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US3854991A - Coated cemented carbide products - Google Patents

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Publication number
US3854991A
US3854991A US00225667A US22566772A US3854991A US 3854991 A US3854991 A US 3854991A US 00225667 A US00225667 A US 00225667A US 22566772 A US22566772 A US 22566772A US 3854991 A US3854991 A US 3854991A
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coating
cemented carbide
hafnium
carbonitride
coated
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US00225667A
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T Hale
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Carboloy Inc
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General Electric Co
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Priority to BE795014D priority Critical patent/BE795014A/en
Application filed by General Electric Co filed Critical General Electric Co
Priority to US00225667A priority patent/US3854991A/en
Priority to GB393473A priority patent/GB1388261A/en
Priority to CA162,535A priority patent/CA989688A/en
Priority to AU51679/73A priority patent/AU478083B2/en
Priority to CH159773A priority patent/CH585273A5/xx
Priority to IT20060/73A priority patent/IT978836B/en
Priority to DE2306504A priority patent/DE2306504C3/en
Priority to SE7301897A priority patent/SE380006B/xx
Priority to FR7304587A priority patent/FR2171334B1/fr
Priority to BR731004A priority patent/BR7301004D0/en
Priority to JP1574473A priority patent/JPS5425482B2/ja
Priority to PL1973160687A priority patent/PL83467B1/pl
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Assigned to CARBOLOY INC., A DE. CORP. reassignment CARBOLOY INC., A DE. CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GENERAL ELECTRIC COMPANY
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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • 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
    • Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer

Definitions

  • ABSTRACT A coated cemented carbide product comprising a cemented carbide substrate and a fully dense hafnium and/or zirconium carbonitride coating on the substrate.
  • the hafnium or hafnium and zirconium carbonitride coating has a carbon-to-nitrogen ratio having an X-ray diffraction lattice parameter between 4.570 and 4.630 angstrom units while the zirconium carbonitride range is between about 4.600 and 4.620 angstrom units.
  • the coated products are prepared by passing a hafnium or zirconium halide, hydrogen gas, nitrogen gas and a hydrocarbon gas over thecarbide substrate at a temperature of from l,000-l ,300" C., the relative proportion of nitrogen and hydrocarbon and the temperature being adjusted to obtain the foregoing carbon-tonitrogen ratios in the coating.
  • carbides other than WC generally results in a significant strength reduction, however, which limits either the amount of TiC and other carbides that can be added or the severity of the application when large amounts of TiC are used.
  • the process of the invention involves the passage of a gaseous mixture of a hafnium or zirconium halide, hy-
  • the relative proportions of carbon and nitrogen in the coating are varied by changing the relative amounts of nitrogen and hydrocarbon in the coating gas and by varying the deposition temperature.
  • cemented carbide as used herein means one or more transitional carbides of a metal of Groups IVb, Vb, and VIb of the Periodic Table, cemented or bonded by one or more matrix metals selected from the Group Fe, Ni and Co.
  • fully dense coating is meant a coating of at least 99 percent of theoretical density and in most cases greater than 99.5 percent.
  • the starting materials are preferably hafnium or zirconium tetrachloride vapor, hydrogen gas, nitrogen gas, and methane gas.
  • Other hafnium or zirconium halides and other hydrocarbons may be used, although 7 the foregoingstarting materials are preferred because tance of TiC and TiN to cracking and the high sensitivity of the substrate carbide to the presence of surface cracks. While it is likely that any coating that is hard and brittle will lower the strength of the coated cemented carbide composite if adherently bonded to the substrate. it is desirable to minimize the strength loss to as great an extent as possible.
  • a 5 to 7 micron thick coating of TiC or TiN on metal-cutting grades of cev series ol coated products were prepared in accormented carbide causes a strength loss of 40-50 percent as measured by the bend or transverse rupture strength test.
  • the reduced toughness of these coated composites is observed in actual use as an increased tendency breakage in some of the more severe applications.
  • the foregoing and other objects of this invention are achieved by the chemical vapor deposition of a hafnium or zirconium carbonitride coating on a cemented carbide substrate.
  • the product contains a cemented carbide substrate and a nonporous, dense hafnium and- /or zirconium carbonitride coating firmly and metallurgically bonded to the substrate.
  • the desired coating will normally be from [-7 microns thickness. It has been found that it is necessary to carefully control the carbon-to-nitrogen ratio of these coatings since the metal-cutting performance is strongly dependent upon the value of this ratio, as will be explained in more detail subsequently.
  • the coated products exhibit metalcutting performance that is substantially equal to or superior to currently available coated composites while they are the least expensive and most readily available raw materials. It is possible that small amounts of other halides, as'for example titanium, tantalumor nobium chloride, maybe included with'the zirconium or hafnium halide without detrimental effects on the properties of the it oated roduct and it is not intended to exclude the res of one or mor such ad "difiona metal carbides in the final product. in place of methane, propane or carbon tetrachloride may be used or any other hydrocarbon conventionally used as a sourceof carbon in vapor deposition processes.
  • halides as'for example titanium, tantalumor nobium chloride
  • the cutting time to a flank wear or crater depth of .010 inch is shown as a measure of cutting performance.
  • Examples 18 and 19 had thicker coatings, in the 4 to 5 micron range.
  • the cutting performance of the uncoated substrate material, Example 20, and a 5 mi- 9 cron thick TiC coated insert, example 21, are also shown in Table III.
  • Examples 13 through 17 all had coating thicknesses in the 1.5 2 micron range and are listed in order of increasing carbon mented carbide tool material is very substantially improved by the hafnium carbonitride coating. It is also evident that the amount of improvement obtained is strongly dependent upon the carbon to nitrogen ratio with a peak in performance at about 4.61 angstrom units. It is probable that thicker coatings of 5 to 10 microns will provide an additional increment of improvement.
  • the strength of the hafnium carbonitride coated composites was measured using a transverse rupture test that comprised three roll loading with a test span to thickness ratio of 3.5 to 1. Using this test it was found that the strength of hafnium carbonitride coated when the carbon to nitrogen ratio is at the optimum value of about 3 (lattice parameter of about 4.610 A). useful performance is obtained within a composition range of 4.57 to 4.63 A, which represents a carbon to nitrogen ratio range of about .73 to 12.
  • the metal-cutting performance of zirconium carbonitride coated inserts prepared in accordance with this invention is shown in the following Table W. In
  • Examples 22 through 32 were a inch X A inch X 3/ l6.inch disposable cutting inserts, coated with zirconium carbonitride at l;-100'-l, 15'0 C. by the vapor deposition technique disclosed above for Examples 6 through'l2.
  • the cemented carbide substrate was tride, upon the carbon-'to-nitrogen ratio with a strong parameter of about I 4.610 was about 190,000 psi.
  • the strength of 5 microns thick TiC-coated composites (using the same substrate carbide) was 150,000. It is therefore evident that zirconium carbonitride-coated composites having the optimum carbon-to-nitrogen ratio for metal cutting possess a superior combination of metal-cutting performance and strength when compared with TiC-coated composites.
  • Example 22-32 are listed by order of increasing carbon-to-nitrogen ratio in the coating, and cutting time to a flank wear of .010 inch is shown as a measure of cutting performance, For comparison purposes. the cutting performance of the coated insert.
  • Example 34. is also shown in Table IV.
  • the cutting performance of the cemented carbide tool material is very substantiallyimcomposed of a solid solution of both hafnium and zirconium carbonitride. This was accomplished by simultaneously passing chlorides of hafnium and zirconium .(along with hydrogen, nitrogen, and methane gases) over the cemented carbide inserts. It is very difficult to characterize the exact compositions of such coatings 1 since the zirconium-to-hafnium ratio'influences the lattice-parameter as does the carbon-to-nitrogen ratio.
  • a coated cemented carbide product comprising a cemented carbide substrate and a fully dense coating selected from the group consisting of hafnium carbonitride, zirconium carbonitride and mixtures of the two, said coating firmly and adherently bonded to said substrate,
  • hafnium carbonitride coating and the hafnium and zirconium carbonitride coatings having an X-ray diffraction lattice parameter within the range of about 4.570 to 4.630 angstrom units and the zirconium carbonitride coating having an X-ray diffraction parameter within the range of about 4.600 to 4.620 angstrom units.
  • cemented carbide substrate comprises tungsten carbide and a cobalt matrix.
  • cemented carbide substrate comprises tungsten carbide. titanium carbide. tantalum carbide and a cobalt matrix.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Vapour Deposition (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Powder Metallurgy (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A coated cemented carbide product comprising a cemented carbide substrate and a fully dense hafnium and/or zirconium carbonitride coating on the substrate. The hafnium or hafnium and zirconium carbonitride coating has a carbon-to-nitrogen ratio having an Xray diffraction lattice parameter between 4.570 and 4.630 angstrom units while the zirconium carbonitride range is between about 4.600 and 4.620 angstrom units. The coated products are prepared by passing a hafnium or zirconium halide, hydrogen gas, nitrogen gas and a hydrocarbon gas over the carbide substrate at a temperature of from 1,000*-1,300* C., the relative proportion of nitrogen and hydrocarbon and the temperature being adjusted to obtain the foregoing carbon-to-nitrogen ratios in the coating.

Description

KR 5925549991. 5R- 1 COATED CEMENTED CARBIDE PRODUCTS Thomas E. Hale, Warren, Mich.
Inventor:
Assignee: General Electric Company,
Schenectady, N.Y.
Filed: Feb. 11, 1972 Appl. No.2 225,667
References Cited I UNITED STATES PATENTS 2/1961 Urahiotes et a1. 117/106 12/1967 Rich et al. l17/l06 4/1972 Reedy 148/166 2/1973 Kieffer at al. 117/106 c 7/1973 Kalish 117/169 I Dec. 17, 1974 Primary Examiner-Douglas J. Drummond Assistant Examiner-.1. W. Massie [57] ABSTRACT A coated cemented carbide product comprising a cemented carbide substrate and a fully dense hafnium and/or zirconium carbonitride coating on the substrate. The hafnium or hafnium and zirconium carbonitride coating has a carbon-to-nitrogen ratio having an X-ray diffraction lattice parameter between 4.570 and 4.630 angstrom units while the zirconium carbonitride range is between about 4.600 and 4.620 angstrom units. The coated products are prepared by passing a hafnium or zirconium halide, hydrogen gas, nitrogen gas and a hydrocarbon gas over thecarbide substrate at a temperature of from l,000-l ,300" C., the relative proportion of nitrogen and hydrocarbon and the temperature being adjusted to obtain the foregoing carbon-tonitrogen ratios in the coating.
6 Claims, No Drawings 1 COATED CEMENTED CARBIDE PRODUCTS This invention relates to,a coated cemented carbide product and to a process for its preparation.
are preferred because they are less reactive with steel 7 workpieces at high machining speeds. The use of carbides other than WC generally results in a significant strength reduction, however, which limits either the amount of TiC and other carbides that can be added or the severity of the application when large amounts of TiC are used.
It is known that the wear resistance of cemented carbides can be enhanced by the application of a thin coating of certain hard substances such as TiC and TiN. In this manner a better combination of toughness and metal-cutting wear resistance is obtained than can nor- .mally be obtained using uncoated compositions. However. the toughness of TiC- and TiN-coated compositions is significantly less than that of the core or substrate material alone, apparently due to the low resisv b having a significantly higher strength as measured by the transverse rupture test.
The process of the invention involves the passage of a gaseous mixture of a hafnium or zirconium halide, hy-
drogen, nitrogen, and a hydrocarbon over the carbide substrate at temperatures between l,000-l,300 C. The relative proportions of carbon and nitrogen in the coating are varied by changing the relative amounts of nitrogen and hydrocarbon in the coating gas and by varying the deposition temperature.
The term cemented carbide" as used herein means one or more transitional carbides of a metal of Groups IVb, Vb, and VIb of the Periodic Table, cemented or bonded by one or more matrix metals selected from the Group Fe, Ni and Co. A typical cemented carbide'may contain WC in a'cobalt matrix or TiC ina nickel 'matrix. By fully dense coating is meant a coating of at least 99 percent of theoretical density and in most cases greater than 99.5 percent.
The starting materials are preferably hafnium or zirconium tetrachloride vapor, hydrogen gas, nitrogen gas, and methane gas. Other hafnium or zirconium halides and other hydrocarbons may be used, although 7 the foregoingstarting materials are preferred because tance of TiC and TiN to cracking and the high sensitivity of the substrate carbide to the presence of surface cracks. While it is likely that any coating that is hard and brittle will lower the strength of the coated cemented carbide composite if adherently bonded to the substrate. it is desirable to minimize the strength loss to as great an extent as possible. A 5 to 7 micron thick coating of TiC or TiN on metal-cutting grades of cev series ol coated products were prepared in accormented carbide causes a strength loss of 40-50 percent as measured by the bend or transverse rupture strength test. The reduced toughness of these coated composites is observed in actual use as an increased tendency breakage in some of the more severe applications.
it is accordingly an object of this invention to provide a coated cemented carbide composite that has a combination of strength and wear resistance that is superior to those presently known.
It is an additional object of this invention to provide a process for producing a firmly adherent, nonporous, dense coating on a cemented carbide substrate.
The foregoing and other objects of this invention are achieved by the chemical vapor deposition of a hafnium or zirconium carbonitride coating on a cemented carbide substrate. The product contains a cemented carbide substrate and a nonporous, dense hafnium and- /or zirconium carbonitride coating firmly and metallurgically bonded to the substrate. The desired coating will normally be from [-7 microns thickness. It has been found that it is necessary to carefully control the carbon-to-nitrogen ratio of these coatings since the metal-cutting performance is strongly dependent upon the value of this ratio, as will be explained in more detail subsequently. The coated products exhibit metalcutting performance that is substantially equal to or superior to currently available coated composites while they are the least expensive and most readily available raw materials. it is possible that small amounts of other halides, as'for example titanium, tantalumor nobium chloride, maybe included with'the zirconium or hafnium halide without detrimental effects on the properties of the it oated roduct and it is not intended to exclude the res of one or mor such ad "difiona metal carbides in the final product. in place of methane, propane or carbon tetrachloride may be used or any other hydrocarbon conventionally used as a sourceof carbon in vapor deposition processes.
dance with the process of the invention by passing hafnium or zirconium tetrachloride vapor, hydrogen, ni-
' trogen, and methane over cemented carbide inserts.
, and 11 below illustrate the manner in which variations in the relative proportions of carbon and nitrogen in the coating were obtained. if different coating temperatures, pressures, and hafnium or zirconium halides are used it is expected that different relative proportions of nitrogen and hydrocarbon will be required to obtain a desired carbon-to-nitrogen ratio in the coating. The carbon-to-nitrogen ratios shown in Tables I and II are estimated from X-ray diffraction lattice parameter measurements, assuming a linear relationship between lattice parameter and carbon-to-nitrogen ratio. Since the actual relationship is probably not exactly linear, the coating compositions of this invention are best characterized by their measured X-ray lattice parameters.
TABLE 1 COATING CONDITIONS EMPLOYED TO OBTAIN HfC.N COATINGS Gas Composition Coatin Ia m ce C/N Temp. Time Thickness Parameter Ratio Examples C. (Hm) Z H Z N, 5% CH HFCI, Microns A (Est) l 1000 1% 24 75 I l 1' 4.559 .50 2 1100 2 75 24 1 I 3 4.571 .75 3 1130 5 24 75 I 1 4 4.589 1.38 4 1 I50 1% 24 75 l l 2 4.607 2.70 5 1 170 5 24 75 1 1 5 4.621 5.25 6 1050 I 98 2 1 2 4.640
' ure TABLE II COATING CONDITIONS EMPLOYED TO OBTAIN 71C ,N COATINGS G25 Comgggition Coating r C/N Temp. Time Thickness Parameter 'Ratio' Examples C.' (Hrs) H %N, ZCI-L 952x0 Microns A (st.)
7 1150 2 24.00 75 0. 1 3-5 4.574 .031 8 1100 4% 23.75 75 0.25 I 4 4.583 .11 9 1135 4 23.67 75 0.33 I 5 4.602 .35 10 1135 2 23.60 75 0.40 I 8 4.611 .48 I1 [I50 2 23.50 75 0.50 I 4 4.617 .61 12 1100 3 87.50 10 L50 I 1.5 4.625 .79
to nitrogen ratio in the coating. The cutting time to a flank wear or crater depth of .010 inch is shown as a measure of cutting performance. Examples 18 and 19 had thicker coatings, in the 4 to 5 micron range. For comparison purposes the cutting performance of the uncoated substrate material, Example 20, and a 5 mi- 9 cron thick TiC coated insert, example 21, are also shown in Table III.
TABLE III CUTITNG PERFORMANCE OF HAFNIUM CARBONITRIDE COATED TOOLS (CUTTING SAE 1045 STEEL. 190 BHN. AT 700 SFPM SPEED) Coatin Character Cuttin Performance I; ttlcc UN Itme to Thickness Parameter Ratio .010" Wcar Example Microns A (Est. Min.
13 1.5 2 4.574 .82 I6 14 1.5 2 4.582 1.08 22 15 1.5 2 4.607 2.71 34 I6 2' 4.620 4.90 I7 1.5-2 4.64 ==(pure HfC) 10 18 4 5 4.587 1.32 I9 4 5 4.597 1.82 20 0 (uncoated substrate) 5 2| 5 (TiC coated) 22 The preferred temperature range for deposition of 50 It can be seen that the cutting performance of the cethe coating is l.000-1.300 C. At lower temperatures the deposition rate becomes very low and at higher temperatures excessive interaction occurs between the coating and the cemented carbide substrate.
The metal-cutting performance of cemented carbide inserts coated with hafnium carbonitride in accordance with this invention is shown in the following Table III. In Table III. examples 13 through 19 were k inch X V2 inch X 3/16 inch disposable cutting inserts, coated with hafnium carbonitridc at l.000l.l70 C. by the vapor deposition technique disclosed above for examples I through 6. The cemented carbide substrate was 72% WC, 8% TiC. 11.5% TaC, and 8.5% Co. Two levels of coating thickness, 1.5 2 microns and 4-5 microns. were prepared. These inserts were then used to machine SAE 1045 steel. 190 Bl-IN hardness, at 700 surfacefeet-per-minute speed. .010 inches-per-revolution feed, and .100 inches depth of cut. Examples 13 through 17 all had coating thicknesses in the 1.5 2 micron range and are listed in order of increasing carbon mented carbide tool material is very substantially improved by the hafnium carbonitride coating. It is also evident that the amount of improvement obtained is strongly dependent upon the carbon to nitrogen ratio with a peak in performance at about 4.61 angstrom units. It is probable that thicker coatings of 5 to 10 microns will provide an additional increment of improvement. When compared with the performance of the 5 micron thick TiC coated insert, it is evident that a substantial performance advantage is obtained for the 1.5 2 micron hafnium carbonitride coated inserts at or near the optimum composition and that a very substantial advantage is obtained when the hafnium carboni tride coating thickness is equal to that of the TiC coatmg.
The strength of the hafnium carbonitride coated composites was measured using a transverse rupture test that comprised three roll loading with a test span to thickness ratio of 3.5 to 1. Using this test it was found that the strength of hafnium carbonitride coated when the carbon to nitrogen ratio is at the optimum value of about 3 (lattice parameter of about 4.610 A). useful performance is obtained within a composition range of 4.57 to 4.63 A, which represents a carbon to nitrogen ratio range of about .73 to 12. The metal-cutting performance of zirconium carbonitride coated inserts prepared in accordance with this invention is shown in the following Table W. In
Table lV, Examples 22 through 32 were a inch X A inch X 3/ l6.inch disposable cutting inserts, coated with zirconium carbonitride at l;-100'-l, 15'0 C. by the vapor deposition technique disclosed above for Examples 6 through'l2. The cemented carbide substrate was tride, upon the carbon-'to-nitrogen ratio with a strong parameter of about I 4.610 was about 190,000 psi. The strength of 5 microns thick TiC-coated composites (using the same substrate carbide) was 150,000. It is therefore evident that zirconium carbonitride-coated composites having the optimum carbon-to-nitrogen ratio for metal cutting possess a superior combination of metal-cutting performance and strength when compared with TiC-coated composites.
in addition to the pure hafnium carbonitride and zirconiumcarbonitride coatings described above. a few coatedinser-ts were preparedin which the coating was 72% WC, 8% TiC, ll.5% TaC, and 8.5% Co. A range of coating thicknesses from 2.5 to 8 microns was obtained. These inserts were-then used to machine SAE i045 steel, 190 BHN hardness, at 700 surface-feet-per-.
minute speed. .010 inches per revolution feed, and .100
.25 inches depth of cut. The Examples 22-32 are listed by order of increasing carbon-to-nitrogen ratio in the coating, and cutting time to a flank wear of .010 inch is shown as a measure of cutting performance, For comparison purposes. the cutting performance of the coated insert. Example 34. is also shown in Table IV.
TABLE IV METAL CUTTING PERFORMANCE OF ZlRCONlUM CARBONlTRlDE TOOLS (CUTTING SAE 1045 STEEL. I90 BHN. AT 700 SFPM SPEED) Cutting Coatin Character Etttce Time to Thickness Parameter 0l0" Wcar Example Microns A Est. C/N (Min.)
22 2.5 4.583 .1 l 6.5 23 3. 4.595 .25 ll. 24 3. 4.60] .33 ll. 25 5. 4.602 .35 ll).
26 3. 4.606 .41 l4. 27 5. 4.609 .45 26. 28 8. 4.6ll .48 23. 29 3.5 4.612 .50 20. 30 5. 4.613 .53 i7. 3| 4. 4.6[6 .58 16. r 32 3. 4.620 .67 i3. 33 uncoated 5.
- substrate 34 $.(TiC 22.
coated) It can be seen that the cutting performance of the cemented carbide tool material is very substantiallyimcomposed of a solid solution of both hafnium and zirconium carbonitride. This was accomplished by simultaneously passing chlorides of hafnium and zirconium .(along with hydrogen, nitrogen, and methane gases) over the cemented carbide inserts. it is very difficult to characterize the exact compositions of such coatings 1 since the zirconium-to-hafnium ratio'influences the lattice-parameter as does the carbon-to-nitrogen ratio. ltwas found, however, that when the resulting lattice parameter was within the desired range described above for pure hafnium carbonitride, i.e., 4.570 to 4.630 anguncoated substrate material. Example 33. and aTiC- proved by the zirconium carbonitride coating. It is also evident that the amount of improvement obtained is strongly dependent. as in the case of hafnium carbonistrom units, excellent metal cutting performance was obtained. vSuch mixtures are accordingly included within the scope of this invention.
l. A coated cemented carbide product comprising a cemented carbide substrate and a fully dense coating selected from the group consisting of hafnium carbonitride, zirconium carbonitride and mixtures of the two, said coating firmly and adherently bonded to said substrate,
the hafnium carbonitride coating and the hafnium and zirconium carbonitride coatings having an X-ray diffraction lattice parameter within the range of about 4.570 to 4.630 angstrom units and the zirconium carbonitride coating having an X-ray diffraction parameter within the range of about 4.600 to 4.620 angstrom units.
2. The coated cemented carbide product of claim 1 in which the coating is hafnium carbonitride.
3. The coated cemented carbide product of claim 1 in which the coating is zirconium carbonitride.
4. The coated cemented carbide product of claim 1 in which the cemented carbide substrate comprises tungsten carbide and a cobalt matrix.
5. The coated cemented carbide product of claim 1 in which the cemented carbide substrate comprises tungsten carbide. titanium carbide. tantalum carbide and a cobalt matrix.
6. The coated cemented carbide product of claim 1 .crons thiek igs t i 4 ii

Claims (6)

1. A COATED CEMENTED CARBIDE PRODUCT COMPRISING A CEMENTED CARBIDE SUBSTRATE AND A FULLY DENSE COATING SELECTED FROM THE GROUP CONSISTING OF HAFNIUM CARBONITRIDE, ZIRCONIUM CARBONITRIDE AND MIXTURES OF THE TWO, SAID COATING FIRMYL AND ADHERENTLY BONDED TO SAID SUBSTRATE; THE HAFNIUM CARBONITRIDE COATING AND THE HAFNIUM AND ZIRCONIUM CARBONITRIDE COATINGS HAVING AN X-RAY DIFFRACTION LATTICE PARAMETER WITHIN THE RANGE OF ABOUT 4,570 TO 4.630 ANGSTROM UNITS AND THE ZIRCONIUM CARBONITRIDE COATING HAVING AN X-RAY DIFFRACTION PARAMETER WITHIN THE RANGE OF ABOUT 4.600 TO 4.620 ANGSTROM UNITS.
2. The coated cemented carbide product of claim 1 in which the coating is hafnium carbonitride.
3. The coated cemented carbide product of claim 1 in which the coating is zirconium carbonitride.
4. The coated cemented carbide product of claim 1 in which the cemented carbide substrate comprises tungsten carbide and a cobalt matrix.
5. The coated cemented carbide product of claim 1 in which the cemented carbide substrate comprises tungsten carbide, titanium carbide, tantalum carbide and a cobalt matrix.
6. The coated cemented carbide product of claim 1 in which the carbonitride coating is from 1 to 10 microns thickness.
US00225667A 1972-02-11 1972-02-11 Coated cemented carbide products Expired - Lifetime US3854991A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
BE795014D BE795014A (en) 1972-02-11 COATED AGGLOMERATED CARBIDE TYPE PRODUCTS
US00225667A US3854991A (en) 1972-02-11 1972-02-11 Coated cemented carbide products
GB393473A GB1388261A (en) 1972-02-11 1973-01-25 Coated cemented carbide products
CA162,535A CA989688A (en) 1972-02-11 1973-01-31 Coated cemented carbide products
AU51679/73A AU478083B2 (en) 1972-02-11 1973-02-01 Coated cemented carbide products
CH159773A CH585273A5 (en) 1972-02-11 1973-02-05
IT20060/73A IT978836B (en) 1972-02-11 1973-02-06 PRODUCTS IN COATED CEMENTED CARBIDE
DE2306504A DE2306504C3 (en) 1972-02-11 1973-02-09 Coated cemented carbide body
SE7301897A SE380006B (en) 1972-02-11 1973-02-09
FR7304587A FR2171334B1 (en) 1972-02-11 1973-02-09
BR731004A BR7301004D0 (en) 1972-02-11 1973-02-09 COATED CEMENTED CARBON PRODUCT AND PROCESS FOR ITS PREPARATION
JP1574473A JPS5425482B2 (en) 1972-02-11 1973-02-09
PL1973160687A PL83467B1 (en) 1972-02-11 1973-02-10

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US00225667A US3854991A (en) 1972-02-11 1972-02-11 Coated cemented carbide products

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US (1) US3854991A (en)
JP (1) JPS5425482B2 (en)
BE (1) BE795014A (en)
BR (1) BR7301004D0 (en)
CA (1) CA989688A (en)
CH (1) CH585273A5 (en)
DE (1) DE2306504C3 (en)
FR (1) FR2171334B1 (en)
GB (1) GB1388261A (en)
IT (1) IT978836B (en)
PL (1) PL83467B1 (en)
SE (1) SE380006B (en)

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US3958070A (en) * 1973-06-22 1976-05-18 Schwarzkopf Development Corporation Decorative metallic articles with differently colored surface zones
DE3003353A1 (en) * 1979-02-07 1980-08-14 Gen Electric COATED SINTER CARBIDE PRODUCT
US4276096A (en) * 1977-04-22 1981-06-30 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Method for producing hard metal bodies of increased wear resistance
US4409003A (en) * 1982-05-20 1983-10-11 Gte Laboratories Incorporated Carbonitride coated silicon nitride cutting tools
US4409004A (en) * 1982-05-20 1983-10-11 Gte Laboratories Incorporated Carbonitride coated composite silicon nitride cutting tools
US4440547A (en) * 1982-05-20 1984-04-03 Gte Laboratories Incorporated Alumina coated silicon nitride cutting tools
US4442169A (en) * 1982-01-28 1984-04-10 General Electric Company Multiple coated cutting tool and method for producing same
US4696352A (en) * 1986-03-17 1987-09-29 Gte Laboratories Incorporated Insert for a drilling tool bit and a method of drilling therewith
US5238711A (en) * 1990-11-05 1993-08-24 The President And Fellows Of Harvard College Method of coating carbon fibers with a carbide
US5521001A (en) * 1990-11-05 1996-05-28 Northeastern University Carbide formed on a carbon substrate
WO2008103605A3 (en) * 2007-02-19 2008-11-13 Tdy Ind Inc Carbide cutting insert
US8440314B2 (en) 2009-08-25 2013-05-14 TDY Industries, LLC Coated cutting tools having a platinum group metal concentration gradient and related processes

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CA1087041A (en) * 1975-09-15 1980-10-07 Mohammad J. Hakim Hafnium carbide and nitride coatings
CH640885A5 (en) * 1978-07-21 1984-01-31 Suisse Horlogerie Rech Lab MACHINE ELEMENTS WITH A HARD COVER.
FR2557152A1 (en) * 1983-12-26 1985-06-28 Instr I Single-layer antiwear coating for tools for the working of metals by removal of material
ATE206772T1 (en) * 1995-08-19 2001-10-15 Widia Gmbh COMPOSITE BODY AND METHOD FOR THE PRODUCTION THEREOF
DE19719195A1 (en) 1997-05-09 1998-11-12 Widia Gmbh Cutting insert for machining and method for producing this cutting insert

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US3356618A (en) * 1963-11-25 1967-12-05 Int Research & Dev Co Ltd Coated boron containing material dispersed in a metal matrix
US3656995A (en) * 1969-05-02 1972-04-18 Texas Instruments Inc Chemical vapor deposition coatings on titanium
US3717496A (en) * 1969-11-28 1973-02-20 Deutsche Edelstahlwerke Ag Machine parts having a wear-and abrasion-resistant surface
US3744979A (en) * 1971-04-14 1973-07-10 Adamas Carbide Corp Method of forming a hard surface on cemented carbides and resulting article

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3958070A (en) * 1973-06-22 1976-05-18 Schwarzkopf Development Corporation Decorative metallic articles with differently colored surface zones
US4276096A (en) * 1977-04-22 1981-06-30 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Method for producing hard metal bodies of increased wear resistance
DE3003353A1 (en) * 1979-02-07 1980-08-14 Gen Electric COATED SINTER CARBIDE PRODUCT
US4268569A (en) * 1979-02-07 1981-05-19 General Electric Company Coating underlayers
US4442169A (en) * 1982-01-28 1984-04-10 General Electric Company Multiple coated cutting tool and method for producing same
US4409003A (en) * 1982-05-20 1983-10-11 Gte Laboratories Incorporated Carbonitride coated silicon nitride cutting tools
US4409004A (en) * 1982-05-20 1983-10-11 Gte Laboratories Incorporated Carbonitride coated composite silicon nitride cutting tools
US4440547A (en) * 1982-05-20 1984-04-03 Gte Laboratories Incorporated Alumina coated silicon nitride cutting tools
US4696352A (en) * 1986-03-17 1987-09-29 Gte Laboratories Incorporated Insert for a drilling tool bit and a method of drilling therewith
US5238711A (en) * 1990-11-05 1993-08-24 The President And Fellows Of Harvard College Method of coating carbon fibers with a carbide
US5521001A (en) * 1990-11-05 1996-05-28 Northeastern University Carbide formed on a carbon substrate
WO2008103605A3 (en) * 2007-02-19 2008-11-13 Tdy Ind Inc Carbide cutting insert
RU2465098C2 (en) * 2007-02-19 2012-10-27 Ти Ди Уай Индастриз, Инк. Hard metal tip
US8512882B2 (en) 2007-02-19 2013-08-20 TDY Industries, LLC Carbide cutting insert
CN103484858A (en) * 2007-02-19 2014-01-01 Tdy工业有限责任公司 Carbide cutting insert
US8440314B2 (en) 2009-08-25 2013-05-14 TDY Industries, LLC Coated cutting tools having a platinum group metal concentration gradient and related processes

Also Published As

Publication number Publication date
BE795014A (en) 1973-05-29
IT978836B (en) 1974-09-20
GB1388261A (en) 1975-03-26
AU5167973A (en) 1974-08-01
PL83467B1 (en) 1975-12-31
FR2171334A1 (en) 1973-09-21
SE380006B (en) 1975-10-27
CH585273A5 (en) 1977-02-28
DE2306504C3 (en) 1986-11-13
BR7301004D0 (en) 1973-09-25
DE2306504A1 (en) 1973-08-16
FR2171334B1 (en) 1977-04-22
JPS5425482B2 (en) 1979-08-28
JPS4892209A (en) 1973-11-30
DE2306504B2 (en) 1981-02-19
CA989688A (en) 1976-05-25

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