US3836392A - Process for increasing the resistance to wear of the surface of hard metal cemented carbide parts subject to wear - Google Patents

Process for increasing the resistance to wear of the surface of hard metal cemented carbide parts subject to wear Download PDF

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US3836392A
US3836392A US00269242A US26924272A US3836392A US 3836392 A US3836392 A US 3836392A US 00269242 A US00269242 A US 00269242A US 26924272 A US26924272 A US 26924272A US 3836392 A US3836392 A US 3836392A
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wear
cemented carbide
oxide
resistance
hard metal
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B Lux
C Triquet
R Funk
H Schachner
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Santrade Ltd
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Sandvik AB
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/403Oxides of aluminium, magnesium or beryllium
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264Up to 3 mils

Definitions

  • This invention relates to a process for increasing the resistance to wear of cutting tools or other cemented carbide hard metal parts subject to wear and to the cutting tools obtained by this process.
  • This invention relates to a process for increasing the wear resistance of cemented carbide articles subject to wear, for instance cutting tools, and to the cemented carbide articles, in particular cutting tools, obtained by this process.
  • cemented carbides consist of a mixture of at least one metal serving as a binder and at least one metal carbide of great hardness.
  • the carbide may be particularly tungsten, titanium, tantalum or niobium carbide or a mixed carbide of tantalum and niobium.
  • the binder metal may be, for example, cobalt, iron or nickel.
  • the surface of such cemented carbide articles is very hard and resistant to abrasion, more than that of common metals and alloys, particularly steel.
  • such parts can be used for many applications in which the surface of the parts must have a great hardness and resistance to abrasion, particularly for producing cutting tools, which cannot be reground, such as those used for machining hard metals such as steel, in drawing dies, etc.
  • a process for increasing the resistance to wear of hard metal blades for cutting tools is already known. This process consists in providing the surface of the blades with a coating having a resistance to wear higher than that of the original surface of the blade, this coating being formed of at least one carbide selected from the same constituents which form the hard metal itself, particularly titanium carbide TiC.
  • THE INVENTION It is therefore the object of the present invention to provide a process for increasing the resistance to wear of the surface of hard cemented carbides metal parts, particularly of cutting blades for cutting tools which cannot be reground, which process provides a resistance to wear higher than that which can be obtained by the known process described above.
  • the process according to the invention comprises coating at least a portion ofthe surface of the cemented carbide article with a layer of a refractory oxide selected from the group including aluminium oxide, zirconium oxide and stabilized zirconium oxide in a thick ness of up to 20 microns.
  • the stabilized zirconium oxide used may be, for example, zirconium oxide stabilized by 10 mole percent of magnesium oxide or 5 mole percent of calcium oxide or at least one rare earth oxide in an appropriate ratio.
  • the refractory oxides mentioned above may be used either alone or in the form of a mixture of these oxides.
  • refractory oxides particularly aluminium oxide and stabilized zirconium oxide
  • these oxides are more brittle than hard metal cemented carbide at least when these oxides are in the form of relatively large bodies of a size of at least some millimetres. Consequently, by coating the surface of a hard metal part with a layer of refractory oxide normally there was not to be expected an adhesion of the coating on the surface of the cemented carbide part which would be sufficient to result in a durable improvement of the resistance to wear of such surface.
  • the advantageous and unexpected result obtained is probably due to the careful choice of the thickness of the layer of refractory oxide.
  • the thickness of the refractory oxide layer must be in the range between 0.1 and 10 microns to obtain the greatest increase in the resistance to wear.
  • the thickness of the refractory oxide layer is less than 0.1 microns it wears off rapidly and when the thickness is greater than about 10 microns its toughness decreases.
  • any appropriate known method may be used which permits to obtain a compact, coherent and homogeneous adhering coating of a thickness which is substantially uniform at least over the portions ofthe surface to be coated in which the resistance to wear is to be increasedl.
  • particles of a refractory oxide powder which at least in part are in a liquid state may be cast on to the surface to be coated by some known appropriate means, for example, a plasma torch.
  • the deposition of the coating layer may advantageously be effected by a treatment at a high temperature and/or by subjecting the surface of the hard metal part, after the application of the coating layer, to a further thermal treatment at a high temperature for increasing the adhesion of the refractory oxide layer on said surface by diffusion with substitution of atoms.
  • the deposition of the coating layer may also be effected by electrophoresis with a subsequent thermal treatment, at a high temperature, of the surface of the coating layer.
  • the termal treatment is advantageously carried out at a temperature between 700 and I200C. for a duration of at least half an hour.
  • the thermal treatment may also be carried out for a duration of more than half an hour at a temperature of about 700C.
  • the oxide layer is preferably deposited from a gaseous state, particularly by evaporation and condensation under vacuum, cathodic spraying and deposition by chemical reaction in the gaseous phase, this method being usually referred to as chemical vapour deposition" or C.V.D.
  • This latter method is particularly employed in the preferred form of putting the invention into practice and it permits to obtain the deposition of a refractory oxide coating layer which to a large extent possesses the above-mentioned desired properties.
  • the temperature and pressure conditions which permit the deposition of the refractory oxide coating layer they must be selected according to the nature of the chemical compounds used as starting compounds. This selection can be made by one skilled in the art as it is evident from the abundant literature which has already been published on the conditions which are suitable for the deposition of various refractory oxides by chemical reaction in the gaseous phase (cf. for example, the book Vapor deposition by C. F. Powell, J. H. Oxley and J. M. Blocher, published by John Wiley and Sons Inc., New York, London, Sidney).
  • Overall pressure of the gaseous phase 1 to 760 torr (preferably between 30 and 80 torr).
  • Temperature of the surface of the part to be coated 700 to 1200C. (preferably between 900 and 1 150C).
  • Overall pressure of the gaseous phase 1 to 760 torr (preferably between 10 and 125 torr).
  • the conditions are similar and may be selected, for example, by taking into account the indications given at page 400 of the above-mentioned book.
  • a zirconium oxide coating layer may also be produced by oxidizing, for example, with oxygen, carbon dioxide or other similar oxygenated compounds, a layer ofzirconium carbide or nitride deposited on a substrate by chemical reaction in the gaseous phase.
  • any device for depositing refractory oxides by chemical reaction in the gaseous phase any device may be used which is suitable for the starting compounds as well as the dimensions and number of articles to be coated. Such devices are known per se and many forms of construction and variations thereof have been described in the relevant technical literature.
  • FIG. 1 is a schematic overall view of the device
  • FIG. 2 is a sectional view, on a larger scale, showing the portion of the device with the part to be coated (the reaction chamber).
  • the device shown in FIG. 1 comprises a reaction chamber 1 of quartz, provided with a movable support bar 2, likewise of quartz, shiftably mounted in a gasket 3 which is cooled by cold water.
  • a coiled copper pipe 4 which is cooled by a flow of water and connected to a high frequency electric current generator, permits the cemented carbide article 5 to be heated by induction, the article 5 being placed on the support bar 2 and being the part to be coated, in the illustrated embodiment, with aluminium oxide.
  • the reaction chamber 1 is supplied through a conduit 6 with a mixture of hydrogen and aluminium chloride from a device 7 for producing aluminium chloride in the gaseous phase and for mixing this gas with hydrogen at a variable ratio.
  • the walls of the conduit 6 are kept at 200C. by heating means not shown in the drawing.
  • a further conduit 8 supplies the reaction chamber 1 with carbon dioxide or with a mixture of hydrogen and water vapour, depending on the type of reaction selected for depositing the aluminium.
  • One or the other of these mixtures is supplied by a device 9 for mixing the gas.
  • the devices 7 and 9 are provided with means for purging and rinsing by an inert gas such as argon which is supplied by an outside storage container not shown in the drawing.
  • a pumping unit 11 is connected to the reaction chamber 1 through a conduit 10 and permits to establish in the reaction chamber a pressure which can be adjusted according to the requirements of the process, this pressure being between 1 and 760 torr.
  • FIG. 2 shows the manner in which the article 5 to be coated is arranged on the support bar 2 in greater detail in FIG. 2.
  • a removable support 12 formed by an aluminium oxide plate is interposed between the article 5 and the support bar 2.
  • FIG. 2 also shows the device for mixing the gas flows supplied to the reaction chamber 1 through the conduits 6 and 8.
  • This device substantially comprises a bellmouthed tube 13 having a smaller diameter than that of the conduit 6.
  • a thermocouple 14, not shown in FIG. 1, permits to measure the temperature of the part 5.
  • a device similar to that which has been described above can be used for depositing a zirconium oxide coating layer or a stabilized zirconium oxide coating layer or a layer consisting of a mixture of at least two of the above-mentioned oxides.
  • the device 7 for producing gaseous aluminium chloride by a device for producing the volatile zirconium compound or the mixture of volatile zirconium and the element corresponding to the oxide stabilizing the zirconium oxide, or by a device for producing a mixture of volatile compounds of aluminium, zirconium and, if desired, a stabilizing compound.
  • EXAMPLE 1 An aluminium oxide coating layer having a thickness of 5 microns was deposited on a cutting blade of a hard cemented carbide metal cutting tool by using said first mentioned reaction (reaction of aluminium chloride with water vapour).
  • Time of treatment 5 hrs. Temperature 1000C.
  • Overall pressure of the gaseous phase 5 torr Feed rate of the gaseous hydrogen mixture (carrier gas) (amount reduced to 20C. and 760 ton")
  • Aluminium chloride Al Water vapour 400 em /min. mg/min. 4 mg/min.
  • the major portion of the coating layer was formed by alpha alumina.
  • composition of the hard metal cemented carbide of the cutting tool was as follows (in percent by weight):
  • EXAMPLE 2 An aluminium oxide coating layer having a thickness of 1 micron was deposited on a cutting blade for a cutting tool of hard metal of the same composition as that described in Example 1 by using said second reaction indicated above (reaction of aluminium chloride with carbon dioxide and hydrogen) under the following reaction conditions:
  • EXAMPLE 3 The process as described in Example 2 was repeated, but with a time of minutes for the depositing operation. Apart from this, all the reaction conditions were the same as described in Example 2. In this manner an alpha, alumina coating layer having a thickness of 6 microns is deposited on the hard metal cemented carbide cutting tool.
  • the cemented carbide of the standard ISO P10 has the following composition (in by weight):
  • a cemented carbide tool provided with a surface coating produced by coating at least a portion of the surface of the cemented carbide with a layer 0.] to 20 microns thick of refractory oxide selected from the group including aluminium oxide, zirconium oxide and stabilized zirconium oxide.
  • cemented carbide tool as claimed in claim 1 wherein said cemented carbide is composed of a carbide of a metal selected from the group consisting of tungsten, titanium, tantalum and niobium, or a mixed carbide of tantalum and niobium; and a binder metal selected from the group consisting of cobalt, iron, and

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Physical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

A process for increasing the resistance to wear of the surface of hard metal parts subject to wear, such as the cutting blade of cutting tools, by coating the surface of the hard cemented carbide articles with a layer of refractory oxide such as aluminium oxide, ziroconium oxide or stabilized zirconium oxide in a thickness of up to 20 microns.

Description

D United States Patent 11 1 1111 3,836,392
Lux et al. 1 1 Sept. 17, 1974 [54] PROCESS FOR INCREASING THE 3,251,337 5/1966 Latta et a1. 117/106 RESISTANCE TO WEAR OF THE SURFACE g t g as 1e a... 0F HARD METAL CEMENTED CARBIDE 3,640,757 2/1972 Grubba 117/169 PARTS SUBJECT TO WEAR 3,642,522 2/1972 Gass et a1 117/106 0 [75] Inventors: Benno Lux, Veyrier, Geneva; SDalEurai e1 6 runner 6 a gggfjfigfg 215 x3233? 3,752,655 8/1973 Ramqvist 117/106 c G ndilancy Ge e a, an of 3,770,512 11/1973 Bopp 148/63 Switzerland; Christian Triquet, Rosleres Belglum Primary ExaminerCharles E. Van Horn [73] Assignee: Sandvik AB, Stockholm, Sweden Assistant Examiner-J. W. Massie Attorney, Agent, or Firm-Robert E. Burns; [22] Filed July 1972 Emmanuel J. Lobato; Bruce L. Adams [21] Appl. No.: 269,242
[30] Foreign Application Priority Data July 7, 1971 Switzerland 9943/71 [57] ABSTRACT [52] US. Cl. 117/169 R, 117/106 R, 148/63, A process for increasing the resistance to wear of the 30/350 surface of hard metal parts subject to wear, such as [51] Int. Cl. C23c 11/08 the Cutting b e 01 Cutting tools, by coating the sur- [58] Field of Search, 1 17/169 R, 106 R, 22, 106 C; face of the hard cemented carbide articles with a layer 148/63, 6; 30/350 of refractory oxide such as aluminium oxide, ziroconium oxide or stabilized zirconium oxide in a [56] References Cited thickness of up to 20 microns.
UNITED STATES PATENTS 3,196,056 7/1965 Ornitz 117/169 3 Claims, 2 Drawing Figures PROCESS FOR INCREASING THE RESISTANCE TO WEAR OF THE SURFACE OF HARD METAL CEMENTED CARBIDE PARTS SUBJECT TO WEAR FIELD OF THE INVENTION This invention relates to a process for increasing the resistance to wear of cutting tools or other cemented carbide hard metal parts subject to wear and to the cutting tools obtained by this process. This invention relates to a process for increasing the wear resistance of cemented carbide articles subject to wear, for instance cutting tools, and to the cemented carbide articles, in particular cutting tools, obtained by this process.
BACKGROUND OF THE INVENTION As is known parts made of hard metal otherwise known as cemented carbides consist of a mixture of at least one metal serving as a binder and at least one metal carbide of great hardness. The carbide may be particularly tungsten, titanium, tantalum or niobium carbide or a mixed carbide of tantalum and niobium. The binder metal may be, for example, cobalt, iron or nickel. The surface of such cemented carbide articles is very hard and resistant to abrasion, more than that of common metals and alloys, particularly steel. Therefore, such parts can be used for many applications in which the surface of the parts must have a great hardness and resistance to abrasion, particularly for producing cutting tools, which cannot be reground, such as those used for machining hard metals such as steel, in drawing dies, etc.
Obviously, it is very desirable to further increase the resistance to wear of the surface of or articles. In particular, in the case of cutting blades such an increase of wear resistance would increase the useful life of the cutting blades for a given cutting speed and would permit to increase the cutting speed for a given useful life or would even permit to increase simultaneously the cutting speed and the useful life.
A process for increasing the resistance to wear of hard metal blades for cutting tools is already known. This process consists in providing the surface of the blades with a coating having a resistance to wear higher than that of the original surface of the blade, this coating being formed of at least one carbide selected from the same constituents which form the hard metal itself, particularly titanium carbide TiC.
THE INVENTION It is therefore the object of the present invention to provide a process for increasing the resistance to wear of the surface of hard cemented carbides metal parts, particularly of cutting blades for cutting tools which cannot be reground, which process provides a resistance to wear higher than that which can be obtained by the known process described above.
The process according to the invention comprises coating at least a portion ofthe surface of the cemented carbide article with a layer of a refractory oxide selected from the group including aluminium oxide, zirconium oxide and stabilized zirconium oxide in a thick ness of up to 20 microns.
The stabilized zirconium oxide used may be, for example, zirconium oxide stabilized by 10 mole percent of magnesium oxide or 5 mole percent of calcium oxide or at least one rare earth oxide in an appropriate ratio. The refractory oxides mentioned above may be used either alone or in the form of a mixture of these oxides.
To increase the resistance to wear and consequently the useful life of a hard metal part by means of a coating of refractory oxide is quite an unexpected result. In fact, although it is well known that refractory oxides, particularly aluminium oxide and stabilized zirconium oxide, are very hard, it is equally well known that these oxides are more brittle than hard metal cemented carbide at least when these oxides are in the form of relatively large bodies of a size of at least some millimetres. Consequently, by coating the surface of a hard metal part with a layer of refractory oxide normally there was not to be expected an adhesion of the coating on the surface of the cemented carbide part which would be sufficient to result in a durable improvement of the resistance to wear of such surface.
The advantageous and unexpected result obtained is probably due to the careful choice of the thickness of the layer of refractory oxide. In fact, preferably the thickness of the refractory oxide layer must be in the range between 0.1 and 10 microns to obtain the greatest increase in the resistance to wear. When the thickness of the refractory oxide layer is less than 0.1 microns it wears off rapidly and when the thickness is greater than about 10 microns its toughness decreases.
For depositing the refractory oxide layer on the surface of the hard metal part any appropriate known method may be used which permits to obtain a compact, coherent and homogeneous adhering coating of a thickness which is substantially uniform at least over the portions ofthe surface to be coated in which the resistance to wear is to be increasedl. For example, particles of a refractory oxide powder which at least in part are in a liquid state may be cast on to the surface to be coated by some known appropriate means, for example, a plasma torch. To obtain a well adhering coating, the deposition of the coating layer may advantageously be effected by a treatment at a high temperature and/or by subjecting the surface of the hard metal part, after the application of the coating layer, to a further thermal treatment at a high temperature for increasing the adhesion of the refractory oxide layer on said surface by diffusion with substitution of atoms. The deposition of the coating layer may also be effected by electrophoresis with a subsequent thermal treatment, at a high temperature, of the surface of the coating layer. In any case the termal treatment is advantageously carried out at a temperature between 700 and I200C. for a duration of at least half an hour. The thermal treatment may also be carried out for a duration of more than half an hour at a temperature of about 700C. The oxide layer is preferably deposited from a gaseous state, particularly by evaporation and condensation under vacuum, cathodic spraying and deposition by chemical reaction in the gaseous phase, this method being usually referred to as chemical vapour deposition" or C.V.D. This latter method is particularly employed in the preferred form of putting the invention into practice and it permits to obtain the deposition of a refractory oxide coating layer which to a large extent possesses the above-mentioned desired properties.
DETAILED DESCRIPTION Among the various chemical reactions which may be used for depositing the refractory oxide coating layer preferably the reaction of a volatile halide, particularly a chloride, of the metal corresponding to the oxide, with water or with a mixture of carbon dioxide and hydrogen is chosen.
Thus, for example, for depositing an aluminium oxide coating layer one of the following two reactions may be used:
2 AlCl 3 H O- Al O 6 HCL 2 AlCl 3 CO 3 H Al O 3 C 6 HCl For depositing a coating layer of stabilized zirconium oxide (also called stabilized zirconium), on the one hand, one of the following two reactions:
ZrCl, 2 CO 2 H --ZrO 2 C0 4 HC] and, on the other hand, one of the following two reactions for the formation of a stabilized ZrO oxide may be used, which is effected simultaneously with the corresponding reaction for the formation of zirconium oxide (merely by way of example, the two reactions are indicated hereafter for the case of the stabilizing oxide component being formed by magnesium oxide):
In this case it is sufficient to select the proportion of zirconium chloride and of the element corresponding to the stabilizing oxide (here magnesium chloride) to obtain the desired proportion of stabilizing oxide (for example, 10 mole percent in the case of magnesium oxide) in the stabilized zirconium oxide.
As to the temperature and pressure conditions which permit the deposition of the refractory oxide coating layer, they must be selected according to the nature of the chemical compounds used as starting compounds. This selection can be made by one skilled in the art as it is evident from the abundant literature which has already been published on the conditions which are suitable for the deposition of various refractory oxides by chemical reaction in the gaseous phase (cf. for example, the book Vapor deposition by C. F. Powell, J. H. Oxley and J. M. Blocher, published by John Wiley and Sons Inc., New York, London, Sidney).
For example, for depositing aluminium oxide by reaction of aluminium chloride with water preferably the following conditions are chosen:
Temperature of the surface of the part to be coated with the aluminium layer: 600 to 1200C.
Overall pressure of the gaseous phase: 1 to 760 torr (preferably between 30 and 80 torr).
For depositing aluminium oxide by reaction of aluminium chloride with carbon dioxide and hydrogen, the following conditions are preferably chosen:
Temperature of the surface of the part to be coated: 700 to 1200C. (preferably between 900 and 1 150C).
Overall pressure of the gaseous phase: 1 to 760 torr (preferably between 10 and 125 torr).
For depositing stabilized or unstabilized zirconium oxide the conditions are similar and may be selected, for example, by taking into account the indications given at page 400 of the above-mentioned book.
A zirconium oxide coating layer may also be produced by oxidizing, for example, with oxygen, carbon dioxide or other similar oxygenated compounds, a layer ofzirconium carbide or nitride deposited on a substrate by chemical reaction in the gaseous phase.
For depositing refractory oxides by chemical reaction in the gaseous phase any device may be used which is suitable for the starting compounds as well as the dimensions and number of articles to be coated. Such devices are known per se and many forms of construction and variations thereof have been described in the relevant technical literature.
A preferred embodiment of the invention will now be described by way of example and with reference to the accompanying drawing which schematically shows a device for depositing an aluminium oxide coating layer on the surface of a cemented carbide article by chemical reaction in the gaseous phase according to one of the reactions'indicated above, and in which:
FIG. 1 is a schematic overall view of the device, and
FIG. 2 is a sectional view, on a larger scale, showing the portion of the device with the part to be coated (the reaction chamber).
The device shown in FIG. 1 comprises a reaction chamber 1 of quartz, provided with a movable support bar 2, likewise of quartz, shiftably mounted in a gasket 3 which is cooled by cold water. A coiled copper pipe 4, which is cooled by a flow of water and connected to a high frequency electric current generator, permits the cemented carbide article 5 to be heated by induction, the article 5 being placed on the support bar 2 and being the part to be coated, in the illustrated embodiment, with aluminium oxide.
The reaction chamber 1 is supplied through a conduit 6 with a mixture of hydrogen and aluminium chloride from a device 7 for producing aluminium chloride in the gaseous phase and for mixing this gas with hydrogen at a variable ratio. The walls of the conduit 6 are kept at 200C. by heating means not shown in the drawing. A further conduit 8 supplies the reaction chamber 1 with carbon dioxide or with a mixture of hydrogen and water vapour, depending on the type of reaction selected for depositing the aluminium. One or the other of these mixtures is supplied by a device 9 for mixing the gas.
The devices 7 and 9 are provided with means for purging and rinsing by an inert gas such as argon which is supplied by an outside storage container not shown in the drawing. A pumping unit 11 is connected to the reaction chamber 1 through a conduit 10 and permits to establish in the reaction chamber a pressure which can be adjusted according to the requirements of the process, this pressure being between 1 and 760 torr.
The manner in which the article 5 to be coated is arranged on the support bar 2 is shown in greater detail in FIG. 2. In the illustrated embodiment, a removable support 12 formed by an aluminium oxide plate is interposed between the article 5 and the support bar 2. FIG. 2 also shows the device for mixing the gas flows supplied to the reaction chamber 1 through the conduits 6 and 8. This device substantially comprises a bellmouthed tube 13 having a smaller diameter than that of the conduit 6. A thermocouple 14, not shown in FIG. 1, permits to measure the temperature of the part 5.
A device similar to that which has been described above can be used for depositing a zirconium oxide coating layer or a stabilized zirconium oxide coating layer or a layer consisting of a mixture of at least two of the above-mentioned oxides. For this purpose it is only necessary to replace the device 7 for producing gaseous aluminium chloride by a device for producing the volatile zirconium compound or the mixture of volatile zirconium and the element corresponding to the oxide stabilizing the zirconium oxide, or by a device for producing a mixture of volatile compounds of aluminium, zirconium and, if desired, a stabilizing compound.
Some practical Examples for carrying out the process of the present invention will now be described in greater detail.
EXAMPLE 1 An aluminium oxide coating layer having a thickness of 5 microns was deposited on a cutting blade of a hard cemented carbide metal cutting tool by using said first mentioned reaction (reaction of aluminium chloride with water vapour).
The reaction conditions were as follows:
Time of treatment 5 hrs. Temperature 1000C. Overall pressure of the gaseous phase 5 torr Feed rate of the gaseous hydrogen mixture (carrier gas) (amount reduced to 20C. and 760 ton") Aluminium chloride (A1Cl Water vapour 400 em /min. mg/min. 4 mg/min.
It was found that the major portion of the coating layer was formed by alpha alumina.
The composition of the hard metal cemented carbide of the cutting tool was as follows (in percent by weight):
Cobalt 9.5 Titanium carbide 11.9 Tantalum carbide 6 Niobium carbide 4 Tungsten carbide 68.6
EXAMPLE 2 An aluminium oxide coating layer having a thickness of 1 micron was deposited on a cutting blade for a cutting tool of hard metal of the same composition as that described in Example 1 by using said second reaction indicated above (reaction of aluminium chloride with carbon dioxide and hydrogen) under the following reaction conditions:
Time of depositing operation 7 minutes Temperature 1000C. Overall pressure of the gaseous phase 50 torr Feed rate of the gaseous mixture (amounts reduced to C. and at a pressure of 760 torr): Hydrogen 200 em /min. Carbon dioxide 200 em /min. Aluminium chloride (AlC1 l0 mg/min [t was found that the coating layer was formed by 60 alpha alumina.
EXAMPLE 3 The process as described in Example 2 was repeated, but with a time of minutes for the depositing operation. Apart from this, all the reaction conditions were the same as described in Example 2. In this manner an alpha, alumina coating layer having a thickness of 6 microns is deposited on the hard metal cemented carbide cutting tool.
EXAMPLE 4 Carbon 0.96
Silicon 0.27 Manganese 0.25 Phosphorus 0.019
Sulphur 0.015 Chrominium 0.15
Iron the remainder These comparative tests have shown that the resistance to wear of the cutting blades produced by the process of the present invention is considerably improved with respect to the resistance to wear of the cut ting blades produced by conventional methods. The results of the comparative tests were as follows:
Series No. 1
Testing operation Test material Turning Steel of the composition as indicated above Cutting conditions Speed m/min. Feed 0,40 mm/revolution Cutting depth 2,0 mm
Different types of test material Life of cutting blade in minutes Hard metal cemented carbide of standard 3.7 180 P30 Hard metal cemented carbide of standard 13.0 ISO P10 Hard metal cemented carbide of standard 21.7 ISO P 30 coated with a layer of TiC having a thickness in the order of 5 microns Hard metal cemented carbide of the 43.1
standard P30 coated with alpha alumina according to Example 3 The cemented carbide of the standard ISO P10 has the following composition (in by weight):
Cobalt 9.5 Titanium carbide 19 Tantalum carbide 12.2 Niobium carbide 3.8 Tungsten carbide 55.5
Series No. 2
Testing operation Turning Test material Steel Cutting conditions Speed m/min. Feed 0.30 mm/revolution Cutting depth 2.0 mm
Different types of test material Life of cutting -Continued Series No. 2
blade in minutes Cemented carbide of the standard lSO P30 Cemented carbide of the standard ISO Pl 10,0 Cemented carbide of the standard 150 P30 19.2 coated with TiC Cemented Carbide of the standard 150 P30 l4i5 coated with alpha alumina according to Example 2 Cemented carbide of standard ISO P30 35.4 coated with alpha alumina according to Example 3 Cemented carbide of the standard lSO P30 25.0
coated with alpha aluminium according to Example 4 therein without departing from the scope of the invention.
What we claim is:
l. A cemented carbide tool provided with a surface coating produced by coating at least a portion of the surface of the cemented carbide with a layer 0.] to 20 microns thick of refractory oxide selected from the group including aluminium oxide, zirconium oxide and stabilized zirconium oxide.
2. A cemented carbide tool as claimed in claim 1, wherein said surface coating has a thickness of between 0.1 and 10 microns.
3. A cemented carbide tool as claimed in claim 1 wherein said cemented carbide is composed of a carbide of a metal selected from the group consisting of tungsten, titanium, tantalum and niobium, or a mixed carbide of tantalum and niobium; and a binder metal selected from the group consisting of cobalt, iron, and
nickel.
Notice of Adverse Decision in Interference In Interference No. 99,433, involving Patent No. 3,836,392, B. Lux, R. Funk, H. Schachner and C. Triquet, PROCESS FOR INCREASING THE RESIS- TANCE TO ,WEAR OF THE SURFACE OF HARD METAL CEMENTED CARBIDE PARTS SUBJECT TO WEAR, final judgment adverse to the patentees was rendered June 29, 1984, as to claims 10-12.
[Oflicial Gazette November 19, 1985.]

Claims (2)

  1. 2. A cemented carbide tool as claimed in claim 1, wherein said surface coating has a thickness of between 0.1 and 10 microns.
  2. 3. A cemented carbide tool as claimed in claim 1 wherein said cemented carbide is composed of a carbide of a metal selected from the group consisting of tungsten, titanium, tantalum and niobium, or a mixed carbide of tantalum and niobium; and a binder metal selected from the group consisting of cobalt, iron, and nickel.
US00269242A 1971-07-07 1972-07-05 Process for increasing the resistance to wear of the surface of hard metal cemented carbide parts subject to wear Expired - Lifetime US3836392A (en)

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CH994371A CH540990A (en) 1971-07-07 1971-07-07 Method for increasing the wear resistance of the surface of a cutting tool

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JP (1) JPS5243188B1 (en)
CH (1) CH540990A (en)
DE (2) DE2233700C2 (en)
FR (1) FR2144824B1 (en)
GB (1) GB1408193A (en)
IT (1) IT964465B (en)
SE (2) SE381288C (en)

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US3885063A (en) * 1973-06-15 1975-05-20 Battelle Memorial Institute Process for protecting a metallic surface against corrosion and wear
US3914473A (en) * 1971-05-26 1975-10-21 Gen Electric Method of making a coated cemented carbide product
US3935034A (en) * 1972-01-24 1976-01-27 Howmet Corporation Boron diffusion coating process
US3977061A (en) * 1973-09-17 1976-08-31 Sandvik Aktiebolag Cutting insert and method of making the same
US4105443A (en) * 1976-01-28 1978-08-08 United Kingdom Atomic Energy Authority Metal-forming dies
JPS55118631A (en) * 1979-03-07 1980-09-11 Fujitsu Ltd Diffusion furnace for treatment of semiconductor wafer
US4268582A (en) * 1979-03-02 1981-05-19 General Electric Company Boride coated cemented carbide
US4282289A (en) * 1980-04-16 1981-08-04 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
US4341834A (en) * 1976-07-10 1982-07-27 Mitsubishi Kinzoku Kabushiki Kaisha Coated super-hard alloy articles
US4357382A (en) * 1980-11-06 1982-11-02 Fansteel Inc. Coated cemented carbide bodies
DE3211047A1 (en) * 1981-03-27 1982-11-25 Kennametal Inc., 15650 Latrobe, Pa. PREFERRED BONDED, CEMENTED CARBIDE BODY AND METHOD FOR THE PRODUCTION THEREOF
US4399168A (en) * 1980-01-21 1983-08-16 Santrade Ltd. Method of preparing coated cemented carbide product
US4442169A (en) * 1982-01-28 1984-04-10 General Electric Company Multiple coated cutting tool and method for producing same
US4471017A (en) * 1981-09-23 1984-09-11 Battelle-Institut E.V. High-temperature and thermal-shock-resistant thermally insulating coatings on the basis of ceramic materials
US4490191A (en) * 1981-12-16 1984-12-25 General Electric Company Coated product and process
US4554201A (en) * 1981-02-23 1985-11-19 Vsesojuzny Nauchno-Issledovatelsky Instrumentalny Institut Multilayer coatings of metal-cutting tools
USRE32111E (en) * 1980-11-06 1986-04-15 Fansteel Inc. Coated cemented carbide bodies
USRE32110E (en) * 1971-05-26 1986-04-15 General Electric Co. Aluminum oxide coated cemented carbide product
EP0032887B1 (en) * 1980-01-21 1986-07-23 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
US4619866A (en) * 1980-07-28 1986-10-28 Santrade Limited Method of making a coated cemented carbide body and resulting body
US4696352A (en) * 1986-03-17 1987-09-29 Gte Laboratories Incorporated Insert for a drilling tool bit and a method of drilling therewith
US4745010A (en) * 1987-01-20 1988-05-17 Gte Laboratories Incorporated Process for depositing a composite ceramic coating on a cemented carbide substrate
US4749629A (en) * 1987-01-20 1988-06-07 Gte Laboratories Ultrathin laminated oxide coatings and methods
US4751109A (en) * 1987-01-20 1988-06-14 Gte Laboratories Incorporated A process for depositing a composite ceramic coating on a hard ceramic substrate
DE3902532C1 (en) * 1989-01-28 1989-11-23 Krupp Widia Gmbh, 4300 Essen, De
US4892792A (en) * 1987-10-01 1990-01-09 Gte Laboratories Incorporated A1N coated silicon nitride based cutting tools
US4943450A (en) * 1987-01-20 1990-07-24 Gte Laboratories Incorporated Method for depositing nitride-based composite coatings by CVD
US4950558A (en) * 1987-10-01 1990-08-21 Gte Laboratories Incorporated Oxidation resistant high temperature thermal cycling resistant coatings on silicon-based substrates and process for the production thereof
US5073411A (en) * 1981-12-16 1991-12-17 Carboloy, Inc. Process for forming a surface oxidized binding layer on hard substrates
US5137774A (en) * 1989-07-13 1992-08-11 Seco Tools Ab Multi-oxide coated carbide body and method of producing the same
USRE34180E (en) * 1981-03-27 1993-02-16 Kennametal Inc. Preferentially binder enriched cemented carbide bodies and method of manufacture
US5543176A (en) * 1989-06-16 1996-08-06 Sandvik Ab CVD of Al2 O3 layers on cutting inserts
US5674564A (en) * 1991-06-25 1997-10-07 Sandvik Ab Alumina-coated sintered body
US5693417A (en) * 1995-05-22 1997-12-02 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Vacuum-coated compound body and process for its production
US5698314A (en) * 1995-05-22 1997-12-16 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Compound body of vacuum-coated sintered material and process for its production
WO1999061211A1 (en) * 1998-05-26 1999-12-02 Ecer Gunes M Self-sharpening blades and method for making same
US6224968B1 (en) * 1996-10-09 2001-05-01 Widia Gmbh Composite body, production process and use
US20020155325A1 (en) * 2001-02-16 2002-10-24 Per Martensson Alpha-alumina coated cutting tool
US20050260432A1 (en) * 2002-10-07 2005-11-24 Volkmar Sottke Composite material
US20070020393A1 (en) * 2003-04-01 2007-01-25 Sandvik Intellectual Property Ab. Oxide coated cutting tool
EP2446988A1 (en) 2010-10-29 2012-05-02 Seco Tools AB Cutting tool insert with an alpha-alumina layer having a multi-components texture
USRE44870E1 (en) 1994-01-14 2014-04-29 Sandvik Intellectual Property Ab Aluminum oxide coated cutting tool and method of manufacturing thereof
WO2023088866A1 (en) * 2021-11-16 2023-05-25 Walter Ag Moderate temperature cvd alpha alumina coating

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CA1328580C (en) * 1987-01-20 1994-04-19 Gte Valenite Corporation Composite coatings
JPH06506178A (en) * 1991-03-27 1994-07-14 クルップ・ヴィデア・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Composites, uses of composites and methods of manufacturing them
EP0732423B1 (en) * 1994-10-04 2001-06-20 Sumitomo Electric Industries, Ltd Coated hard alloy

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Cited By (57)

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Publication number Priority date Publication date Assignee Title
US3914473A (en) * 1971-05-26 1975-10-21 Gen Electric Method of making a coated cemented carbide product
USRE32110E (en) * 1971-05-26 1986-04-15 General Electric Co. Aluminum oxide coated cemented carbide product
US3935034A (en) * 1972-01-24 1976-01-27 Howmet Corporation Boron diffusion coating process
US3885063A (en) * 1973-06-15 1975-05-20 Battelle Memorial Institute Process for protecting a metallic surface against corrosion and wear
US3977061A (en) * 1973-09-17 1976-08-31 Sandvik Aktiebolag Cutting insert and method of making the same
US4105443A (en) * 1976-01-28 1978-08-08 United Kingdom Atomic Energy Authority Metal-forming dies
US4341834A (en) * 1976-07-10 1982-07-27 Mitsubishi Kinzoku Kabushiki Kaisha Coated super-hard alloy articles
US4463033A (en) * 1976-07-10 1984-07-31 Mitsubishi Kinzoku Kabushiki Kaisha Process for production of coated super-hard alloy articles
US4268582A (en) * 1979-03-02 1981-05-19 General Electric Company Boride coated cemented carbide
JPS6250970B2 (en) * 1979-03-07 1987-10-28 Fujitsu Ltd
JPS55118631A (en) * 1979-03-07 1980-09-11 Fujitsu Ltd Diffusion furnace for treatment of semiconductor wafer
US4399168A (en) * 1980-01-21 1983-08-16 Santrade Ltd. Method of preparing coated cemented carbide product
EP0032887B1 (en) * 1980-01-21 1986-07-23 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
US4282289A (en) * 1980-04-16 1981-08-04 Sandvik Aktiebolag Method of preparing coated cemented carbide product and resulting product
US4619866A (en) * 1980-07-28 1986-10-28 Santrade Limited Method of making a coated cemented carbide body and resulting body
US4357382A (en) * 1980-11-06 1982-11-02 Fansteel Inc. Coated cemented carbide bodies
USRE32111E (en) * 1980-11-06 1986-04-15 Fansteel Inc. Coated cemented carbide bodies
US4554201A (en) * 1981-02-23 1985-11-19 Vsesojuzny Nauchno-Issledovatelsky Instrumentalny Institut Multilayer coatings of metal-cutting tools
DE3211047A1 (en) * 1981-03-27 1982-11-25 Kennametal Inc., 15650 Latrobe, Pa. PREFERRED BONDED, CEMENTED CARBIDE BODY AND METHOD FOR THE PRODUCTION THEREOF
DE3211047C2 (en) * 1981-03-27 1988-02-11 Kennametal Inc., Latrobe, Pa., Us
USRE34180E (en) * 1981-03-27 1993-02-16 Kennametal Inc. Preferentially binder enriched cemented carbide bodies and method of manufacture
US4471017A (en) * 1981-09-23 1984-09-11 Battelle-Institut E.V. High-temperature and thermal-shock-resistant thermally insulating coatings on the basis of ceramic materials
US4490191A (en) * 1981-12-16 1984-12-25 General Electric Company Coated product and process
US5073411A (en) * 1981-12-16 1991-12-17 Carboloy, Inc. Process for forming a surface oxidized binding layer on hard substrates
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
US4745010A (en) * 1987-01-20 1988-05-17 Gte Laboratories Incorporated Process for depositing a composite ceramic coating on a cemented carbide substrate
US4749629A (en) * 1987-01-20 1988-06-07 Gte Laboratories Ultrathin laminated oxide coatings and methods
US4751109A (en) * 1987-01-20 1988-06-14 Gte Laboratories Incorporated A process for depositing a composite ceramic coating on a hard ceramic substrate
US4965140A (en) * 1987-01-20 1990-10-23 Gte Laboratories Incorporated Composite coatings on refractory substrates
US4943450A (en) * 1987-01-20 1990-07-24 Gte Laboratories Incorporated Method for depositing nitride-based composite coatings by CVD
US4892792A (en) * 1987-10-01 1990-01-09 Gte Laboratories Incorporated A1N coated silicon nitride based cutting tools
US4950558A (en) * 1987-10-01 1990-08-21 Gte Laboratories Incorporated Oxidation resistant high temperature thermal cycling resistant coatings on silicon-based substrates and process for the production thereof
DE3902532C1 (en) * 1989-01-28 1989-11-23 Krupp Widia Gmbh, 4300 Essen, De
US5543176A (en) * 1989-06-16 1996-08-06 Sandvik Ab CVD of Al2 O3 layers on cutting inserts
US5137774A (en) * 1989-07-13 1992-08-11 Seco Tools Ab Multi-oxide coated carbide body and method of producing the same
US5162147A (en) * 1989-07-13 1992-11-10 Sandvik Ab Kappa-alumina oxide coated carbide body and method of producing the same
US5674564A (en) * 1991-06-25 1997-10-07 Sandvik Ab Alumina-coated sintered body
USRE44870E1 (en) 1994-01-14 2014-04-29 Sandvik Intellectual Property Ab Aluminum oxide coated cutting tool and method of manufacturing thereof
US5693417A (en) * 1995-05-22 1997-12-02 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Vacuum-coated compound body and process for its production
US5698314A (en) * 1995-05-22 1997-12-16 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Compound body of vacuum-coated sintered material and process for its production
US6224968B1 (en) * 1996-10-09 2001-05-01 Widia Gmbh Composite body, production process and use
WO1999061211A1 (en) * 1998-05-26 1999-12-02 Ecer Gunes M Self-sharpening blades and method for making same
US6105261A (en) * 1998-05-26 2000-08-22 Globix Technologies, Inc. Self sharpening blades and method for making same
US6389699B1 (en) * 1998-05-26 2002-05-21 Globix Technologies, Inc. Self sharpening blades and method for making same
US20020155325A1 (en) * 2001-02-16 2002-10-24 Per Martensson Alpha-alumina coated cutting tool
US6869668B2 (en) 2001-02-16 2005-03-22 Sandvik Aktiebolag α-alumina coated cutting tool
US7011867B2 (en) 2001-02-16 2006-03-14 Sandvik Aktiebolag α-alumina coated cutting tool
US20040202877A1 (en) * 2001-02-16 2004-10-14 Sandvik Aktiebolag Alpha-alumina coated cutting tool
US20050260432A1 (en) * 2002-10-07 2005-11-24 Volkmar Sottke Composite material
US7326461B2 (en) * 2002-10-07 2008-02-05 Kennametal Widia Gmbh & Co. Kg Composite material
US20070020393A1 (en) * 2003-04-01 2007-01-25 Sandvik Intellectual Property Ab. Oxide coated cutting tool
US7531214B2 (en) * 2003-04-01 2009-05-12 Sandvik Intellectual Property Aktiebolag Method for manufacturing an oxide coated cutting tool
EP2446988A1 (en) 2010-10-29 2012-05-02 Seco Tools AB Cutting tool insert with an alpha-alumina layer having a multi-components texture
WO2012055906A2 (en) 2010-10-29 2012-05-03 Seco Tools Ab Alumina layer with multitexture components
US9149871B2 (en) 2010-10-29 2015-10-06 Seco Tools Ab Alumina layer with multitexture components
WO2023088866A1 (en) * 2021-11-16 2023-05-25 Walter Ag Moderate temperature cvd alpha alumina coating

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Publication number Publication date
SE421712B (en) 1982-01-25
DE2233700C2 (en) 1989-05-24
JPS5243188B1 (en) 1977-10-28
GB1408193A (en) 1975-10-01
SE381288B (en) 1975-12-01
FR2144824A1 (en) 1973-02-16
IT964465B (en) 1974-01-21
FR2144824B1 (en) 1976-10-29
CH540990A (en) 1973-08-31
DE2233700A1 (en) 1973-01-25
SE381288C (en) 1982-07-19
SE8008832L (en) 1980-12-16

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