then rinsed free of salts for 12 hours at room temperature. The gel compositions were then matured for 24 hours at 70 ° C in deionized water. A portion of the gel compositions were then exchanged for solvent and dried from heptane as outlined in the previous examples. The volume density and wear of a representative sample of the gel compositions were determined according to the methods described herein. The results are given in Table 4 below. Example 27 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. In this Example, the procedures used in Example 26 were substantially repeated except that the gel compositions incorporated the modified CB-B from Example 2. Modified CB-B was dispersed in an acetone beaker, vacuum filtered , and then repeatedly rinsed with deionized water until the pH of the rinse water was almost neutral. Modified CB-B was then dried at 140 ° C for 12 hours. As in Example 24, the Modified CB-B was dispersed in the solution containing sodium silicate combined with sulfuric acid in such a way that 10% of the total solids content was CB-B Modified and the balance was silica. In contrast to the unmodified CB-B, the addition of Modified CB-B was limited due to the stability of the surface groups. Only at pH values greater than 3 could the Modified CB-B be introduced into the solution in such a way that the modification of the surface could be preserved. Accordingly, the pH was carefully raised to 3 with the controlled addition of 1M NaOH and the proper amount of Modified CB-B dispersed in the solution. The gelation was achieved, as before, by the controlled addition of 1M NaOH until the pH of the solution reached 5. After gelation the materials were matured at 50 ° C for 1-2 hours as before, removed from The molds were then rinsed free of salts for 12 hours at room temperature. The gel compositions were matured for 24 hours at 70 ° C in deionized water. The gels were then exchanged for solvent and dried from heptane as outlined in the above Examples. The volume density and wear of a representative sample of the gel compositions were determined according to the methods described herein. The results are given in Table 4 below. Example 28 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. In this Example, the procedures used in Example 26 were substantially repeated with the exception that the gel compositions incorporated the CB-B Phenolic of Example 3. The CB-B Phenolic was dispersed in a beaker of acetone, filtered under vacuum, and then repeatedly rinsed with deionized water until the pH of the rinse water was almost neutral. The CB-B Phenolic was then dried at 140 ° C for 12 hours. As in Example 24, the CB-B Phenolic was dispersed in the solution containing sodium silicate combined with sulfuric acid in such a way that 10% of the total solids content was CB-B Phenolic and the balance was silica. In contrast to unmodified CB-B, the addition of CB-B Phenolic was limited due to the stability of the surface groups. Only at pH values higher than 3 could the CB-B Phenolic be introduced into the solution in such a way that the modification of the surface could be preserved. Accordingly, the pH was carefully raised to 3 with the controlled addition of 1M NaOH and the appropriate amount of CB-B Phenolic dispersed in the solution. The gelation was achieved, as before, by the controlled addition of 1M NaOH until the pH of the solution reached 5. After gelation the materials were matured at 50 ° C for 1-2 hours as before, removed from The molds were then rinsed free of salts for 12 hours at room temperature. The gel compositions were matured for 24 hours at 70 ° C in deionized water. The gels were then exchanged for solvent and dried from heptane as outlined in the above Examples.

The volume density and wear of a representative sample of the gel compositions were determined according to the methods described herein. The results are given in Table 4 below.

Table: Sodium Silicate Precursor Gels (< 50% Coal) Examples 29-34 are directed to gels produced from an alkoxide precursor and greater than 50% by weight (solids) of a carbonaceous component. EXAMPLE 29 The steps of Example 11 were repeated with the exception that the amount of CB-A was increased to 60% of the total solids content and the maturation and drying steps were changed. As before, the appropriate amount of CB-A was added and the solution was diluted with ethyl alcohol to maintain a constant total solids content. The gelation was started in the same manner as in previous examples 5-22. The gels were matured for 24 hours at 50 ° C in sealed cylindrical molds.

Instead of rinsing with water and maturing at 70 ° C, these gels were dried directly from the mother liquor, first at 50 ° C for 10 hours, then at 140 ° C for 10 hours. The resulting products were incoherent bodies that largely comprised fine powders. The volume density of a representative sample of the resulting product was determined by the method described herein. The result is established in Table 5 below. EXAMPLE 30 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bound to a gel component. In this Example, the procedures used in Example 29 were substantially repeated with the exception that the gel compositions incorporated the Modified CB-A of Example 1. As in the previous examples, the Modified CB-A was rinsed and then dispersed in the partially hydrolyzed silica solution in such a way that 60% of the total solids content was CB-A Modified and the balance was silica. As before, the solution was diluted with ethyl alcohol to maintain a constant total solids content and gelation initiated in an analogous manner. The gels were then directly dried from the mother liquor as in Example 29, by maturing for 24 hours at 50 ° C in sealed cylindrical molds, then at 140 ° C for 10 hours. The resulting products were found in the form of solid one-piece granules, which were physically hard. There was a negligible amount of fine carbon powders and the gel article was very durable and consistent when compared to a gel article made with an unmodified carbonaceous material in Example 29. The bulk density of a sample representative of the resulting product was determined by the method described herein. The result is established in Table 5 below. Example 31 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. The steps of Example 30 were repeated with the exception that the amount of Modified CB-A was increased to 70% total solids, silica being the balance. As before, the solution was diluted with ethyl alcohol to maintain a constant total solids content and gelation initiated in an analogous manner. The gels were then matured for 24 hours at 50 ° C in sealed cylindrical molds and then dried directly from the mother liquor, first at 50 ° C for 10 hours, then at 140 ° C for 10 hours. The resulting granules were hard and could be easily handled without breaking or generating fine grains. The volume density of a representative sample of the resulting product was determined by the method described herein. The result is established in Table 5 below. Example 32 In this Example, the procedures used in Example 29 were substantially repeated using a different natural gas carbon black, designated herein as "CB-C", which has the analytical properties set forth in Table 1. The CB-C was dispersed in the partially hydrolyzed silica solution in such a way that 80% of the total solids content was CB -C and the balance was silica. As before, the solution was diluted with ethyl alcohol to maintain a constant total solids content and gelation initiated in an analogous manner. The gels were then matured for 24 hours at 50 ° C in sealed cylindrical molds and then dried directly from the mother liquor, first at 50 ° C for 10 hours, then at 140 ° C for 10 hours. The resulting article was analogous to that of Example 29, that is, a weak, broken gel was formed, which consisted largely of fine carbon powders. The network was not consistent and lacked the structural integrity observed in the examples of the gel compositions of the present invention. The volume density of a representative sample of the resulting product was determined by the method described herein. The result is established in Table 5 below. EXAMPLE 33 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. In this Example, the procedures used in Example 32 were substantially repeated with the exception that the gel compositions incorporated the Modified CB-C from Example 4. As in the previous examples, the Modified CB-C was rinsed and then dispersed in the partially hydrolyzed silica solution in such a way that 80% of the total solids content was CB-C Modified and the balance was silica. As before, the solution was diluted with ethyl alcohol to maintain a constant total solids content and gelation initiated in an analogous manner. The gels were matured for 24 hours at 50 ° C in sealed cylindrical molds, and then dried directly from the mother liquor, first at 50 ° C for 10 hours, then at 140 ° C for 10 hours. The resulting articles were granules similar in appearance and integrity to those produced in Examples 30 and 31. Only a minimal amount of fine carbon powders existed and the gel was very consistent. The volume density of a representative sample of the resulting product was determined by the method described herein. The result is established in Table 5 below. Example 34 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. The steps of Example 33 were repeated with the exception that the amount of Modified CB-C that was used in the gel composition was increased to 85% total solids. As before, the appropriate amount of CB-C Modified was added and the solution was diluted with ethyl alcohol to maintain a constant total solids content and gelation initiated in an analogous manner. The gels were then matured for 24 hours at 50 ° C in sealed cylindrical molds and then dried directly from the mother liquor, first at 50 ° C for 10 hours, then at 140 ° C for 10 hours. The resulting granules could be easily handled without breaking or generating fine powders. The volume density of a representative sample of the resulting product was determined by the method described herein. The result is established in Table 5 below. Example 35 This example illustrates the production of a gel composition of the present invention comprising a natural gas carbon black bonded to a gel component. The steps of Example 33 were repeated with the exception that the amount of Modified CB-C that was used in the gel composition was increased to 90% of the total solids content. As before, the appropriate amount of CB-C Modified was added and the solution was diluted with ethyl alcohol to maintain a constant total solids content and gelation initiated in an analogous manner. The gels were then matured for 24 hours at 50 ° C in sealed cylindrical molds and then dried directly from the mother liquors, first at 50 ° C for 10 hours, then at 140 ° C for 10 hours. The resulting granules could be easily handled without breaking or generating fine powders. The volume density of a representative sample of the resulting product was determined by the method described herein. The result is established in Table 5 below. Table 5: Alkoxide Precursor Gels (>50% carbon) The results of Examples 29-35 illustrate that the gel compositions of the present invention, Examples 30, 31 and 33-35, produced with a carbonaceous component attached to the gel component are coherent solids. In contrast, gel compositions produced with a carbonaceous component that did not bind to the gel component, Examples 29 and 32, were torn apart. These results would indicate, to one of ordinary skill in the art, that the gel compositions of the present invention, Examples 30, 31 and 33-35, are advantageous for use as adsorbents, as compared to the gel compositions of Examples 29. and 32 that were torn apart. Summary of Results As a whole, the SEM and wear data from the previous examples illustrate that in the gel compositions of the present invention the carbonaceous component (CB-A Modified, CB-B Modified, CB-B Phenolic and CB- Modified C) is attached to the gel component. In particular, the gel compositions of the present invention produced in Examples 12-17, 19-20, 22, 25 and 27-28, which have the carbonaceous component attached to the gel component have a lower wear than the gel compositions. comparables produced in Examples 6-11, 18, 21, 24 and 26 wherein the carbonaceous component does not bind to the gel component. Although the data are not presented above, similar results would be expected for the gel compositions of the present invention produced in 30-31 and 33-35, which have the carbonaceous component bonded to the gel component, compared to the gel compositions produced in Examples 29 and 32 wherein the carbonaceous component does not bind to the gel component. Similarly, the photographs by SEM, in particular Figure 3 of the gel composition of the present invention of Example 14, Figure 5 of the gel composition of the present invention of Example 19, Figure 6 of the composition in The gel of the present invention of Example 20 and Figure 8 of the gel composition of the present invention of Example 22, illustrate that the modified natural gas carbon blacks are bonded to the silica gel component in the gel compositions of the invention. present invention. As illustrated in Figures 3, 5, 6 and 8, the minimum or none of the bonded carbonaceous component (modified natural gas carbon black) appear as a distinct aggregate in the SEM 's of the fracture surface of these compositions in gel. These results indicate that the modified natural gas carbon black binds to the silica gel component in several places and that the silica bond to the natural gas carbon black is stronger than the silica bonds with silica in the compositions in conventional gels that do not include a carbonaceous component attached to the gel component. In contrast, as illustrated in Figures 2, 4 and 7, the SEM 's of the fracture surface of the gel compositions including a carbonaceous component that does not bind to the gel component, show aggregates other than carbon black of natural gas. In these gel compositions, the natural gas carbon black does not bind to the silica gel component. It should be clearly understood that the forms of the present invention described herein are illustrative only and are not intended to limit the scope of the invention.

Claims (20)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and therefore the property described in the following claims is claimed as property. A gel composition comprising: a carbonaceous component attached to the gel component. The gel composition according to claim 1, characterized in that the carbonaceous component is selected from the group consisting of natural gas carbon blacks bondable to the gel component, carbon fibers bondable to the gel component, activated carbons bondable to the component in gel and graphitic carbons that are bondable to the gel component. 3. The gel composition according to claim 1, characterized in that the carbonaceous component is a natural gas carbon black that can be attached to the gel component. 4. The gel composition according to claim 1, characterized in that the gel component is selected from the group consisting of metal oxide gels and polymer gels. The gel composition according to claim 4, characterized in that the metal oxide gel component is selected from the group consisting of silica gels, titanium gels and aluminum gels. 6. The gel composition according to claim 1, characterized in that the gel component is silica. 7. The gel composition according to claim 3, characterized in that the gel component is silica. The gel composition according to claim 4, characterized in that the polymer gel is selected from the group consisting of: resorcinol-formaldehyde gels, melamine formaldehyde gels, and phenol-furfural gels. 9. A gel composition comprising: a gel component and a natural gas carbon black product having at least one organic group, the organic group comprising at least one aromatic group, and b) at least one group ion, at least one ionizable group, or a mixture of an ionic group and an ionizable group, wherein at least one aromatic group of the organic group is directly attached to the natural gas carbon black. The gel composition according to claim 9, characterized in that the organic group is selected from the group consisting of: a sulfophenyl group or a salt thereof and carboxyphenyl or a salt thereof. 11. The gel composition according to claim 9, characterized in that the organic group is p-sulfophenyl or a salt thereof. The gel composition according to claim 9, characterized in that the ionic or ionizable group is selected from the group consisting of: a carboxylic acid or a salt thereof; a sulfonic acid or a salt thereof; and a salt of quaternary ammonia. The gel composition according to claim 9, characterized in that the gel component is selected from the group consisting of: metal oxide gels and polymeric gels. 14. The gel composition according to claim 9, characterized in that the gel component is silica. 15. A gel composition comprising: a gel component and a natural gas carbon black product having at least one organic group, the organic group comprising a) at least one C? -C? 2 alkyl group and ) at least one ionic group, at least one ionizable group, or a mixture of an ionic group and an ionizable group, wherein at least one alkyl group of the organic group is directly attached to the natural gas carbon black. 16. The gel composition according to claim 15, characterized in that the ionic or ionizable group is selected from the group consisting of: a sulphonic acid of ethane or a salt thereof. 17. The gel composition according to claim 15, characterized in that the gel component is selected from the group consisting of metal oxide gels and polymer gels. 18. The gel composition according to claim 15, characterized in that the gel component is silica. 19. The thermal insulation comprising: a gel composition comprising a carbonaceous component attached to a gel component. 20. The thermal insulation according to claim 19, characterized in that the carbonaceous component is a natural gas carbon black that can be bonded to a gel component in which the gel component is silica. Summary New gel compositions comprising a carbonaceous component bound to a gel component. Preferably, the carbonaceous component is selected from the group consisting of: natural gas carbon blacks, carbon fibers, activated carbons and graphitic carbons; and the gel component is selected from the group consisting of: metal oxide gels and polymeric gels. Also disclosed are new gel compositions comprising: a gel component and a natural gas carbon black product having at least one organic group, the organic group comprising at least one aromatic group, and b) at least one ionic group, at least one ionizable group, or a mixture of an ionic group and an ionizable group, wherein at least one aromatic group of the organic group is directly attached to the natural gas carbon black. Further new gel compositions are disclosed which comprise: a gel component and a natural gas carbon black product having at least one organic group, the organic group comprising a) at least one C1-C12 alkyl group, and b) at least one ionic group, at least one ionizable group, or a mixture of an ionic group and an ionizable group, wherein at least one alkyl group of the organic group is directly attached to the natural gas carbon black. The uses for the gel compositions are also set forth.