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WO1983001917A1 - Poudre de carbure de nickel-chrome et procede de frittage - Google Patents

Poudre de carbure de nickel-chrome et procede de frittage Download PDF

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Publication number
WO1983001917A1
WO1983001917A1 PCT/US1982/001653 US8201653W WO8301917A1 WO 1983001917 A1 WO1983001917 A1 WO 1983001917A1 US 8201653 W US8201653 W US 8201653W WO 8301917 A1 WO8301917 A1 WO 8301917A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder
chromium
nickel
particles
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1982/001653
Other languages
English (en)
Inventor
Products Corporation Gte
David L. Houck
Richard F. Cheney
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osram Sylvania Inc
Original Assignee
GTE Products Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GTE Products Corp filed Critical GTE Products Corp
Publication of WO1983001917A1 publication Critical patent/WO1983001917A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/148—Agglomerating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • This invention relates to a powder for thermal spray applications and a process to produce it. 5
  • These powders require various agglomeration methods to make free flowing powders from normally non-flowing small particles.
  • One such agglomeration method is spray drying. Agglomerates are formed in spray drying by atom ⁇ izing a slurry of powder, binder and liquid into a dry-
  • the organic binder may cause fouling of the plasma gun due to vaporization of the organic.
  • Chromium carbide (Cr3C2) in combination with nickel-20% chromium powders are used to produce plasma- spray coatings for jet turbine engine applications.
  • These powders, as presently produced, are mechanical blends of the two components. As a result they have a tendency to become segregated both during shipment and durinq thermal spraying, yielding coatings which are not completely homogeneous. It is therefore desirable to have a powder which is comprised of particles each of which contains like amounts of both constituents.
  • an agglomerated powder which can be plasma densified to a thermal spray powder of a substantially uniform composition consisting essentially of nickel and chromium with the balance being about 50 to about 95 percent chromium carbide, said nickel and chromium being present in a weight ratio of about 1 part chromium to about 4 parts nickel.
  • the chromium may be partially or completely combined with the nickel to form a nickel- chromium alloy.
  • a powder blend is prepared consisting of 1 part chromium to 4 parts nickel with the balance chromium carbide.
  • the amount of chromium carbide present may be varied from 50 to 95 percent.
  • the nickel and chromium in the blend may be present as a mixture of elemental nickel powder and elemental chromium powder or as an alloy of nickel and chromium provided the ratio of chro ⁇ mium to nickel is about 1:4.
  • the overall powder blend has an average particle size less than about 10 microns.
  • the ratio of chromium to nickel is described in terms of the ratio of chromium to nickel excluding the chromium in the chromium carbide.
  • the powders are mixed by methods known in the art, such as by V-blending, tumbling or even by milling to obtain suitable particle sizes if size reduction is desired.
  • the uniform powder blend is next agglomerated by methods known in the art.
  • Such agglomeration tech- niques include forming powder compacts and subsequently crushing and screening them.
  • agglomeration by spray drying is in general preferred for its flexibility and economy of operation on a production scale as well as its close control over the size of the agglomerated particles produced.
  • the agglomerates may be conveniently classified to obtain a desired particle size distribution. It is generally desired to have at least 80% of the particles within a 50 micron average particle size range.
  • the classified agglomerates are passed through a furnace at low temperatures to decompose the binders used for agglomeration and further treated at high tem- peratures to strengthen them for subsequent handling.
  • binders include such materials as waxes and polyvinyl alcohols. As previously mentioned, these materials decompose during heat treatment, and thus contribute nothing to the constitution of the powder.
  • Alternative binders include soluble salts of nickel and chromium. These can be introduced into the slurry for spray drying. Upon drying, these salts serve to bind the fine powders - together to form agglomerates. When the agglomerates are passed through a high temperature furnace under a reducing atmosphere the binder decc-poses to yield the desired quantity of nickel and chro-ium. - -ft -
  • the sintered agglomerates can be subsequently • screened to yield a particle size distribution suitable for creating thermal sprayed coatings. Typically these distributions fall within two ranges, -200 +325 mesh or 5 -270 mesh.
  • the coarser distribution powder typically contains 10% +200 and 10% -325 material.
  • the finer distribution powder generally has a restriction .on the percentage of ultra fine particles allowable, e.g. a • maximum of 20% -20um.
  • the agglomerated and sintered par ⁇ ticles can also be subsequently plasma densified so as to produce fine, spherical, densified particles.
  • the densification process comprises entraining agglomerated powders in a carrier gas and feeding the entrained par-
  • the solidified particles are substantially spherical, have smooth surfaces and thus excellent flow-
  • the solidified particles have the same general size range as the starting material. How ⁇ ever, depending on the porosity of the starting mate ⁇ rial, they may have a smaller mean particle size, due to densification during melting. Preferably the melting
  • each par ⁇ ticle becomes prealloyed, i.e., the nickel and chromium alloy together and achieve intimate contact with the
  • a major portion and preferably substantially all of the densified powder consists essentially of particles 5 wherein each particle has a substantially uniform composition.
  • the powder particles preferably have essentially the same composition so that the powder is uniform particle to particle.
  • the plasma densification is preferably carried out 10 in a plasma flame reactor. Details of the principles and operation of such plasma flame reactors are well known.
  • the temperature within the plasma flame can be adjusted between 10,000 P and 30,000 F.
  • the temperature which the particles experience is a function of the rate 1 . 5 at which they are fed through the reactor.
  • Commercially available feeding devices allow rates between approximately 1/2 and 30 pounds per hour, depending on the bulk density of the material being fed.
  • Conditions for plasma densification are established such that the 0 particles reach a temperature at least above the melting point of the highest melting component and preferably below the vaporization point of the lowest vaporizing component.
  • the melted particles must be cooled at a rate suf- 5 ficient to solidify at least an outer layer of the par ⁇ ticles prior to their contact with a solid surface or with each other in order to maintain their sphericity and particle integrity. While any of several methods may be used to achieve this result, it has been found 0 convenient to feed the melted particles into a liquid cooled chamber containing a gaseous atmosphere. The chamber may conveniently serve as a collection vessel. After the powders have been plasma densified they can be classified to achieve the desired particle size 5 distribution for use in thermal spray applications. Particle size distributions similar to those for the agglomerated and sintered particles are desired.
  • the plasma densified powders can be crushed and classified to yield a powder with a finer particle size distribution, preferably one for which all the particles pass through a 270-mesh U.S. screen and at least 60 percent of the particles are less than 20 microns in average diameter.
  • a typical particle size distribution has less than 10 percent of the particles below about 5 microns.
  • the bulk density is from about 1.5 to about 3.0 grams/cc.
  • a sintered agglomerated powder is prepared by blending 80/20 nickel-chromium alloy powder, with a particle size less than approximately 10 micron with chromium carbide powder of the same particle size in amounts sufficient to result in a blend comprising 25% of the nickel-chromium alloy and 75% chromium carbide.
  • a slurry is prepared by combining the resulting powder- blend with polyvinyl alcohol in the " ratio of 98:2 respectively, with enough water to make a 50-80% solids concentration.
  • Spray drying is carried out by pumping the slurry at low pressure through a two fluid nozzle located at the top of a commercially available spray dryer. The slurry is continually agitated throughout the spray drying run. The atomization air pressure to the nozzle is 40-60 psi.
  • the inlet air temperature is 370 C to 430 C with an outlet temperature of 140 to 150 C.
  • the spray dried powder is slowly passed through a hydrogen furnace at 450 C to remove the organic - binder. It is then fired for approximately " 7 hours at 1000 C to strengthen the agglomerated particles.
  • the resulting particles are screened to yield powders with a -200+325 or a -.270+20 urn particle size distribution. These particles can then be used as thermal spray powders.
  • Example 1 The agglomerated spray dried and sintered particles of Example 1 are fed through a commercially available plasma torch into a jacketed water cooled collection tank. A mixture of 126 cubic feet per hour of argon and 70 cubic feet per hour of hydrogen is fed to the plasma torch. The torch power is about 28KVA. Nitrogen gas is fed to a powder feeder at the rate of 7 cubic feet per hour to entrain the powder which is fed through the torch. The powder produced is then screened as in Example 1. Analysis of the -270 powder indicated 15%-15 u particles. These prealloyed powder particles can then be used as a thermal spray powder. EXAMPLE 3 A plasma densified spray powder as produced in
  • Example 2 is comminuted and air classified to produce a powder having the following distribution: 60-90% less ' than 20 um and no more than 15% less than 5 microns.
  • EXAMPLE 4 A sintered agglomerate is prepared according to the process described in Example 1 by substituting nickel powder and chromium powder in the ratio of 4 to 1 for the 80/20 nickel-chromium alloy. Similar results are obtained.
  • EXAMPLE 5 A sintered agglomerate is prepared according to the process described in Example 1 by substituting nickel powder and chromium powder in the ratio of 4 to 1 for the 80/20 nickel-chromium alloy. Similar results are obtained.
  • EXAMPLE 5 A sintered agglomerate is prepared according to the process described in Example 1 by substituting nickel powder and chromium powder in the ratio of 4 to 1 for the 80/20 nickel-chromium alloy. Similar results are obtained.
  • EXAMPLE 5 A sintered agglomerate is prepared according to the process described in Example 1 by substituting nickel powder and chromium powder
  • Example 4 The sintered agglomerate powder of Example 4 is plasma densified according to the process as set forth in Example 2. The results were similar.
  • EXAMPLE 6 The densified plasma spray powder of Example 5 is comminuted and classified as in Example 3 with similar results.
  • EXAMPLE 7 The densified plasma spray powder of Example 5 is comminuted and classified as in Example 3 with similar results.
  • a sintered agglomerate is prepared according to the process described in Example 1 by substituting nickel acetate and chromic acetate or nickel nitrate and chro- mic nitrate for the nickel-chromium alloy.
  • the quantity of these salts is chosen such that upon decomposition they yield the proper ratios of nickel to chromium and chromium carbide. Polyvinyl alcohol is not required.
  • Example 7 The agglomerated spray dried and sintered particles of Example 7 are fed through a commercially available plasma torch into a jacketed water cooled collection tank. A mixture of 126 cubic feet per hour of argon and 70 cubic feet per hour of hydrogen is fed to the plasma torch. The torch power is about 28 KVA. Nitrogen gas is fed to the powder feeder at the rate of 7 cubic feet per hour to entrain the powder which is fed through the torch. The powder produced is then screened as in Example 7. Analysis of the -270 powder indicates
  • EXAMPLE 9 A plasma densified spray powder as produced in Example 7 is comminuted and air classified to produce a powder having the following distribution: 60-90% less then minus 20 microns, less than 15% less than 5 microns.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Poudre se composant essentiellement de chrome et de nickel, le reste étant de 50 à 95 % en poids du carbure de chrome, le chrome et le nickel étant présents dans un rapport de poids d'environ une partie en poids de chrome pour quatre parties en poids de nickel. Procédé de production de la poudre par le procédé consistant à agglomérer un mélange des constituants et à fritter les agglomérés dans un réacteur à température élevée.
PCT/US1982/001653 1981-11-27 1982-11-22 Poudre de carbure de nickel-chrome et procede de frittage Ceased WO1983001917A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32541681A 1981-11-27 1981-11-27
US325,416811127 1981-11-27

Publications (1)

Publication Number Publication Date
WO1983001917A1 true WO1983001917A1 (fr) 1983-06-09

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Application Number Title Priority Date Filing Date
PCT/US1982/001653 Ceased WO1983001917A1 (fr) 1981-11-27 1982-11-22 Poudre de carbure de nickel-chrome et procede de frittage

Country Status (2)

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EP (1) EP0094961A1 (fr)
WO (1) WO1983001917A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4606948A (en) * 1984-06-04 1986-08-19 Sherritt Gordon Mines Limited Process for the production of nickel-chromium/chromium carbide coatings on substrates
US4894090A (en) * 1985-09-12 1990-01-16 Santrade Limited Powder particles for fine-grained hard material alloys
US5102452A (en) * 1989-05-24 1992-04-07 Outokumpu Oy Method for the treatment and production of free-flowing wc-ni-co powders
EP0515944A1 (fr) * 1991-05-27 1992-12-02 Daido Tokushuko Kabushiki Kaisha Procédé pour la production d'une poudre en alliage contenant en dispersion des particules dures
US5419976A (en) * 1993-12-08 1995-05-30 Dulin; Bruce E. Thermal spray powder of tungsten carbide and chromium carbide
WO2004104250A1 (fr) * 2003-05-20 2004-12-02 Exxonmobil Research And Engineering Company Cermets a base de carbure resistant a l'erosion et a la corrosion pour utilisation de longue duree aux temperatures elevees
US7438741B1 (en) 2003-05-20 2008-10-21 Exxonmobil Research And Engineering Company Erosion-corrosion resistant carbide cermets for long term high temperature service
CN112496329A (zh) * 2020-12-10 2021-03-16 湖南人文科技学院 一种球形高松装密度Cr3C2-NiCr热喷涂粉的制备方法
US11504768B2 (en) 2017-02-17 2022-11-22 Teknologian Tutkimuskeskus Vtt Oy Method for producing hard metal powder, and hard metal powder

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3150938A (en) * 1958-05-28 1964-09-29 Union Carbide Corp Coating composition, method of application, and product thereof
US3617358A (en) * 1967-09-29 1971-11-02 Metco Inc Flame spray powder and process
US3973948A (en) * 1973-11-12 1976-08-10 Gte Sylvania Incorporated Free flowing powder and process for producing it
US3974245A (en) * 1973-12-17 1976-08-10 Gte Sylvania Incorporated Process for producing free flowing powder and product
US4039296A (en) * 1975-12-12 1977-08-02 General Electric Company Clearance control through a Ni-graphite/NiCr-base alloy powder mixture
US4075371A (en) * 1975-07-11 1978-02-21 Eutectic Corporation Wear resistant alloy coating containing tungsten carbide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3150938A (en) * 1958-05-28 1964-09-29 Union Carbide Corp Coating composition, method of application, and product thereof
US3617358A (en) * 1967-09-29 1971-11-02 Metco Inc Flame spray powder and process
US3973948A (en) * 1973-11-12 1976-08-10 Gte Sylvania Incorporated Free flowing powder and process for producing it
US3974245A (en) * 1973-12-17 1976-08-10 Gte Sylvania Incorporated Process for producing free flowing powder and product
US4075371A (en) * 1975-07-11 1978-02-21 Eutectic Corporation Wear resistant alloy coating containing tungsten carbide
US4039296A (en) * 1975-12-12 1977-08-02 General Electric Company Clearance control through a Ni-graphite/NiCr-base alloy powder mixture

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4606948A (en) * 1984-06-04 1986-08-19 Sherritt Gordon Mines Limited Process for the production of nickel-chromium/chromium carbide coatings on substrates
US4894090A (en) * 1985-09-12 1990-01-16 Santrade Limited Powder particles for fine-grained hard material alloys
US5032174A (en) * 1985-09-12 1991-07-16 Santrade Limited Powder particles for fine-grained hard material alloys and a process for the preparation of powder particles for fine-grained hard material alloys
US5102452A (en) * 1989-05-24 1992-04-07 Outokumpu Oy Method for the treatment and production of free-flowing wc-ni-co powders
EP0515944A1 (fr) * 1991-05-27 1992-12-02 Daido Tokushuko Kabushiki Kaisha Procédé pour la production d'une poudre en alliage contenant en dispersion des particules dures
US5419976A (en) * 1993-12-08 1995-05-30 Dulin; Bruce E. Thermal spray powder of tungsten carbide and chromium carbide
WO2004104250A1 (fr) * 2003-05-20 2004-12-02 Exxonmobil Research And Engineering Company Cermets a base de carbure resistant a l'erosion et a la corrosion pour utilisation de longue duree aux temperatures elevees
US7438741B1 (en) 2003-05-20 2008-10-21 Exxonmobil Research And Engineering Company Erosion-corrosion resistant carbide cermets for long term high temperature service
US11504768B2 (en) 2017-02-17 2022-11-22 Teknologian Tutkimuskeskus Vtt Oy Method for producing hard metal powder, and hard metal powder
CN112496329A (zh) * 2020-12-10 2021-03-16 湖南人文科技学院 一种球形高松装密度Cr3C2-NiCr热喷涂粉的制备方法

Also Published As

Publication number Publication date
EP0094961A1 (fr) 1983-11-30

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