Chemistry of inorganic compounds – Carbon or compound thereof – Elemental carbon
Reexamination Certificate
1997-09-25
2001-03-06
Cain, Edward J. (Department: 1714)
Chemistry of inorganic compounds
Carbon or compound thereof
Elemental carbon
C423S449900
Reexamination Certificate
active
06197274
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to novel silica coated carbon blacks and a method s for their preparation. More particularly, the invention relates to improved silica coated carbon blacks produced from a fine dispersion, and to compositions and articles incorporating such carbon blacks.
DESCRIPTION OF BACKGROUND
Carbon blacks are widely used as pigments, fillers and reinforcing agents in the compounding and preparation of rubber and other elastomeric compounds. Carbon blacks are particularly useful as reinforcing agents in the preparation of elastomeric compounds used in the manufacture of tires.
Carbon blacks are generally produced in a furnace-type reactor by pyrolyzing a hydrocarbon feedstock with hot combustion gases to produce combustion products containing particulate carbon black. Carbon black exists in the form of aggregates. The aggregates, in turn are formed of carbon black particles. However, carbon black particles do not generally exist independently of the carbon black aggregate.
Carbon blacks are generally characterized on the basis of analytical properties, including, but not limited to particle size and specific surface area; aggregate size, shape, and distribution; and chemical and physical properties of the surface. The properties of carbon blacks are analytically determined by tests known to the art. For example, nitrogen adsorption surface area (measured by ASTM test procedure D3037-Method A) and cetyl-trimethyl ammonium bromide adsorption value (CTAB) (measured by ASTM test procedure D3765 [09.01]), are measures of specific surface area. Dibutylphthalate absorption of the crushed (CDBP) (measured by ASTM test procedure D3493-86) and uncrushed (DBP) carbon black (measured by ASTM test procedure D2414-93), relates to the aggregate structure. The bound rubber value relates to the surface activity of the carbon black. The properties of a given carbon black depend upon the conditions of manufacture and may be modified, e.g., by altering temperature, pressure, feedstock, residence time, quench temperature, throughput, and other parameters.
It is generally desirable in the production of tires to employ carbon black-containing compounds when constructing the tread and other portions of the tire. For example, a suitable tread compound will employ an elastomer compounded to provide high abrasion resistance and good hysteresis balance at different temperatures. A tire having high abrasion resistance is desirable because abrasion resistance is proportional to tire life. The physical properties of the carbon black directly influence the abrasion resistance and hysteresis of the tread compound. Generally, a carbon black with a high surface area and small particle size will impart a high abrasion resistance and high hysteresis to the tread compound. Carbon black loading also affects the abrasion resistance of the elastomeric compounds. Abrasion resistance increases with increased loading, at least to an optimum point, beyond which abrasion resistance actually decreases.
The hysteresis of an elastomeric compound relates to the energy dissipated under cyclic deformation. In other words, the hysteresis of an elastomeric composition relates to the difference between the energy applied to deform the elastomeric composition and the energy released as the elastomeric composition recovers to its initial unreformed state. Hysteresis is characterized by a loss tangent, tan &dgr;, which is a ratio of the loss modulus to the storage modulus (that is, viscous modulus to elastic modulus).
Tires made with a tire tread compound having a lower hysteresis measured at higher temperatures, such as 40° C. or higher, will have reduced rolling resistance, which in turn, results in reduced fuel consumption by the vehicle using the tire. At the same time, a tire tread with a higher hysteresis value measured at low temperature, such as 0° C. or lower, will result in a tire with high wet traction and skid resistance which will increase driving safety. Thus, a tire tread compound demonstrating low hysteresis at high temperatures and high hysteresis at low temperatures can be said to have a good hysteresis balance.
There are many other applications where it is useful to provide an elastomer exhibiting a good hysteresis balance, but where abrasion resistance is not an important factor. Such applications include, but are not limited to, tire components such as undertread, wedge compounds, sidewall, carcass, apex, bead filler and wire skim; engine mounts; and base compounds used in industrial drive and automotive belts.
Silica is also used as a reinforcing agent (or filler) for elastomers. However, using silica alone as a reinforcing agent for elastomer leads to poor performance compared to the results obtained with carbon black alone as the reinforcing agent. It is theorized that strong filler-filler interaction and poor filler-elastomer interaction accounts for the poor performance of silica used alone. The silica-elastomer interaction can be improved by chemically bonding the two with a chemical coupling agent, such as bis (3-triethoxysilylpropyl) tetra-sulfane, commercially available as Si-69 from Degussa AG, Germany. Coupling agents such as Si-69 create a chemical linkage between the elastomer and the silica, thereby coupling the silica to the elastomer.
When the silica is chemically coupled to the elastomer, certain performance characteristics of the resulting elastomeric composition are enhanced. When incorporated into vehicle tires, such elastomeric compounds provide improved hysteresis balance. However, elastomer compounds containing silica as the primary reinforcing agent exhibit low thermal conductivity, high electrical resistivity, high density, and poor processability.
When carbon black alone is used as a reinforcing agent in elastomeric compositions it does not chemically couple to the elastomer, but the carbon black surface provides many sites for interacting with the elastomer. While the use of a coupling agent is with carbon black might provide some improvement in performance to an elastomeric composition, the improvement is not comparable to that obtained when using a coupling agent with silica.
It is therefore desirable to combine the properties of silica and carbon black, particularly in elastomeric compositions. This can be accomplished by using silica coated carbon blacks. One process for making silica coated carbon blacks is as follows.
A carbon black slurry is prepared using a conventional method. An alkli silicate solution, for example, soda water glass (sodium silicate), is added to the slurry of carbon black. An acid, for example, sulfuric acid, is also added to the slurry. The pH of the slurry is maintained at greater than 7. The silica precipitates onto the carbon black surface. After a certain period of precipitation, the products are filtered and dried.
When using such conventional methods, however, the carbon black slurry does not form a good dispersion thus making the coating of the carbon black quite difficult.
SUMMARY OF THE INVENTION
The present invention is directed to a method of preparing silica coated carbon black, to the blacks so produced, and to compositions and articles incorporating the blacks, particularly elastomeric compositions. The invention is also directed to silica coated carbon black/elastomeric formulations using a variety of elastomers useful in a variety of product applications.
DETAILED DESCRIPTION OF THE INVENTION
The silica coated carbon blacks of the present invention may be obtained by coating a silicon oxide compound onto at least a portion of the carbon black aggregate, present in the form of a finely dispersed slurry. Any carbon black may be used.
A finely dispersed carbon black solution can be prepared using the methods described in U.S. patent application Ser. No. 08/356,653, entitled “Reaction of Carbon Materials with Diazonium Salts and Resultant Carbon Products,” filed Dec. 15, 1994, and WO 96/18688, the disclosures of which are fully incorporated by reference herein. Suitable methods are also disclose
Belmont James A.
Mahmud Khaled
Reznek Steven R.
Wang Meng-Jiao
Cabot Corporation
Cain Edward J.
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