US3846084A - Chromium-chromium carbide powder and article made therefrom - Google Patents

Chromium-chromium carbide powder and article made therefrom Download PDF

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US3846084A
US3846084A US00388433A US38843373A US3846084A US 3846084 A US3846084 A US 3846084A US 00388433 A US00388433 A US 00388433A US 38843373 A US38843373 A US 38843373A US 3846084 A US3846084 A US 3846084A
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chromium
powder
carbide
coating
carbon
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J Pelton
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Praxair ST Technology Inc
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Union Carbide Corp
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Priority to US00388433A priority Critical patent/US3846084A/en
Priority to US482990A priority patent/US3901689A/en
Priority to AU71306/74A priority patent/AU7130674A/en
Priority to CA206,050A priority patent/CA1036390A/fr
Priority to DE19742438998 priority patent/DE2438998B2/de
Priority to FR7428281A priority patent/FR2245774B1/fr
Priority to IT52604/74A priority patent/IT1018969B/it
Priority to CH1107774A priority patent/CH594740A5/xx
Priority to SE7410371A priority patent/SE7410371L/xx
Priority to GB35735/74A priority patent/GB1484583A/en
Priority to ES429279A priority patent/ES429279A1/es
Priority to IL45473A priority patent/IL45473A/en
Priority to JP9245874A priority patent/JPS548361B2/ja
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Assigned to MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. reassignment MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MORGAN BANK ( DELAWARE ) AS COLLATERAL ( AGENTS ) SEE RECORD FOR THE REMAINING ASSIGNEES. MORTGAGE (SEE DOCUMENT FOR DETAILS). Assignors: STP CORPORATION, A CORP. OF DE.,, UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,, UNION CARBIDE CORPORATION, A CORP.,, UNION CARBIDE EUROPE S.A., A SWISS CORP.
Assigned to UNION CARBIDE CORPORATION, reassignment UNION CARBIDE CORPORATION, RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: MORGAN BANK (DELAWARE) AS COLLATERAL AGENT
Assigned to UNION CARBIDE COATINGS SERVICE TECHNOLOGY CORPORATION reassignment UNION CARBIDE COATINGS SERVICE TECHNOLOGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: UNION CARBIDE COATINGS SERVICE CORPORATION
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B55/00—Internal-combustion aspects of rotary pistons; Outer members for co-operation with rotary pistons
    • F02B55/08—Outer members for co-operation with rotary pistons; Casings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S75/00—Specialized metallurgical processes, compositions for use therein, consolidated metal powder compositions, and loose metal particulate mixtures
    • Y10S75/956—Producing particles containing a dispersed phase
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12146—Nonmetal particles in a component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Definitions

  • a composite powder for use in producing articles or coatings having unique wear and frictional characteristics consisting essentially of a chromium matrix with at least one chromium carbide taken from the class of carbides consisting of Cr C Cr C and Cr C and each particle containing from about 0.2 wt. percent to about 5.4 wt. percent carbon.
  • This invention relates to a novel powder for use in producing articles and coatings having unique wear and frictional characteristics. More particularly this invention relates to powders which are to be applied as a coating on a substrate using metal spraying techniques and to the articles and coatings made thereby.
  • Chromium metal has been used as an electroplated coating (i.e., hard chromium plating") for many years to restore Worn or damaged parts to their original dimensions, to increase wear resistance, reduce friction, and provide corrosion resistance. Chromiums excellent wear and frictional characteristics have been attributed to its low ratio of energy of adhesion to hardness when mated against a number of materials that are commonly used in engineering applications. Hard chromium electroplate, however, has a number of limitations. The electroplating of chromium is economically feasible when the configuration of the part is relatively simple and the number of the parts and/ or their size is relatively small. When the configuration of the part becomes complex. obtaining a uniform coating thickness by electro-deposition is ditficult and requires precise placement of electrodes and thieves.
  • An alternative method of depositing chromium metal is by metal spraying such as with a plasma or detonation gun. These methods offer a number of processing advantages. Surface preparation is relatively simple and inexpensive. The coatings can be applied to almost any metallic substrate without using undercoats. The rate of deposition is very high so that a large volume of parts can be coated with a minimal capital investment. The coating thickness can be controlled very closely so that any subsequent finishing can be kept to a minimum.
  • plasma-deposited chromium is not as wear-resistant at ambient temperature as hard electroplated chromium. This is because the wear-resistance of chromium plate is not an inherent property of elemental chromium but is believed to arise largely from impurities and stresses incorporated in the coating during plating. Plasma deposited chromium being a purer form of chromium thus lacks the wear resistances of hard chromium plate while retaining the corrosion-resistance characteristics of chromium.
  • coatings made by the plasma or detonation-gun process can be made that are remarkably superior to hard chromium electroplate in compatibility, frictional characteristics and wear resistance by incorporating a dispersion of chromium carbide particles in a chromium matrix.
  • Coatings of this type have been made from mechanical mixtures of powders as described in my co-pending ap plication Ser. No. 388,434 filed Aug. 15, 1973. While such mechanical mixtures are advantageous, there are certain limitations to the quality of coatings made from them. Both plasma and detonation-gun deposition result in a coating with a multilayer structure of overlapping, thin, lenticular particles or splats. Each coating particle or splat is derived from a single particle of the powder used to produce the coating. There is little, if any, combining or alloying of two or more powder particles during the coating deposition process.
  • each splat is a mixture of chromium and chromium carbide. This in turn requires that each powder particle contain a mixture of chromium metal and chromium carbide.
  • each splat is a mixture of chromium metal and chromium carbides.
  • Another object is to provide such a powder which contains chromium and chromium carbide in each particle.
  • a further object is to provide a method for making such powder.
  • Yet another object is to provide a chromium/chromium carbide coating having superior property to hard chromium electroplate.
  • Still another object is to provide a coated trochoid surface for a rotary combustion engine.
  • FIG. 1 is a pictorial representation of the structure obtained by depositing mechanical mixture of chromium and chromium carbides
  • FIG. 2 is a pictorial representation of the type structure obtained by depositing the powder of this invention.
  • FIGS. 3, 4 and 5 show possible distribution of the carbide phases in the powder particles
  • FIG. 6 shows the variation of wear scar volumes with carbon content of the powder used to produce the coating tested, compared to coatings of hard chrome plate
  • FIG. 7 shows the hardness of coatings obtained with powders of various carbon content compared to hardness of hard chrome plate.
  • the methods of this invention produce a composite powder containing the desired amount of chromium carbide and chromium in which substantially each particle contains at least some chromium and chromium carbide.
  • Examples of the possible distributions of the carbide phases in the powder particles are shown in FIGS. 3, 4 and 5.
  • the exact composition of the carbide phases in the powder or the distribution of the carbide phases as shown in FIGS. 3, 4 and 5 are not important, only the total carbon content, since during deposition the particles become essentially completely molten.
  • the carbides reprecipitate from the melt forming Cr C Cr C or Cr C or a combination of these, depending on the total amount of C present and the rate of solidification.
  • the preferred composition results in a predominantly 'Cr C dispersion.
  • the material is prepared by chemical reaction of an intimate mixture of a source of Cr and a source of C; temperatures of 1000-1400" C. are suitable for solid state reactions. Times of from about l-5O hours are suitable. Temperatures in excess of l500 C. are required for production of the powder by melting referred to hereinafter.
  • the principal reaction involved is The principal product is Cr C with minor amount of CI'qCg and CI'3C2.
  • reaction (1) When oxygen is present in the Cr (as Cr O or Cr O is used as the Cr source, reaction (1) is preceded or accompanied by The Cr formed in reaction (2) may react with C present in excess of the amount required to bring reaction (2) to completion to form Cr carbide by reaction (1).
  • the source of Cr may be commercial Cr powder (e.g., Union Carbide Mining and Metals Division electrolytic chromium powder), Cr 'O as in reaction (2), or any compound that decomposes on heating or by reaction with C or H on heating to form essentially Cr and volatile products.
  • commercial Cr powder e.g., Union Carbide Mining and Metals Division electrolytic chromium powder
  • Cr 'O as in reaction (2)
  • any compound that decomposes on heating or by reaction with C or H on heating to form essentially Cr and volatile products may be commercial Cr powder (e.g., Union Carbide Mining and Metals Division electrolytic chromium powder), Cr 'O as in reaction (2), or any compound that decomposes on heating or by reaction with C or H on heating to form essentially Cr and volatile products.
  • the source of carbon may be any commercial carbon consisting of essentially elemental C and volatile impurities. Decolorizing carbon, lampblack, and powdered graphite have been used with equal success.
  • a higher carbide of Cr may be used as the C source, since it may react with Cr to form another carbide, the resulting product having the characteristic intimacy of the invention.
  • a gaseous hydrocarbon or hydrocarbon/hydrogen gas mixture is also a suitable carbon source, provided its composition is such that the carbon activity is high enough to permit carbide formation.
  • This reaction has not been used directly, but powdered mixtures of Cr and C heated in a H atmosphere are found to consist, after reaction, of two-phase particles in which the carbide phase essentially encapsulates the original Cr particles as shown in FIG. 3.
  • This structure differs from that found in similar mixtures heated in the absence of H which show mainly isolated areas of carbide formation on the Cr particles, as shown in FIG. 4, corresponding to points of 4 solid-solid contact of the original Cr and C particles.
  • the difference in structure is clear evidence that carbon has been transported through the vapor phase in the H atmospbere, by the reaction occurring at the carbon particles and the reaction also occurs.
  • the intimately mixed Cr/ Cr carbide structure may also be prepared by melting Cr and C (present either as the element or as a Cr carbide) mixtures of appropriate total analysis, allowing the homogeneous liquid to freeze and the Cr carbide to precipitate out, and then crushing the solidified melt to powder. Temperatures greater than 1500 C. are required for this method. Limitations of higher melting temperatures and difficulty in crushing the solidified melt practically limit this method of preparation to carbon content of 3% by weight or more.
  • the reaction of Cr and C is preferably carried out in vacuum because this promotes the removal of the gaseous CO formed in reaction (2) or (6).
  • the vacuum does not have to'be extraordinarily good, ultimate system pressures between 0.01 and microns having been found 0 to yield products of essentially the same oxygen content.
  • the reaction can also 'be carried out in any atmosphere with oxygen potential sutficiently low to prevent oxidation of Cr.
  • a hydrogen atmosphere is quite suitable and is particularly useful for the preparation of a composite of low C content with a uniform carbide distribution, since the H takes part in the reaction and promotes uniform distribution.
  • the product of the Cr+C or Cr O +C reaction is a sintered cake, however the reaction is carried out. Sintering is least, and reduction to powder by ball-milling, hammer-milling, and other conventional techniques is easier, when the Cr O +C reaction is used or when the Cr+C reaction is carried out in H Lower reaction temperatures favor ease of reduction when the Cr+C reaction is carried out in vacuum.
  • the carbide distribution within the powder particle is a. function of the method of production.
  • the predominant form is that shown in FIG. 4 because the carbon tends to react with the chromium surface closest to it.
  • the finer and more uniform the distribution of carbon in the starting mixture the more uni-form the distribution of carbides around the surface of the chromium will be.
  • the ultimate extension of this trend is achieved when a gaseous source of carbon is used either by directly supplying a hydrocarbon gas or by heating the solid carbon plus chromium in a hydrogen atmosphere (which results in a hydrocarbon gas).
  • the carbide distribution which results is like that in FIG. 3.
  • a distribution of carbon particles throughout the powder particle, FIG. 5, may result when a solid ingot of the proper total composition is reduced to powder.
  • Oxygen content (in the range 0.03 to 1%) does not affect the wear properties of coatings made from powders of this invention.
  • the carbon content of the powder of this invention may be between 0.2% and 5.4% by Weight.
  • plasma deposits made from the powder are superior in tests to similar deposits made from commercial electrolytic chromium powder.
  • the high end of the range is defined by the complete conversion to the compound Cr C which contains 5.6% by weight; at this point, the material no longer contains free Cr.
  • the wear resistance of coatings made from the powder varies with carbon content as shown in the band curve on FIG. 6.
  • the range of values observed for commercial hard chrome plate is also shown in the FIG. 6 by the cross-hatched area adjacent to the vertical axis.
  • the optimum composition is believed to lie in the range 0.81.7% C. by weight, and may vary somewhat with the method of preparation. Coatings, made from powders in this composition range, are equivalent to or superior to commercial electrolytic Cr plate in laboratory lubricated rubbing wear tests at high load (see FIG. -6). Furthermore, the hardness, see FIG. 7, is at a minimum, making it possible to readily finish the coating with conventional grinding or honing tools. Low-surface-speed, high-deposition-rate plasma plating produces well-bonded, uncracked coatings.
  • powders containing about 1 wt. percent carbon produce plasma deposited coatings on interior trochoid surfaces of rotary combustion engines which have remarkedly and unexpectedly superior properties, as shown hereinafter in Example 9.
  • the coating of this invention is characterized -by the presence in substantially every splat of both Cr and Cr carbide.
  • the relative amounts of Cr and Cr Carbides will vary between splats as a necessary result of the use of powder with a range of partial sizes and advantitious difference in the degree to which each Cr particle is carburized and in the conditions to which the various particles are subjected in passing through the coating device.
  • the coating of this invention is distinguished from that produced from a powder which is a simple mixture of Cr and Cr carbide, which is pictorially represented in FIG. l, in that the splats in the latter type of coating are each individually either all Cr or all Cr carbide.
  • FIG. 2 is to be understood as being merely illustrative of one feature of the distribution of the carbides in the coating.
  • the majority of the carbide particles were found to be of sub-micron size and most were predominantly in the shape of a lace-like network, suggesting that the coatings contained fine-grained interlocking, continuous networks of both carbide and Cr, the separation between the interstices of these networks being so small that they are not resolvable in optical microscopy.
  • the coatings produced with the powder of this invention have a number of advantages in addition to the general procesing advantages previously described as being associated with metal spray deposition.
  • Coatings are superior to those formed by the plasma deposition of commercial electrolytic chromium powder in that increased wear resistance and resistance to spalling are found, though there is minimal increase in hardness as measured by diamond pyramid indentations.
  • Coatings are superior to coatings in which nitrogen rather than carbon is the strengthening additive, in that carbide-strengthened material is much less brittle and much less prone to spalling.
  • Coatings of this invention performed far superior to electrolytic chrome plate coating on internal troc-hoid surfaces in rotary combustion engines as described in detail in Example 9.
  • EXAMPLE 1 8879 grams of Union Carbide Mining and Metals Division electrolytic chromium, screened through a 230-mesh sieve, was mixed with 200 grams of Fisher Scientific Company Norit A decolorizing carbon, similarly screened, and blended for two hours in a cone blender. A portion of this mixture was used to fill eight pans, each about 0.6 cm. deep, so that each pan contained between 210 and 230 grams of the mixture. The pans were vertically stacked in a vacuum furnace so that there was about 0.4 clearance between pans. The furnace was evacuated slowly to about 500-micron pressure and then more rapidly to about 0.5 micron, using an oil-diffusion pump.
  • the 325- mesh powders from the five furnace runs were individually analyzed for combined carbon, free carbon, and oxygen. All showed less than 0.1% free carbon, between 300 and 420 p.p.m. oxygen, and 1.05-1.08% combined carbon.
  • the distribution of carbides on the chromium was similar to that in FIG. 4.
  • EXAMPLE 2 Numerous mixtures differing only in the amounts of electrolytic chromium and decolorizing carbon used were processed as described in Example 1. The resulting powders, which ranged in carbon content from 0.6 to 5.4%, were used to form plasma-deposited coatings and tested for wear resistance using the techniques and procedures described in Example 1. Results of these tests are included in FIG. 6.
  • EXAMPLE 3 5400 grams of the same electrolytic chromium powder used in preceding examples was mixed with 87 grams of lampblack for one hour in a ceramic ball mill and then further mixed for 30 minutes in a cone blender. The mixed powders were loaded into pans and heated in the vacuum furnace exactly as described in Example 1. The product, after reduction to 325 mesh powder, analyzed 0.81% carbon and 335 ppm. oxygen. Plasma-deposited coatings were made and tested as described in Example 1. Scar volumes of 21 to 34x10 cm. were observed; these results are included in FIG. 6.
  • EXAMPLE 4 1476 grams of the same electrolytic chromium powder used in previous examples and 24 grams of the same screened decolorizing carbon used in previous examples were blended for two hours in a cone blender. Two boats, each 0.6 cm. deep and about 25 cm. long, were filled with this powder and placed in a cm. diameter ceramic tube furnace which was then sealed and evacuated with a mechanical pump for several hours. The furnace was then filled wtih hydrogen, heated to 1150 C., and maintained at this temperature for 22 hours, a flow of s.c.f.h. of hydrogen being maintained during the entire cycle. The
  • EXAMPLE 5 1773 grams of the same electrolytic chromium powder used in previous examples and 27 grams of the same screened decolorizing carbon used in earlier examples were blended by shaking and rolling in a 32-oz. glass jar. Using this powder, eight separate heats, each with between 80 and 105 grams of mix, were made in a 4 cm. diameter tube furnace. Each heat was for five hours at 1140 C. in a fiow of about 110 s.c.f.h. hydrogen without preliminary evacuation. The eight cakes were easily powdered by light hammering and when blended together and screened yielded a 325 mesh powder containing 1.13% C. and 1730 p.p.m. oxygen. The microstructure of this powder was very similar to that of the powder described in Example 4, consisting of chromium carbide surrounding chromium; in addition, a small amount of very fine precipitates was noted decorating the carbide-chromium interface.
  • EXAMPLE 6 A powder analyzing 1.13% C prepared by the method described in Example 1 was plated onto test blocks using a detonation gun. Microstructural differences between these coatings and those formed by plasma deposition were observed consistent with the difference in method of coating formation. For wear-test conditions identical with those employed for the plasma-deposited materials, scar volumes of 15-19 10" cm. were measured on the detonation-gun coatings.
  • EXAMPLE 7 Four hundred lb. of Cr O was blended with 94.8 lb. of lampblack in a twin-shell blended and then more thoroughly blended in a vibratory ball mill. This product was then mixed with 9.5 lb. cornstarch binder and enough water to make a mix suitable for forming briquettes in a standard briquetting press. It was then pressed into briquettes of about 2-inch maximum dimension and dried to remove excess water. The briquetted mix, charged to a large vacuum furnace in an 19-inch-deep bed covered with graphite plates, was heated to 1000 C. without letting the pressure exceed 5000 microns, held one hour at 1000 C. after the pressure had dropped below 2000 microns, then heated to 1400 C.
  • EXAMPLE 8 A mixture of 9900 grams of commercial grade electrolytic chromium sized to pass through a 65-mesh screen and grams of lampblack was blended dry, then mixed with water and cornstarch binder and formed into briquettes as described in Example 7. The briquetted mixture was then furnaced in vacuum under graphite covers for one hour to 1000 C. and for eight hours at 1385 C. The pressure in the furnace was maintained below 500 microns and was 50 microns at the end of the heating period. This material was then crushed, yielding about 30% 325 mesh material that analyzed 1.3% C and 721 ppm. oxygen, with a carbide dispersion similar to FIG. 4. Wear samples made from this powder by plasma deposition and tested in the standard manner exhibited wear scars of 18-23 x 10* cm.
  • EXAMPLE 9 Plasma deposited coatings produced in a manner similar to Example 1 were applied to the interior trochoid surfaces of rotary combustion engines fitted with graphite-aluminum composite rotor apex seals. The engines were run in laboratory test stands and in test vehicles. The trochoids were made of several different types of materials and of two different sizes, examples of which are shown in Table I. Over 3113 hr. of test stand operation have accumulated on the small engine size and 331 hr. of test stand and 7000 hr. of vehicle operation on the large engine size. In comparison with hard electroplated chromium the coatings of this invention showed the following advantages:
  • the wear of the mating seal surface is approximately one-half that caused by hard electroplated chromium, which is greater than .005 per 100 hr.
  • Performance of the coating is less sensitive to surface finish than hard electroplated chromium. There was no appreciable dilference in wear of either the coated surface or the seal surface between as-ground coating sur faces of 16 to 32 microinches rms and honed surfaces of approximately 6 rms. In comparison, a hard electroplated chromium surface must be finished to better than 6 microinches rms to perform satisfactorily.
  • Troehoid type size (in.) (1n.) (hr.) 100 hr.)
  • each particle has a core of chromium substantially completely surrounded by a shell of said chromium carbides.
  • each particle contains chromium and said chromium carbides on the surface of said chromium.
  • each particle contains chromium and said chromium carbides dispersed within said chromium.
  • An article consisting of a metal substrate having a coating thereon consisting essentially of a composite of chromium and at least one chromium carbide taken from the class consisting of Cr C CI'7C3 and Cr C wherein the composite coating contains from 0.2 wt. percent to about 5.4 wt. percent Carbon and the composite is characterized by a multilayer structure of overlapping thin,
  • a coated trochoid surface of a rotary combustion engine comprising a metallic surface having a coating thereon consisting essentially of a composite of chromium and at least one chromium carbide taken from the class consisting of Cr C Cr C and Cr C wherein the composite coating contains from 0.2 wt. percent to about 5.4 wt. percent Carbon and the composite is characterized by a multilayer structure of over-lapping thin, lenticular particles, each particle containing a mixture of said chromium and chromium carbides.
US00388433A 1973-08-15 1973-08-15 Chromium-chromium carbide powder and article made therefrom Expired - Lifetime US3846084A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US00388433A US3846084A (en) 1973-08-15 1973-08-15 Chromium-chromium carbide powder and article made therefrom
US482990A US3901689A (en) 1973-08-15 1974-06-25 Method for producing chromium-chromium carbide powder
AU71306/74A AU7130674A (en) 1973-08-15 1974-07-17 Chromium-chromium carbide powder
CA206,050A CA1036390A (fr) 1973-08-15 1974-07-31 Poudre de chrome et de carbure de chrome, et methode de preparation et article connexes
IL45473A IL45473A (en) 1973-08-15 1974-08-14 Chromium-chromium carbide powder,method for producing same and article made therefrom
IT52604/74A IT1018969B (it) 1973-08-15 1974-08-14 Polvere antiusura ed antifrizione a base di cromo e carburo di cromo e metodo per la sua produzione
CH1107774A CH594740A5 (fr) 1973-08-15 1974-08-14
SE7410371A SE7410371L (fr) 1973-08-15 1974-08-14
DE19742438998 DE2438998B2 (de) 1973-08-15 1974-08-14 Pulver zur herstellung von abriebbestaendigen ueberzuegen, verfahren zu seiner herstellung und seine verwendung
ES429279A ES429279A1 (es) 1973-08-15 1974-08-14 Procedimiento para preparar un polvo para uso de la produc-cion de articulos y revestimientos.
FR7428281A FR2245774B1 (fr) 1973-08-15 1974-08-14
JP9245874A JPS548361B2 (fr) 1973-08-15 1974-08-14
GB35735/74A GB1484583A (en) 1973-08-15 1974-08-14 Chromium-chromium carbide powder method for producing same and article made therefrom

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JP (1) JPS548361B2 (fr)
AU (1) AU7130674A (fr)
CA (1) CA1036390A (fr)
CH (1) CH594740A5 (fr)
DE (1) DE2438998B2 (fr)
ES (1) ES429279A1 (fr)
FR (1) FR2245774B1 (fr)
GB (1) GB1484583A (fr)
IL (1) IL45473A (fr)
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Cited By (15)

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US4530891A (en) * 1981-03-17 1985-07-23 Hoya Electronics Co., Ltd. Photo-mask blank for use in lithography including a modified chromium compound
US4617055A (en) * 1982-04-02 1986-10-14 Toyota Jidosha Kabushiki Kaisha Metal cored ceramic surfaced fine powder material and apparatus and method for making it
US4725508A (en) * 1986-10-23 1988-02-16 The Perkin-Elmer Corporation Composite hard chromium compounds for thermal spraying
US5835841A (en) * 1992-10-21 1998-11-10 Kabushiki Kaisha Toyota Chuo Kenkyusho Composite material and production thereof
US5863618A (en) * 1996-10-03 1999-01-26 Praxair St Technology, Inc. Method for producing a chromium carbide-nickel chromium atomized powder
US6071324A (en) * 1998-05-28 2000-06-06 Sulzer Metco (Us) Inc. Powder of chromium carbide and nickel chromium
US6503290B1 (en) 2002-03-01 2003-01-07 Praxair S.T. Technology, Inc. Corrosion resistant powder and coating
US20060110626A1 (en) * 2004-11-24 2006-05-25 Heraeus, Inc. Carbon containing sputter target alloy compositions
US20070062762A1 (en) * 2005-09-20 2007-03-22 Ernst Ach Elevator installation with drivebelt pulley and flat-beltlike suspension means
US20080274010A1 (en) * 2004-05-28 2008-11-06 Praxair Surface Technologies, Inc. Wear Resistant Alloy Powders and Coatings
US20090014505A1 (en) * 2006-12-15 2009-01-15 General Electric Company Braze materials and processes therefor
US20110014102A1 (en) * 2009-02-12 2011-01-20 A123 Systems, Inc. Materials and methods for the removal of sulfur compounds from feedstock
CN103420373A (zh) * 2013-08-01 2013-12-04 西安交通大学 一种耐高温腐蚀的Cr23C6 金属陶瓷制备方法
CN103468991A (zh) * 2013-08-01 2013-12-25 西安交通大学 一种提高Cr23C6 化合物抗氧化和高温力学性能的方法
US10343219B2 (en) * 2014-03-04 2019-07-09 University Of Florida Research Foundation, Inc. Method for producing nanoparticles and the nanoparticles produced therefrom

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JPS60191059A (ja) * 1984-03-10 1985-09-28 株式会社クボタ 高温鋼材搬送用炉外ロール
DE3546113A1 (de) * 1985-12-24 1987-06-25 Santrade Ltd Verbundpulverteilchen, verbundkoerper und verfahren zu deren herstellung
DE102005020999A1 (de) * 2005-05-03 2006-11-09 Alfred Flamang Verfahren zur Beschichtung von verschleißbeaufschlagten Bauteilen und beschichtetes Bauteil
EP1923480A3 (fr) * 2005-07-22 2008-06-18 Heraeus, Inc. Procédé amélioré de fabrication d'une cible de pulvérisation
US20070017803A1 (en) * 2005-07-22 2007-01-25 Heraeus, Inc. Enhanced sputter target manufacturing method

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4530891A (en) * 1981-03-17 1985-07-23 Hoya Electronics Co., Ltd. Photo-mask blank for use in lithography including a modified chromium compound
US4617055A (en) * 1982-04-02 1986-10-14 Toyota Jidosha Kabushiki Kaisha Metal cored ceramic surfaced fine powder material and apparatus and method for making it
US4725508A (en) * 1986-10-23 1988-02-16 The Perkin-Elmer Corporation Composite hard chromium compounds for thermal spraying
US5835841A (en) * 1992-10-21 1998-11-10 Kabushiki Kaisha Toyota Chuo Kenkyusho Composite material and production thereof
US6228481B1 (en) 1992-10-21 2001-05-08 Kabushiki Kaisha Toyota Chuo Kenkyusho Composite material having discontinuous three-dimensional network structure and production thereof
US5863618A (en) * 1996-10-03 1999-01-26 Praxair St Technology, Inc. Method for producing a chromium carbide-nickel chromium atomized powder
US6071324A (en) * 1998-05-28 2000-06-06 Sulzer Metco (Us) Inc. Powder of chromium carbide and nickel chromium
US6254704B1 (en) * 1998-05-28 2001-07-03 Sulzer Metco (Us) Inc. Method for preparing a thermal spray powder of chromium carbide and nickel chromium
US6503290B1 (en) 2002-03-01 2003-01-07 Praxair S.T. Technology, Inc. Corrosion resistant powder and coating
WO2003074216A1 (fr) 2002-03-01 2003-09-12 Praxair S. T. Technology, Inc. Poudre et revetement resistant a la corrosion
US20080274010A1 (en) * 2004-05-28 2008-11-06 Praxair Surface Technologies, Inc. Wear Resistant Alloy Powders and Coatings
EP1662018A3 (fr) * 2004-11-24 2006-11-08 Heraeus, Inc. Composition d'une alliage pour une cible de pulverisation comprenant du carbone
EP1780300A2 (fr) * 2004-11-24 2007-05-02 Heraeus Inc Composition d'une alliage pour une cible de pulverisation comprenant du carbone
EP1780300A3 (fr) * 2004-11-24 2008-03-05 Heraeus Inc Composition d'une alliage pour une cible de pulverisation comprenant du carbone
US20060110626A1 (en) * 2004-11-24 2006-05-25 Heraeus, Inc. Carbon containing sputter target alloy compositions
EP1662018A2 (fr) * 2004-11-24 2006-05-31 Heraeus, Inc. Composition d'une alliage pour une cible de pulverisation comprenant du carbone
US20070062762A1 (en) * 2005-09-20 2007-03-22 Ernst Ach Elevator installation with drivebelt pulley and flat-beltlike suspension means
US8342386B2 (en) * 2006-12-15 2013-01-01 General Electric Company Braze materials and processes therefor
US20090014505A1 (en) * 2006-12-15 2009-01-15 General Electric Company Braze materials and processes therefor
US20110014102A1 (en) * 2009-02-12 2011-01-20 A123 Systems, Inc. Materials and methods for the removal of sulfur compounds from feedstock
US8956479B2 (en) * 2009-02-12 2015-02-17 A123 Systems Llc Materials and methods for the removal of sulfur compounds from feedstock
CN103420373A (zh) * 2013-08-01 2013-12-04 西安交通大学 一种耐高温腐蚀的Cr23C6 金属陶瓷制备方法
CN103468991A (zh) * 2013-08-01 2013-12-25 西安交通大学 一种提高Cr23C6 化合物抗氧化和高温力学性能的方法
CN103468991B (zh) * 2013-08-01 2015-07-01 西安交通大学 一种提高Cr23C6化合物抗氧化和高温力学性能的方法
US10343219B2 (en) * 2014-03-04 2019-07-09 University Of Florida Research Foundation, Inc. Method for producing nanoparticles and the nanoparticles produced therefrom
US11618077B2 (en) 2014-03-04 2023-04-04 University Of Florida Research Foundation, Inc. Method for producing nanoparticles and the nanoparticles produced therefrom
US11781199B2 (en) 2014-03-04 2023-10-10 University Of Florida Research Foundation, Inc. Method for producing nanoparticles and the nanoparticles produced therefrom

Also Published As

Publication number Publication date
DE2438998A1 (de) 1975-03-06
DE2438998B2 (de) 1977-03-17
CA1036390A (fr) 1978-08-15
IL45473A0 (en) 1974-11-29
SE7410371L (fr) 1975-02-17
GB1484583A (en) 1977-09-01
CH594740A5 (fr) 1978-01-31
FR2245774A1 (fr) 1975-04-25
ES429279A1 (es) 1976-08-16
IT1018969B (it) 1977-10-20
IL45473A (en) 1976-09-30
FR2245774B1 (fr) 1978-11-24
AU7130674A (en) 1976-01-22
JPS5050415A (fr) 1975-05-06
JPS548361B2 (fr) 1979-04-14

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