US3840367A - Tool alloy compositions and methods of fabrication - Google Patents

Tool alloy compositions and methods of fabrication Download PDF

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Publication number
US3840367A
US3840367A US00226013A US22601372A US3840367A US 3840367 A US3840367 A US 3840367A US 00226013 A US00226013 A US 00226013A US 22601372 A US22601372 A US 22601372A US 3840367 A US3840367 A US 3840367A
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composition
carbide
molybdenum
titanium
binder
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US00226013A
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E Rudy
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TDY Industries LLC
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Individual
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Priority to BE794383D priority Critical patent/BE794383A/xx
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Priority to US00226013A priority patent/US3840367A/en
Priority to CA157,528A priority patent/CA976388A/en
Priority to IT55157/72A priority patent/IT974419B/it
Priority to GB184673A priority patent/GB1419982A/en
Priority to FR7301286A priority patent/FR2172097B1/fr
Priority to DE2302317A priority patent/DE2302317C3/de
Priority to BR73967A priority patent/BR7300967D0/pt
Priority to AT132773A priority patent/AT329289B/de
Priority to JP48017586A priority patent/JPS4889807A/ja
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Publication of US3840367A publication Critical patent/US3840367A/en
Assigned to TELEDYNE INDUSTRIES, INC., 1901 AVENUE OF THE STARS, LOS ANGELES, CA. A CORP. OF CA. reassignment TELEDYNE INDUSTRIES, INC., 1901 AVENUE OF THE STARS, LOS ANGELES, CA. A CORP. OF CA. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: RUDY, ERWIN
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    • 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
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9265—Special properties
    • Y10S428/932—Abrasive or cutting feature

Definitions

  • a composition of material comprising a titanium molybdenum carbide and an iron group metal binder is disclosed which is particularly useful as a metal cutting tool.
  • the carbide phase of the composition is substantially richer in carbon than the prior art.
  • the carbide phase contains more carbon than the composition line TiC- Mo C for the same ratio.
  • the carbide phase can contain higher amounts of molybdenum than was used in the prior art.
  • the present invention relates to improved cemented carbide alloys and more particularly to improved monocarbide alloys of titanium and molybdenum which are substantially richer in carbon than the prior art alloys of those metals and which, with a proper binder from the iron metal group, exhibits superior wear resistant characteristics.
  • Wear resistance of these improved tools which can be termed TiC-Mo C-Mo-Ni tools, in cutting soft'and medium hard steels is generally much higher than the tungstencarbide-based sintered carbides, but tool reliability is usually low because of their brittleness and their tendency to notch at the scale line. As a result, the full potential of their inherent high wear and cratering resistance is rarely realized in practice.
  • An additional shortcoming of the tool materials is their inability to machine hard steels, such as steels having a Rockwell hardness (R of 50 or higher, at competitive metal removal rates. Current usage is thus limited to machining of soft to medium hard low alloy steels under light cutting conditions, and machining of cast irons'and steels.
  • cemented carbide alloys which are based on the monocarbide solid solution (Ti, M0)C and which have carbon contents higher than the composition line TiC-Mo- C.
  • This monocarbide solid solution is cemented with an iron group metal binder which forms between 5 and 25 percent by weight of the total composition.
  • the carbon content higher than the composition line TiC-Mo C is greater for higher exchange ratios of molybdenum for titanium.
  • the value ofz can range from 0.972 to 0.985.
  • the monocarbide solid solution within the ranges just described is cemented with between 8 and 12 percent by weight of an iron group metal binder, preferablynickel or cobalt or a combination of these metals.
  • FIG. 1 is a graphical representation of the monocarbide solid solution phase of the present invention and also shows the composition of the carbide alloys of the prior art tool developments in this area which were discussed above;
  • FIGS. 2' and 3 wear curves comparing the wear of tools according to the present invention and according to the prior art when subjected to identical test condi tions;
  • FIGS. 4 through 6 show the wear rate of tools in accordance with the present invention as a function of the exchange ratio of molybdenum forv titanium (or the mole percent of molybdenum in the total metal content) for different test conditions.
  • compositions of the carbide component used in the fabrication of the carbide-bindermetal composites of the invention can be expressed either in atomic percent of the constituent elements, for example as Ti- ,Mo C (u v w where u, v, and ware, re spectively, the atomic percent of titanium, molybdenum and carbon present in the alloy; or as relative mole fractions of metal and interstitial elements in the form (Ti,Mo )C (x y 1), whereby x and y are, respectively, the relative mole fractions (metal exchange) of titanium and molybdenum, and 2 measures the number of gramatoms carbon per gramatom metal.
  • IOOy defines mole percent molybdenum exchange in (Ti,Mo,,)C and 100): defines mole percent titanium exchange.
  • the two sets of composition variables are readily interconverted by the relatrons The latter method of defining the overall composition of the carbide component, the designation (Ti Mo )C-, is particularly useful in describing the concentration spaces of interstitial alloys and is used throughout the remainder of this specification.
  • FIG. 1 is a graphical representation of the gross composition of the monocarbide solid solution (Ti, Mo,,)C and illustrates this phase of the composition of the present invention as well as the composition of the carbide alloys of the prior art tool developments in this area.
  • the format of FIG. 1 was selected to show these compositions rather than the conventional triangular graph for showing ternary systems because in such a graph the ranges discussed below would be poorly shown due to excess compressions.
  • the ordinate in FIG. 1 is the subscript z in the composition (Ti,Mo )C while the abscissa is the subscript y. Of course, the abscissa also defines x, since x y l.
  • the ordinate is also shown as atomic percent carbon of the gross composition, with this atomic percent being equal to 1/1 z. The ordinate is linear for z, and is thus somewhat non-linear for atomic percent carbon.
  • the abscissa is also shown as the percent exchange ratio of molybdenum for titanium, or the mole percent of molybdenum in the total metal content. This mole percent is equal to IOO-y.
  • the line in FIG. 1 represents the composition line Ti-C-Mo C, or the composition in the chosen notation of a mixture of TiC and Mo C for varying ratios of the two compounds.
  • the area bounded by ABCD represents the composition range investigated by R. Kieffer and D. Fister in the above referenced report.
  • the area bounded by AB'C'D' represents the gross composition of most current commercial tools in this area.
  • the composition at the point D, (Ti Mo -,)C approximately corresponds to the prior art comparison tool TiC-Mo C-Ni discussed below, and the point midway between B and C, or (Ti Mo )C when combined with a binder of 10 percent nickel, represents the optimum composition for the tools described in the above mentioned US. Pat. No. 2,967,349. This is the approximate composition of the prior art comparison tool TiC- Mo C-Mo-Ni discussed below.
  • the gross carbide composition of the tool alloys in accordance with the present invention generally fall within the composition area bounded by EFGH, but preferably within the more confined area EF'GH.
  • Carbide alloys located outside the area EF'GH', but inside the area EFGH, provide alloys of lesser quality when employed as cutting tools, but have other useful applications.
  • the composition point, E corresponds to (Tl M0 )C point P to .l(7 .l.'l) .tl-'n Point to jo Qsol Jai d Point H to (Ti r,uM0,;,,,)C Point E corresponds to (Ti It is seen from FIG.
  • the carbide phase of the composition of the present invention is characterized by being substantially richer in carbon than the prior art composition.
  • the composition contains more carbon than the composition line TiC-Mo C for the same ratio.
  • the prior art had assumed that this composition line represented the maximum possible carbon content for any given exchange ratio.
  • higher amounts of molybdenum can be used than was possible with the prior art compositions. As is discussed in more detail below, this enables tools to cut under severe machining conditions as well as the light machining conditions to which the prior art TiC-Mo- C- Mo-Ni tools were limited.
  • the carbide-metal composites of the invention may be fabricated by several different powder metallurgy techniques.
  • a typical fabrication procedure is as follows: A mixture of carbide and binder alloy in the desired proportions are ball-milled in stainless steel jars for 3 to 4 days, using tungsten carbide-cobalt alloy balls and naphta or benzene as milling fluid. Depending on the power density, 3 to 5 weight percent pressing lubricant, usually paraffine, is added in solution with a suitable solvent such as benzene. The solvent for the paraffine is then evaporated, and the'dry powder mixture compactedinto the desired shapes at pressures ranging between 6 and '10 tons per square inch.
  • the pressing lubricant is then removed by heating at temperatures between 200 and 700C under vacuum and the compacts, stacked on suitable support materials such as graphite, are sintered for l to 1% hrs. at temperatures between l350 and l450C under vacuum.
  • suitable support materials such as graphite
  • the sintered parts are ground on diamond wheels 'to the desired tool geometry.
  • compositions formed in the manner just described can be termed-prehomogenized solid solutions.
  • compositions of the present invention other method for making the compositions of the present invention is to first form such a prehomogenized solid solution which is a. molybdenum rich monocarbide solid solution, such as (Ti ,Mo )C and then reactively sintering it with suitable quantities of titanium monocarbide and binder material to bring the gross composition of the material to the desired levels.
  • a prehomogenized solid solution which is a. molybdenum rich monocarbide solid solution, such as (Ti ,Mo )C
  • suitable quantities of titanium monocarbide and binder material to bring the gross composition of the material to the desired levels.
  • the bulk of the carbide grains in such composites if properly fabricated, will have a grain size equal orlcss than that in the as-milled condition. Wear-resistance. but especially top catering resistance, in machine-tool applications appears markedly improved by the presence of unreacted TiC in the core of a fraction of the carbide grains. Tendency towards plastic deformation under highcutting loads is somewhat'higher than in composites preparedfrom preformed solid. solutions and binder alloy with the same gross composition. Consequently, a lower binder content is used in reactively sintered composites for machine tool applications.
  • TEST CONDITION A (wear test) 4340 steel, R22 to 29; cutting speed, 500 surface feet per minute; feed rate, 0.0151 inch per revolution; depth of cut, 0.060 inch; no coolant. SNG 433 inserts.
  • TEST CONDITION B (roughing test) 4340 steel, R22 to 29; cutting speed, 500 surface feet per minute; feed rate, 0.0203 inch per revolution; depth ofcut, 0.125 inch; no coolant. SNG 433 inserts.
  • TEST CONDITION D finishing hardened steel 4340 steel, R46 to 55; cutting speed, 250 surface feet per minute; feed rate, 0.0051 inch per revolution; depth of cut, 0.050 inch; no coolant. SNG 432 inserts.
  • the wearland was measured at suitable time intervals with the aid of a tool microscope. Plastic deformation of the cutting edge and crater depth were measured on a metallograph.
  • the flank data presented in the graphs and tables refer to the uniform wear zone of the tools.
  • FIGS. 2 and 3 and the following Tables 1 through 4 show the performance of these four examples and of the leading prior art tools when subjected to the above described test conditions.
  • EXAMPLE 1 v A powder blend consisting of 91.50 weight'percent of an alloy (Ti Mo )C and 8.50 weight percent nickel was prepared as a prehomogenized solid solution in the manner described above and the compacts sintered for 1 hour and 10 minutes at 1385C under vacuum. Average linearshrinkage during sintering was 16.4 percent. Average grain size of the carbide phase was approximately 4 micrometers and the hardness was 93.0 on the Rockwell A scale.
  • EXAMPLE 2 titanium-molybdenum monocarbide solid solutions, with the outermost layer approximately corresponding to a carbide containing approximately (Ti r,Mo,.-,:,)C A hardness of 92.9 on the Rockwell A scale was measured for the sintered composite.
  • EXAMPLE 3 A powder blend consisting of 33.6 weight percent of a prehomogenized solid solution having the composition (TL M JC 55.1 weight percent TiC [resulting in a gross carbide composition of (Ti Mo JC L 5.65 percent nickel and 5.65 percent cobalt, was reactively sintered in the manner described before the compacts sintered for 1 hour and 30 minutes at l395C under vacuum.
  • the carbide phase in the sintered compact had an average grain size of 3 micrometers and the v measured hardness of the composite RA 93.1.
  • FIG. 2 shows the averaged corner and flank wear as a function of cutting time for tools formed from the above Examples l and 2 and the prior art tools TlCMOgC'MO'Nl and K7H when subjected to the Test Condition A.
  • Curve 12 shows the wear of the K7H tool, curve 14 the wear of the TiC-Mo C-Mo-Ni tool, curve 16 the wear of the Example 1 tool and curve 18 the wear of the Example 2 'tool.
  • FIG. 3 shows the averaged corner and flank wear as a function of cutting time for tools formed from the above Examples 1 and 2 and. the prior art tool K7H when subjected to the Test Condition D. No curve for the prior art tool TiC-Mo C-Mo-Ni is shown since this tool failed almost instantly when subjected to this test condition.
  • Curve 20 shows the wear of the K7H tool when machining steel having a hardness of R,- 49 to 52.
  • Curve 22 shows the wear of the Example 1 tool 20 when machining steel having a hardness of R.- 51 to 54.
  • Curve 24 shows the wear of the Example 2 tool when machining steel having a hardness of R 47 to 49.
  • Table 6 shows the wear rate Of repr the total metal content of the carbide phase, for differsentative prior art commercial carbide tools w en sub- 7 20 ent test conditions.
  • the curve 26 shows the avjected to the Test Condition B: eraged corner and flank wear rates and the curve 28 Table 6 Carbide Range of Observed Wear Rates Class Mils per Minute Flank Crater REMARKS C-5.
  • C-5A 9. to 12 4 to 5 3 to 5 mils thermal deformation at 1.5 minutes
  • FIG. 5 shows the top cratering rate for Test Condition A.
  • the curve 30 shows the averaged corner and flank wear rates and the curve 32 shows the top cratering rate for Test Condition B.
  • FIG. 6 shows averaged corner and flank wear rates for Test Condition D.
  • curve 34 shows these rates for machining hardened corner delamination usually at start of second pass
  • the curve 36 shows these compositions according to the present invention are rates for machining hardened steel having an R.- 50 shown in FIG. 6, described below. to 55.
  • FIGS. 4, 5 and 6 show the wear rate of tools formed within the composition range of the present invention, from compositions in accordance with the present infor progressively more severe machining test, it is desirvention as a function of the exchange ratio of molybdeable to have higher exchange ratios of molybdenum for num for titanium, or the mole per cent molybdenum in titanium.
  • the composition of the present invention is formed from the above described carbides bonded with a binder from the iron metal group, such as nickel, cobalt and iron.
  • the binder can form from 5 to percent by weight of the composition. If too little binder is used, the composition will be too brittle. If too much binder is used, the composition will be too soft and will deform. Preferably, the binder forms from 8 to 12 percent by weight of the composition.
  • the selection of the proper binder is somewhat dependent upon the mole per cent molybdenum in the carbide phase of the composition. For compositions in which the carbide phase contains less than 40 mole per cent molybdenum, cutting performance of cobalt or nickel bonded tools is considered equivalent. Carbides with more than 55 mole per cent molybdenum show embrittlement when using a cobalt binder. Iron binders are useful only for carbides containing less than 35 mole per cent molybdenum. Carbides with more than 60 mole percent molybdenum are unstable inv the presence of cobalt, and iron and decompose under formation of titanium-richer monocarbide solutions, n-carhides, and free carbon. -n-carbide formation is especially pronounced in substantially carbon-deficient carbide solutions.
  • the properties of the carbide-metal composites can be extensively modified by alloying.
  • the following summary of the effects of the principal alloying ingredients are based on performance studies of the composites as tool materials in turning 4340 steel. However, low level alloying with other elements may also be accomplished without departing from the spirit of the invention.
  • Tungsten can be alloyed in substantial quantities (up to mole per cent) in exchange for molybdenum in the composites of the inventionwithout impairment of performance.
  • Small additions of tungsten (less than 5 mole per cent in exchange for molybdenum) are beneficial in retarding grain growth during sintering.
  • Titanium carbide-rich alloys containing more than mole per cent TiC are especially insensitive towards higher concentrations of tungsten, while molybdenum-rich alloys tend to reject free graphite from the solid solution if thetungsten exchange for molybdenum exceeds 20 mole per cent. Formation of free graphite can be avoided by lowering thecarbon content of the alloys between 0.5 and 1.5 atomic per cent.
  • Table 8 shows the wear rates for'a number of tools formed from compositions incorporating some of the alloy substitutions just discussed when these tools were subjected to Test Condition A:
  • the composites of the invention also may be modified and adapted for special applications by surface coatings of wear-resistant alloys based on carbides and nitrides of the refractory transition metals.
  • the wear data also indicate that no performance advantage in cutting steels is being gained by increasing the titanium exchange in the composites of the invention substantially above 80 mole percent (approximately 69 weight percent TiC): tool reliability decreases rapidly, especially in somewhat heavier cuts, and the failure mechanisms become similar to those of the prior art TiC'MOgC-MO'Ni tool materials.
  • a composition of material comprising sintered carbide-binder metal in which said carbide has titanium and molybdenum as its base metal and has a gross composition falling within the area EFGH of FIG. 1, and in which said binder is selected from the iron group metals and comprises between and 25 weight percent of the composition.
  • the method of claim 9 which further comprises the step of grinding the sintered composite into predetermined shape to form a metal cutting tool.

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  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
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US00226013A 1972-02-14 1972-02-14 Tool alloy compositions and methods of fabrication Expired - Lifetime US3840367A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
BE794383D BE794383A (fr) 1972-02-14 Alliages de carbures pour outils de coupe
US00226013A US3840367A (en) 1972-02-14 1972-02-14 Tool alloy compositions and methods of fabrication
CA157,528A CA976388A (en) 1972-02-14 1972-11-27 Tool alloy compositions and methods of fabrication
IT55157/72A IT974419B (it) 1972-02-14 1972-12-29 Composizione di materiale metalli co per utensili e metodo per produrla
GB184673A GB1419982A (en) 1972-02-14 1973-01-12 Metallic compositions
FR7301286A FR2172097B1 (US06650917-20031118-M00005.png) 1972-02-14 1973-01-15
DE2302317A DE2302317C3 (de) 1972-02-14 1973-01-18 Karbid-Hartlegierung und Verfahren zu ihrer Herstellung
BR73967A BR7300967D0 (pt) 1972-02-14 1973-02-08 Composicao de material sinterizado e processo de formacao da mesma
AT132773A AT329289B (de) 1972-02-14 1973-02-14 Sinterhartmetall und verfahren zu seiner herstellung
JP48017586A JPS4889807A (US06650917-20031118-M00005.png) 1972-02-14 1973-02-14

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AT (1) AT329289B (US06650917-20031118-M00005.png)
BE (1) BE794383A (US06650917-20031118-M00005.png)
BR (1) BR7300967D0 (US06650917-20031118-M00005.png)
CA (1) CA976388A (US06650917-20031118-M00005.png)
DE (1) DE2302317C3 (US06650917-20031118-M00005.png)
FR (1) FR2172097B1 (US06650917-20031118-M00005.png)
GB (1) GB1419982A (US06650917-20031118-M00005.png)
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4047897A (en) * 1975-10-14 1977-09-13 Ngk Spark Plug Co., Ltd. Sintered alloy for cutting tools
US4049380A (en) * 1975-05-29 1977-09-20 Teledyne Industries, Inc. Cemented carbides containing hexagonal molybdenum
US4066451A (en) * 1976-02-17 1978-01-03 Erwin Rudy Carbide compositions for wear-resistant facings and method of fabrication
US4101318A (en) * 1976-12-10 1978-07-18 Erwin Rudy Cemented carbide-steel composites for earthmoving and mining applications
US4120719A (en) * 1976-12-06 1978-10-17 Sumitomo Electric Industries, Ltd. Cemented carbonitride alloys containing tantalum
US4716019A (en) * 1987-06-04 1987-12-29 Gte Products Corporation Process for producing composite agglomerates of molybdenum and molybdenum carbide
DE3806602A1 (de) * 1988-03-02 1988-07-07 Krupp Gmbh Hartmetallkoerper
US20050106056A1 (en) * 2003-11-18 2005-05-19 Dwa Technologies, Inc. Manufacturing method for high yield rate of metal matrix composite sheet production
US20050159494A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Method for producing fluids having suspended ultrasmall particles using multi-carbide grinding media
US20050158227A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Method for producing fine dehydrided metal particles using multi-carbide grinding media
US20060162492A1 (en) * 2003-05-20 2006-07-27 Chun Changmin Advanced erosion resistant carbide cermets with superior high temperature corrosion resistance
CN100398440C (zh) * 2003-03-11 2008-07-02 普里梅精密材料有限公司 多元碳化物材料的制造和用途
US7442338B2 (en) * 2001-11-13 2008-10-28 Fundacion Inasmet Product manufacture in structural metallic materials reinforced with carbides
AU2006275742B2 (en) * 2005-07-29 2010-09-09 Primet Precision Materials, Inc. Grinding media and methods associated with the same
US10195612B2 (en) 2005-10-27 2019-02-05 Primet Precision Materials, Inc. Small particle compositions and associated methods

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3971656A (en) * 1973-06-18 1976-07-27 Erwin Rudy Spinodal carbonitride alloys for tool and wear applications
AU501073B2 (en) * 1974-10-18 1979-06-07 Sumitomo Electric Industries, Ltd. Cemented carbonitride alloys

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FR874342A (fr) * 1940-08-12 1942-08-04 Comm Aciers Soc Ind Procédé pour la fabrication d'alliages durs pour outils et instruments de travail
FR986190A (fr) * 1948-07-10 1951-07-27 Metallwerk Plansee G M B H Alliage de métaux durs et son procédé de fabrication
DE918050C (de) * 1950-06-03 1954-09-16 Boehler & Co Ag Geb Hartmetallegierung
FR1043475A (fr) * 1951-10-05 1953-11-09 Boehler & Co Ag Geb Procédé pour la fabrication d'alliages frittés de métaux durs

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049380A (en) * 1975-05-29 1977-09-20 Teledyne Industries, Inc. Cemented carbides containing hexagonal molybdenum
US4047897A (en) * 1975-10-14 1977-09-13 Ngk Spark Plug Co., Ltd. Sintered alloy for cutting tools
US4066451A (en) * 1976-02-17 1978-01-03 Erwin Rudy Carbide compositions for wear-resistant facings and method of fabrication
US4120719A (en) * 1976-12-06 1978-10-17 Sumitomo Electric Industries, Ltd. Cemented carbonitride alloys containing tantalum
US4101318A (en) * 1976-12-10 1978-07-18 Erwin Rudy Cemented carbide-steel composites for earthmoving and mining applications
US4716019A (en) * 1987-06-04 1987-12-29 Gte Products Corporation Process for producing composite agglomerates of molybdenum and molybdenum carbide
DE3806602A1 (de) * 1988-03-02 1988-07-07 Krupp Gmbh Hartmetallkoerper
US4944800A (en) * 1988-03-02 1990-07-31 Krupp Widia Gmbh Process for producing a sintered hard metal body and sintered hard metal body produced thereby
US7442338B2 (en) * 2001-11-13 2008-10-28 Fundacion Inasmet Product manufacture in structural metallic materials reinforced with carbides
US7267292B2 (en) * 2003-03-11 2007-09-11 Primet Precision Materials, Inc. Method for producing fine alumina particles using multi-carbide grinding media
US7140567B1 (en) * 2003-03-11 2006-11-28 Primet Precision Materials, Inc. Multi-carbide material manufacture and use as grinding media
US20050158229A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Method of increasing a reactive rate per mass of a catalyst
US20050158231A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Method for producing highly transparent oxides of titanium using multi-carbide grinding media
US20050155455A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Methods for producing titanium metal using multi-carbide grinding media
US20050158232A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Method for producing fine silicon carbide particles using multi-carbide grinding media
US20050158227A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Method for producing fine dehydrided metal particles using multi-carbide grinding media
US20050158234A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Method of making particles of an intermetallic compound
US20050158230A1 (en) * 2003-03-11 2005-07-21 Robert Dobbs Methods for producing fine oxides of a metal from a feed material using multi-carbide grinding media
US20050161540A1 (en) * 2003-03-11 2005-07-28 Robert Dobbs Method for producing an ultrasmall device using multi-carbide grinding media
US20050200035A1 (en) * 2003-03-11 2005-09-15 Robert Dobbs Method of making multi-carbide spherical grinding media
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DE2302317C3 (de) 1975-05-07
CA976388A (en) 1975-10-21
AT329289B (de) 1976-05-10
DE2302317A1 (de) 1973-09-06
DE2302317B2 (de) 1974-07-25
GB1419982A (en) 1976-01-07
FR2172097A1 (US06650917-20031118-M00005.png) 1973-09-28
BE794383A (fr) 1973-07-23
JPS4889807A (US06650917-20031118-M00005.png) 1973-11-24
IT974419B (it) 1974-06-20
ATA132773A (de) 1975-07-15
FR2172097B1 (US06650917-20031118-M00005.png) 1976-11-05
BR7300967D0 (pt) 1973-09-25

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