WO2003087013A1 - A composite body of silicon carbide and binderless carbon and process for producing - Google Patents

A composite body of silicon carbide and binderless carbon and process for producing Download PDF

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Publication number
WO2003087013A1
WO2003087013A1 PCT/US2003/011206 US0311206W WO03087013A1 WO 2003087013 A1 WO2003087013 A1 WO 2003087013A1 US 0311206 W US0311206 W US 0311206W WO 03087013 A1 WO03087013 A1 WO 03087013A1
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WIPO (PCT)
Prior art keywords
recited
silicon carbide
carbon
binderless
composite body
Prior art date
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Ceased
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PCT/US2003/011206
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English (en)
French (fr)
Inventor
Joseph F. Demendi
Xin E. Chen
William R. Clemens
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John Crane Inc
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John Crane Inc
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Publication date
Application filed by John Crane Inc filed Critical John Crane Inc
Priority to EP03723985A priority Critical patent/EP1499572A4/en
Priority to AU2003230879A priority patent/AU2003230879B2/en
Priority to KR10-2004-7016097A priority patent/KR20050003355A/ko
Priority to BR0309201-1A priority patent/BR0309201A/pt
Priority to JP2003583972A priority patent/JP2005523225A/ja
Priority to CA002480156A priority patent/CA2480156C/en
Priority to MXPA04009915A priority patent/MXPA04009915A/es
Publication of WO2003087013A1 publication Critical patent/WO2003087013A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Definitions

  • the present invention relates to a composite body of silicon carbide and binderless allotropic carbon, and to the process of making such a composite body. More specifically, it relates to making such composite bodies for use in tribological applications such as mechanical seals, bearings and other sliding or rubbing components, which require good durability and wear performance under less than ideal lubricating conditions.
  • Boecker et al describes a graphite containing silicon carbide produced by pressureless sintering in U.S. Patent No. 4,525,461, issued on June 25, 1985. This approach utilizes addition of small graphite particles not exceeding an average size of 8 micrometers. However, the addition of the amount and size of the graphite particles is limited by this procedure due to the inherently high shrinkage associated with the direct sintering process.
  • Moehle et al describes a graphite containing silicon carbide in U.S. Patent No. 4,942,145, issued on July 17, 1990. This approach is based upon using an organosihcon binder such as polysilazanes, silicon carbide, and graphite fillers.
  • organosihcon binder such as polysilazanes, silicon carbide, and graphite fillers.
  • the graphite containing silicon carbide is mixed with polysilazane dissolved in an organic solvent, dried, molded and pyrolyzed around 1300°C.
  • such graphite containing silicon carbide sample was found to have 2.18 gM/CM3 density and a bending strength of 15.9 ] ⁇ g/MM2 (22,600 psi).
  • the silicon carbide molding powder using sub-micrometer silicon carbide and the appropriate additives is produced by similar spray drying technique.
  • the desired amount of graphite agglomerates are added and blended with the spray dried silicon carbide molding powders.
  • the desired graphite containing silicon carbide composite parts are processed according to teaching of U.S. Patent No. 4,041,117 by Prochazka, issued on August 9, 1977.
  • the slurry is spray dried to form spherical granules having an average size of less than 500 micrometers.
  • the spray dried molding compound is pressed to the desired shape, carbonized to 850T, and sintered at preferably 2000 to 2200°C in inert atmosphere such as helium or argon.
  • the sintered silicon carbide-graphite composite contains between 2 to 30 percent by weight carbon bonded graphite.
  • the composite, especially at higher carbon bonded graphite concentrations, contains structural defects described in the patent as microcracks.
  • the shape of the carbon bonded graphite particles is also irregular, which maximizes stress concentrations in the sintered composite material.
  • the large and uncontrolled particle size distribution of the resin coated graphite affects the reproducibility of the inherently high shrinkage of the silicon carbide matrix.
  • the invention disclosed and claimed herein comprises a composite body of silicon carbide having binderless allotropic carbon distributed throughout, a process for producing such a composite body, and an article of manufacture for use in tribological applications, which utilizes such a composite body.
  • the steps for producing the composite body include forming a mixture of silicon carbide and binderless, allotropic carbon-yielding precursor granules, then shaping and heating the mixture to form the desired composite body.
  • Articles made according to the present invention can be produced in a variety of shapes for use in tribological applications such as mechanical
  • Fig. 1 is a schematic description of the process for producing a silicon carbide- binderless carbon composite body in accordance with the present invention.
  • Fig. 2 shows the surface topography of a polished ring of the composite body, formed from a mixture of spray dried silicon carbide powder and green coke.
  • Fig. 3 shows the surface topography of a polished ring of the composite body, formed from a mixture of spray dried silicon powder and spray dried phenolic resin.
  • Fig. 4 shows the surface topography of a polished ring of the composite body, formed from a mixture of spray dried silicon carbide powder and spherical green mesophase microbeads.
  • the performance characteristics of a self-sintered silicon carbide in rubbing applications for example, in a mechanical face seal, a bearing, etc.
  • binderless, carbon- yielding precursor granules such as uncalcined green coke, phenol formaldahyde resin, spherical mesophase carbon, coal tar pitch, petroleum pitch, carbon-yielding resins, bitumen, bituminous coal, petroleum coke, lampblack, carbon black, or other carbonaceous granules into a self-sintered silicon carbide matrix.
  • Articles made according to the present invention can be produced in variety of shapes such as rods, tubes, plates, etc.
  • Silicon carbide composite bodies made according to the present invention may be produced according to any of a number of standard pressureless, self-sintered silicon carbide manufacturing processes. The schematic description of the processes for producing the silicon carbide-binderless carbon composite body is shown in Figure 1.
  • alpha phase silicon carbide produced by the Acheson process
  • the alpha silicon carbide contains a variety of different crystal structures with hexagonal and rhombohedral polytypes being the most predominant.
  • the silicon carbide made by Acheson process can be green or black depending upon the type and amount of impurities.
  • the green colored silicon carbide contains less impurities than the black.
  • the major impurities in the black silicon carbide grains are aluminum, carbon and free silicon.
  • the preferred silicon carbide for the present invention is green. However, the more abundant black silicon carbide can also be used.
  • Beta phase silicon carbide, amorphous silicon carbide, alpha phase silicon carbide and the mixture thereof can also be used, and the silicon carbide can have spherical, ellipsoidal or irregular morphology.
  • the silicon carbide powder for the self-sintered process must have fine particle size, predominantly in the sub-micrometer range.
  • the surface area of the silicon carbide powder is preferred to be in the 5 to 15 square meter per gram range determined by the B.E.T. method.
  • the coarse silicon carbide can be milled to the desired particle size range by standard ball milling technique, utilizing silicon carbide grinding media. However, it may require further chemical purification to remove impurities that inhibit the sintering process.
  • the starting silicon carbide feed stock should be smaller than 100 micrometers to achieve economical milling throughput.
  • the milling process is the preferred method due to the simultaneous milling and mixing of the desired amount of sintering aid, such as boron carbide, which is required for the pressureless self- sintering process. Elemental boron, aluminum, beryllium, carbon, or a combination thereof can also be used to catalyze the silicon carbide densification process.
  • the preferred boron carbide concentration is about 0.5 - 2.0 weight percent.
  • sub- micrometer boron carbide is available on a commercial scale from a number of vendors.
  • the silicon carbide having the desired particle size distribution contains a considerable amount of surface oxides. To facilitate sintering, these surface oxides are removed by reacting the powder with uncombined carbon according to the following equation:
  • the uncombined carbon is uniformly distributed over the surface of the silicon carbide particles. This can be achieved by adding liquid carbonaceous precursor to the silicon carbide powder. Although any water or solvent soluble carbonaceous precursor can be used, water soluble phenol formaldehyde resin is the preferred material in the 2 to 8 weight percent range based upon the silicon carbide content of the batch.
  • Another additive needed to facilitate the formation of a strong green body is preferably a water soluble, organic resin material having very low char yield.
  • acceptable temporary fugitive binders include soluble polyvinyl alcohol, acrylic water soluble resin, phenolic resin, coal tar pitch, and other carbonaceous materials.
  • an organic lubricating compound such as polyvinyl alcohol, oleic acid, acrylic resin, wetting agent, stearic acid, paraffin wax, or fatty acids must be added to the batch.
  • concentration of this additive is in the range of 0.5 to 3.0 weight percent based upon the silicon carbide content, or 0.1 to 15.0 weight percent of the total mixture.
  • the key ingredient for producing a self-lubricating silicon carbide - carbon composite is the binderless, carbon-yielding precursor granules.
  • the linear shrinkage of the artifact produced can be as much as 17 percent.
  • incorporating non-shrinking carbon such as graphite will either inhibit the densification process or yield structural defects.
  • the particle size and concentration of the graphite has to be small and low respectively.
  • free graphite or carbon can be incorporated into the silicon carbide matrix at a high concentration without structural defects by utilizing binderless, carbon-yielding precursor granules such as uncalcined green coke, phenol formaldehyde resin, spherical mesophase carbon, and other carbonaceous granules.
  • the green powder has a typical composition of 93.5 percent carbon, 4.5 percent hydrogen, 1.0 percent nitrogen and 1.0 percent oxygen.
  • the average particle size of the green powder is available in the 1 to 80 micrometer range.
  • the concentration of mesophase microbeads in the silicon carbide matrix can range from 2 to 30 weight percent.
  • the average particle size can range from 25 to 80 micrometers.
  • the highly oriented aromatic precursor will shrink and convert to graphite.
  • the use of spherical particles will also yield a silicon carbide - carbon composite with less internal stress than a composite produced from irregular shape carbon. Nevertheless, highly oriented green needle coke can also be used for producing silicon carbide - graphite composite.
  • the silicon carbide-carbon composite can be tailor-made according to the application requirement.
  • the tribological performance of silicon carbide - carbon matrix can be controlled by either the use of a graphite-yielding, highly oriented aromatic precursor, or an amorphous carbon-yielding, less oriented heterocyclic carbonaceous precursor.
  • the process of producing self-sintered silicon carbide - carbon composite starts with making a silicon carbide water slurry of fine silicon carbide powder.
  • the desired amount of submicron boron carbide, or other sintering aid is added to the slurry. Since the ultrafine silicon carbide contains a considerable amount of surface oxides, one must add a carbonaceous precursor such as water soluble phenol formaldehyde resin to the slurry. The preferred amount of resin is in the range of 2 to 8 weight percent of the silicon carbide powder.
  • a temporary binder preferably a water soluble acrylic resin, is added to silicon carbide slurry. The preferred amount of temporary binder is in the range of 2 to 8 percent of the silicon carbide powder.
  • An organic lubricating compound such as stearic acid, is also added to the slurry in the range of 0.5 to 3.0 weight percent based upon the silicon carbide content of the slurry.
  • the preferred method of adding this ingredient is by dry blending it with the spray dried silicon carbide slurry.
  • the slurry containing all the ingredients described above is spray dried following standard spray drying technology. Then, the spray dried particles are mixed with the desired amount of carbon-yielding precursor granules. Next, the mixture is pressed into the desired shape, cured, and green machined if needed.
  • the coking and sintering processes are carried out separately in different equipment.
  • First the artifacts are heat treated in an inert atmosphere to about 600°C.
  • the artifacts can be sintered under reduced pressure to facilitate the carbon surface oxide reactions.
  • the sintering is carried out first in a vacuum up to 1800°C, then in argon or helium at 300 to 500 torr absolute pressure
  • the peak sintering temperature is in the range of 2100 to 2200°C.
  • Oleic Acid 1.0 The submicron silicon carbide powder had a B.E.T. surface area of 15m 2/ g. The median particle size was 0.6 micron. A commercially available boron carbide was used, f having a B.E.T. surface area of 15-20 m g and a median particle size of 0.5 micron.
  • the liquid water based phenolic resin had 70 percent solid content.
  • the water emulsion acrylic resin had 45 percent solid content.
  • the polyvinyl alcohol had 21 percent solid content.
  • a distilled, tallow based oleic acid was used in this formulation.
  • Green coke having a volatile content of 14 percent was milled and screened through 100 mesh to produce a powder having particle size less than 150 micrometers. This powder was dry blended with the silicon carbide molding powder described in Example 1. A mixture was made according to the following formula:
  • Example 4 The above mixture was blended for five minutes in a V-shaped blender equipped with an intensifier bar. Tubes were isostatically pressed from the above described powder mixture at 17,000 psi pressure. The molded tubes were cured to 175°C and green machined to the desired ring configuration. The machined rings were first carbonized to 600°C in nitrogen atmosphere, then sintered in a vacuum to 2100°C. The density of the sintered parts were measured to be about 2.95g/cm 3 . Figure 3 shows the surface topography of the polished rings. It must be noted that the rings made according to the described process were found to be free of microcracks and/or interconnected porosity. The rings were also tested and passed for imperviousness using nitrogen at 100 psig. Example 4
  • Spherical green mesophase carbonaceous powder made from coal tar pitch has been used as an additive to the silicon carbide molding powder.
  • the average size of the mesophase microbeads was about 25 micrometers.
  • the following formula was used:

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EP03723985A EP1499572A4 (en) 2002-04-12 2003-04-10 COMPOSITE BODY OF SILICON CARBIDE AND BINDER-FREE CARBON AND MANUFACTURING METHOD THEREFOR
AU2003230879A AU2003230879B2 (en) 2002-04-12 2003-04-10 A composite body of silicon carbide and binderless carbon and process for producing
KR10-2004-7016097A KR20050003355A (ko) 2002-04-12 2003-04-10 탄화규소 및 무결합제성 탄소로 이루어진 복합체 및 이의제조방법
BR0309201-1A BR0309201A (pt) 2002-04-12 2003-04-10 Corpo composto de carbureto de silìcio e carbono sem aglutinante e processo para produção do mesmo
JP2003583972A JP2005523225A (ja) 2002-04-12 2003-04-10 炭化ケイ素とバインダーレス炭素との複合体ならびに製造方法
CA002480156A CA2480156C (en) 2002-04-12 2003-04-10 A composite body of silicon carbide and binderless carbon and process for producing
MXPA04009915A MXPA04009915A (es) 2002-04-12 2003-04-10 Cuerpo compuesto de carburo de silicio y carbono sin aglutinante y proceso de produccion de los mismos.

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