Tungsten carbide coating and method for producing the same

• US 6,800,383 B1
• Filed: 12/03/2001
• Issued: 10/05/2004
• Est. Priority Date: 02/11/1999
• Status: Expired due to Term

• Current Assignee: Hardide PLC
• Original Assignee: Hardide Limited
• Inventors: Kuzman, Vladimir P., Lakhotkin, Jury V.
• Primary Examiner(s): TURNER, ARCHENE A
• Application Number:
  US09/913,324
• Time in Patent Office: 1,037 Days
• Field of Search: 513/07, 513/09, 427/255.1, 427/255.2, 427/255.7, 428/216, 428/332, 428/469, 428/412, 428/698
• US Class Current: 428/698
• CPC Class Codes: C23C 16/0281 of metallic sub-layers C23C16/029 takes precedence
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/32 Carbides
• CPC Class Codes: C23C 16/452 by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
• CPC Class Codes: C23C 28/322 only coatings of metal elements only
• CPC Class Codes: C23C 28/34 including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
• CPC Class Codes: C23C 28/341 with at least one carbide layer
• CPC Class Codes: C23C 28/347 with layers adapted for cutting tools or wear applications
• CPC Class Codes: C23C 28/42 characterized by the composition of the alternating layers
• CPC Class Codes: C23C 28/44 characterized by a measurable physical property of the alternating layer or system, e.g. thickness, density, hardness
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Abstract

New tungsten carbides alloyed with fluorine in amounts up to 0.5 wt % and possibly with fluorocarbon compositions are described. It is possible to produce them by means of a new process of chemical vapor deposition, in which tungsten hexafluoride, hydrogen and a carbon-containing gas are used. A specific feature of the new process is the preliminary thermal activation of the carbon-containing gas. The tungsten carbide coatings are deposited on construction materials and items made from them. They possess enhanced resistance to wear, corrosion and chemicals.

Claims

1. Material for wear, erosion and corrosion resistant coatings, consisting of tungsten carbide alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

2. Material in accordance with claim 1, wherein the said material is tungsten monocarbide WC alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

3. Material in accordance with claim 1, wherein the said material is tungsten semicarbide W₂C alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

4. Material in accordance with claim 1, wherein the said material is tungsten subcarbide W₃C alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

5. Material in accordance with claim 1, wherein the said material is tungsten subcarbide W₁₂C alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

6. Material in accordance with claim 1, wherein the said material additionally contains fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %.

7. Coating in accordance with claim 6, characterized in that its outer layer additionally contains a mixture of at least two tungsten carbides alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt % and possible with fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %.

8. Coating, characterized in that it contains:

an internal layer consisting of tungsten deposited on a substrate;

and an external layer deposited on the said internal layer and containing tungsten carbide in accordance with claim 1.

9. Coating in accordance with claim 8, characterized in that its outer layer additionally contains tungsten.

10. Coating in accordance with claim 8, characterized in that its outer layer additionally contains carbon.

11. Coating in accordance with any of claim 8, characterized in that its internal layer has a thickness of 0.5-300 μ

m and its outer layer has a thickness of 0.5-300 μ

m, with the ratio of thicknesses of the internal and external layers ranging from 1;

1 to 1;

600.

12. Multilayer coating made from alternating layers of tungsten and layers containing tungsten carbide in accordance with claim 1.

13. Multilayer coating in accordance with claim 12, characterized in that the thickness of its individual layers ranges from 2 to 10 μ

m and the ratio of the thicknesses of the alternating layers ranges from 1;

1 to 1;

5.

96. Coating, characterised in that it contains:

an internal layer consisting of tungsten deposited on a substrate;

and an external layer deposited on the said internal layer and containing tungsten carbide material in accordance with claim 1.

97. Coating in accordance with claim 96, wherein the external layer additionally contains a mixture of at least two tungsten carbides alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt % and optionally with fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %.

98. Coating in accordance with claim 96, wherein the external layer additionally contains tungsten.

99. Coating in accordance with claim 96, wherein the external layer additionally contains carbon.

100. Coating in accordance with claim 96, wherein the internal layer has a thickness of 0.5-300 μ

m and the external layer has a thickness of 0.5-300 μ

m, with the ratio of thicknesses of the internal and external layers ranging from 1;

1 to 1;

600.

14. Material for wear, erosion and corrosion resistant coatings comprising a mixture of at least two tungsten carbides alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt % and possibly with fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %.

15. Multilaminar coating made from alternating layers of tungsten and layers containing tungsten carbide in accordance with claim 14.

16. Process for producing tungsten carbides by chemical vapour deposition on a heated substrate using a mixture of gases including tungsten hexafluoride, hydrogen, a carbon-containing gas and, optionally, an inert gas, characterized in that the carbon-containing gas is thermally activated beforehand by heating to temperature 500-850°

C.

17. Process in accordance with claim 16, characterized in that the said carbon-containing gas is propane.

18. Process in accordance with claim 16, characterized in that it is performed at a pressure of 2-150 kPa, substrate temperature 400-900°

C., ratio of carbon-containing gas to hydrogen 0.2-1.7 and ratio of tungsten hexafluoride to hydrogen 0.02-0.12.

19. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 1.0-1.5 and ratio of tungsten hexafluoride to hydrogen 0.08-0.10, and that the carbon-containing gas is heated beforehand to temperature 750-850°

C.;

in this case, tungsten monocarbide WC is obtained.

20. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.75-0.90 and ratio of tungsten hexafluoride to hydrogen 0.06-0.08, and that the carbon-containing gas is heated beforehand to temperature 600-750°

C.;

in this case, tungsten semicarbide W₂C is obtained.

21. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.60-0.65 and ratio of tungsten hexafluoride to hydrogen 0.05-0.55, and that the carbon-containing gas is heated beforehand to temperature 560-720°

C.;

in this case, tungsten subcarbide W₃C is obtained.

22. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.35-0.45 and ratio of tungsten hexafluoride to hydrogen 0.040-0.045, and that the carbon-containing gas is heated beforehand to temperature 500-700°

C.;

in this case, tungsten subcarbide W₁₂C is obtained.

23. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.90-1.00 and ratio of tungsten hexafluoride to hydrogen 0.07-0.09, and that the carbon-containing gas is heated beforehand to temperature 670-790°

C.;

in this case, a mixture of the carbides WC and W₂C is obtained.

24. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.70-0.75 and ratio of tungsten hexafluoride to hydrogen 0.055-0.060, and that the carbon-containing gas is heated beforehand to temperature 580-730°

C.;

in this case, a mixture of the carbides W₂C and W₃C is obtained.

25. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.60-0.65 and ratio of tungsten hexafluoride to hydrogen 0.045-0.060, and that the carbon-containing gas is heated beforehand to temperature 570-700°

C.;

in this case, a mixture of the carbides W₂C and W₁₂C is obtained.

26. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.45-0.60 and ratio of tungsten hexafluoride to hydrogen 0.40-0.050, and that the carbon-containing gas is heated beforehand to temperature 550-680°

C.;

in this case, a mixture of the carbides W₃C and W₁₂C is obtained.

27. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.65-0.70 and ratio of tungsten hexafluoride to hydrogen 0.045-0.060, and that the carbon-containing gas is heated beforehand to temperature 570-710°

C.;

in this case, a mixture of the carbides W₂C, W₃C and W₁₂C is obtained.

28. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.70-0.90 and ratio of tungsten hexafluoride to hydrogen 0.08-0.09, and that the carbon-containing gas is heated beforehand to temperature 600-720°

C.;

in this case, a mixture of the carbide WC and tungsten is obtained.

29. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.70-0.90 and ratio of tungsten hexafluoride to hydrogen 0.08-0.09, and that the carbon-containing gas is heated beforehand to temperature 600-720°

C.;

in this case, a mixture of the carbides W₂C and tungsten is obtained.

30. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.60-0.65 and ratio of tungsten hexafluoride to hydrogen 0.055-0.070, and that the carbon-containing gas is heated beforehand to temperature 560-700°

C.;

in this case, a mixture of the carbide W₃C and tungsten is obtained.

31. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.20-0.35 and ratio of tungsten hexafluoride to hydrogen 0.045-0.070, and that the carbon-containing gas is heated beforehand to temperature 500-680°

C.;

in this case, a mixture of the carbide W₁₂C and tungsten is obtained.

32. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 0.35-0.60 and ratio of tungsten hexafluoride to hydrogen 0.05-0.07, and that the carbon-containing gas is heated beforehand to temperature 500-680°

C.;

in this case, a mixture of the carbides W₃C, W₁₂C and tungsten is obtained.

33. Process in accordance with claim 18, characterized in that it is performed at a ratio of carbon-containing gas to hydrogen 1.50-1.70 and ratio of tungsten hexafluoride to hydrogen 0.10-0.12, and that the carbon-containing gas is heated beforehand to temperature 750-850°

C.;

in this case, a mixture of the carbide WC and carbon is obtained.

34. Process for the deposition of coatings consisting of an internal layer of tungsten and an external layer containing tungsten subcarbide W₁₂C on substrates, preferably on construction materials and on items made from them, characterised in that the said process includes the following stages:

(a) placing the substrate in a chemical vapour deposition reactor;

(b) evacuating the reactor;

(c) heating the said substrate;

(d) supplying tungsten hexafluoride and hydrogen to the reactor;

(e) retaining the substrate in the said gaseous medium for the time interval necessary for the formation of the tungsten layer on the substrate;

(f) in addition to the said tungsten hexafluoride and hydrogen, supplying a previously thermally activated carbon-containing gas to the reactor;

(g) retaining the substrate in the gaseous medium formed at stage (f) for the time necessary for the formation of the outer layer containing tungsten carbides and mixtures of them with each other, with tungsten or with free carbon.

35. Process in accordance with claim 34, characterized in that it is performed at a reactor pressure of 2-150 kPa, substrate temperature 400-900°

C., ratio of carbon-containing gas to hydrogen 0.2-1.7 and ratio of tungsten hexafluoride to hydrogen 0.02-0.12.

36. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 1.00-1.50 and a ratio of tungsten hexafluoride to hydrogen 0.08-0.10, and that the carbon-containing gas is heated beforehand to temperature 750-850°

C.;

in this case, an external layer containing tungsten monocarbide WC is obtained.

37. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.75-0.90 and a ratio of tungsten hexafluoride to hydrogen 0.06-0.08, and that the carbon-containing gas is heated beforehand to temperature 600-750°

C.;

in this case, an external layer containing tungsten semicarbide W₂C is obtained.

38. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.60-0.65 and a ratio of tungsten hexafluoride to hydrogen 0.050-0.055, and that the carbon-containing gas is heated beforehand to temperature 560-720°

C.;

in this case, an external layer containing tungsten subcarbide W₃C is obtained.

39. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.35-0.40 and a ratio of tungsten hexafluoride to hydrogen 0.040-0.045, and that the carbon-containing gas is heated beforehand to temperature 500-700°

C.;

in this case, an external layer containing tungsten monocarbide W₁₂C is obtained.

40. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.90-1.00 and a ratio of tungsten hexafluoride to hydrogen 0.07-0.09, and that the carbon-containing gas is heated beforehand to temperature 670-790°

C.;

in this case, an external layer containing a mixture of the carbides WC and W₂C is obtained.

41. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.70-0.75 and a ratio of tungsten hexafluoride to hydrogen 0.055-0.060, and that the carbon-containing gas is heated beforehand to temperature 580-730°

C.;

in this case, an external layer containing a mixture of the carbides W₂C and W₃C is obtained.

42. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.65-0.70 and a ratio of tungsten hexafluoride to hydrogen 0.045-0.060, and that the carbon-containing gas is heated beforehand to temperature 570-710°

C.;

in this case, an external layer containing a mixture of the carbides W₂C, W₃C and W₁₂C is obtained.

43. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.60-0.65 and a ratio of tungsten hexafluoride to hydrogen 0.045-0.060, and that the carbon-containing gas is heated beforehand to temperature 570-700°

C.;

in this case, an external layer containing a mixture of the carbides W₂C and W₁₂C is obtained.

44. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.40-0.60 and a ratio of tungsten hexafluoride to hydrogen 0.045-0.050, and that the carbon-containing gas is heated beforehand to temperature 550-680°

C.;

in this case, an external layer containing a mixture of the carbides W₃C and W₁₂C is obtained.

45. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.70-0.90 and a ratio of tungsten hexafluoride to hydrogen 0.08-0.09, and that the carbon-containing gas is heated beforehand to temperature 600-720°

C.;

in this case, an external layer containing a mixture of the carbide W₂C and tungsten is obtained.

46. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.60-0.65 and a ratio of tungsten hexafluoride to hydrogen 0.055-0.070, and that the carbon-containing gas is heated beforehand to temperature 560-700°

C.;

in this case, an external layer containing a mixture of the carbide W₃C and tungsten is obtained.

47. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.35-0.60 and a ratio of tungsten hexafluoride to hydrogen 0.050-0.070, and that the carbon-containing gas is heated beforehand to temperature 500-690°

C.;

in this case, an external layer containing a mixture of the carbides W₃C and W₁₂C with tungsten is obtained.

48. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.20-0.35 and a ratio of tungsten hexafluoride to hydrogen 0.045-0.070, and that the carbon-containing gas is heated beforehand to temperature 500-680°

C.;

in this case, an external layer containing a mixture of the carbide W₁₂C and tungsten is obtained.

49. Process in accordance with claim 35, characterized in that it is performed at a ratio of the carbon-containing gas to hydrogen 0.70-0.90 and a ratio of tungsten hexafluoride to hydrogen 0.08-0.09, and that the carbon-containing gas is heated beforehand to temperature 600-720°

C.;

in this case, an external layer containing a mixture of the carbide WC and tungsten is obtained.

50. Process in accordance with claim 34, characterized in that, before the application of a coating to materials or items made from materials selected from a group including iron, carbon steels, stainless steels, cast irons, titanium alloys and hard alloys containing titanium, a coating is applied to them consisting of materials which are chemically resistant to hydrogen fluoride, namely nickel, cobalt, copper, silver, gold, platinum, iridium, tantalum, molybdenum and alloys, compounds and mixtures of these, by electrochemical or chemical precipitation from aqueous solutions, electrolysis of melts or physical and chemical vapour precipitation.

51. Process in accordance with any of claim 34, characterized in that the coatings are deposited onto frictional assemblies.

52. Process in accordance with any of claim 34, characterized in that the coatings are deposited onto forming tools used for processing materials by means of pressing.

53. Process in accordance with any of claim 34, characterized in that the coatings are deposited onto components and units of machines and mechanisms operating with compressed gases and liquids or other pneumatic or hydraulic systems.

54. Material comprising:

a substrate made from construction material;

a coating deposited on the said substrate, consisting of an internal tungsten layer and an external layer containing tungsten carbide alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt % and possibly with fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %.

55. Material in accordance with claim 54, wherein the said tungsten carbide is monocarbide WC.

56. Material in accordance with claim 55, characterized in that the external layer of the said coating additionally contains tungsten.

57. Material in accordance with claim 55, characterized in that the external layer of the said coating additionally contains carbon.

58. Material in accordance with claim 55, characterized in that the internal layer of the said coating has thickness 0.5-300 μ

m and the ratio of thicknesses of internal and external layers ranges from 1;

1 to 1;

600.

59. Material according to claim 55, characterized in that the said substrate layer adjacent to the coating contains alloys with nickel content exceeding 25 wt %, e.g. Invar, Nichrome, Monel.

60. Material in accordance with claim 54, wherein the said tungsten carbide is semicarbide W₂C.

61. Material in accordance with claim 54, wherein the said tungsten carbide is subcarbide W₃C.

62. Material in accordance with claim 54, wherein the said tungsten carbide is subcarbide W₁₂C.

63. Material comprising:

a substrate made from construction material;

and a coating deposited on the said substrate, consisting of an internal tungsten layer and an external layer containing a mixture of at least two tungsten carbides alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt % and possibly with fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %.

64. Material in accordance with claim 63, characterized in that the external layer of the said coating contains a mixture of the tungsten carbides WC and W₁₂C.

65. Material in accordance with claim 63, characterized in that the external layer of the said coating contains a mixture of the tungsten carbides W₃C and W₂C.

66. Material in accordance with claim 63, characterized in that the external layer of the said coating contains a mixture of the tungsten carbides W₃C and W₁₂C.

67. Material in accordance with claim 63, characterized in that the external layer of the said coating contains a mixture of tungsten carbides W₂C and W₁₂C.

68. Material in accordance with claim 63, characterized in that the external layer of the said coating contains a mixture of the tungsten carbides W₂C, W₃C and W₁₂C.

69. Process for the deposition of multilaminar coatings on substrates, preferably on construction materials and items made from them, consisting of alternating layers of tungsten and layers containing tungsten carbide or mixtures of tungsten carbides with each other, with tungsten or with free carbon, said process to include the following stages:

(a) placing the substrate in a chemical vapour deposition reactor;

(b) evacuating the reactor;

(c) heating the said substrate;

(d) supplying tungsten hexafluoride and hydrogen to the reactor;

(e) retaining the substrate in the said gaseous medium for the time interval necessary for the formation of the tungsten layer on the substrate;

(f) in addition to the said tungsten hexafluoride and hydrogen, supplying a previously thermally activated carbon-containing gas to the reactor;

(g) retaining the substrate in the gaseous medium formed at stage (f) for the time necessary for the formation of the outer layer containing tungsten carbide or mixtures of tungsten carbides with each other, with tungsten and with free carbon;

stages (d) and (g) are repeated several times in order to form alternating layers of tungsten and layers containing tungsten carbides.

70. Process in accordance with claim 69, characterized in that it is conducted at reactor pressure 2-150 kPa, substrate temperature 400-900°

C., ratio of carbon-containing gas to hydrogen 0.2-1.7 and ratio of tungsten hexafluoride to hydrogen 0.02-0.12.

71. Process in accordance with claim 69, characterized in that, before the application of a coating to materials or items made from materials selected from a group including iron, carbon steels, stainless steels, cast irons, titanium alloys and hard alloys containing titanium, a coating is applied to them consisting of materials which are chemically resistant to hydrogen fluoride, namely nickel, cobalt, copper, silver, gold, platinum, iridium, tantalum, molybdenum and alloys, compounds and mixtures of these, by electrochemical or chemical precipitation from aqueous solutions, electrolysis of melts or physical and chemical vapour precipitation.

72. Process in accordance with any of claim 69, characterized in that the coating is deposited onto friction assemblies.

73. Process in accordance with any of claim 69, characterized in that the coating is deposited onto a forming tool used for processing materials by means of pressing.

74. Process in accordance with any of claim 69, characterized in that the coating is deposited onto units of machines and mechanisms operating with compressed gases and liquids or of other pneumatic or hydraulic systems.

75. Construction material comprising a substrate and a multilaminar coating consisting of alternating layers of tungsten and layers containing tungsten carbide alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt % and possibly with fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %.

76. Material in accordance with claim 75, wherein the said tungsten carbide is tungsten monocarbide WC.

77. Material in accordance with claim 75, wherein the said tungsten carbide is tungsten semicarbide W₂C.

78. Material in accordance with claim 75, wherein the said tungsten carbide is tungsten subcarbide W₃C.

79. Material in accordance with claim 75, wherein the said tungsten carbide is tungsten subcarbide W₁₂C.

80. Material in accordance with any of claim 75, characterized in that the said carbide layers additionally contain tungsten.

81. Material in accordance with any of claim 75, characterized in that the said carbide layers additionally contain carbon.

82. Materials according to any of claim 75, characterized in that the thickness of its layers ranges from 2 to 10 μ

m and the ratio of the thicknesses of the alternating layers ranges from 1;

1 to 1;

5.

83. Construction material comprising a substrate and a multilaminar coating consisting of alternating layers of tungsten and layers containing a mixture of at least two tungsten carbides alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt % and possibly with fluorocarbon compositions with carbon content up to 15 wt % and fluoride content up to 0.5 wt %.

84. Material in accordance with claim 83, wherein the said carbide layers contain a mixture of tungsten carbides WC and W₂C.

85. Material in accordance with claim 83, wherein the said carbide layers contain a mixture of tungsten carbides W₂C and W₃C.

86. Material in accordance with claim 83, wherein the said carbide layers contain a mixture of tungsten carbides W₃C and W₁₂C.

87. Material in accordance with claim 83, wherein the said carbide layers contain a mixture of tungsten carbides W₂C and W₁₂C.

88. Material in accordance with claim 83, wherein the said carbide layers contain a mixture of tungsten carbides W₂C, W₃C and W₁₂C.

89. Material for wear, erosion and corrosion resistant coatings, consisting of tungsten carbide alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %, wherein the material is deposited on a heated substrate by way of chemical vapour deposition in a chemical vapour deposition reactor using a mixture of gases including tungsten hexafluoride, hydrogen, a carbon-containing gas and, optionally, an inert gas, and wherein the carbon-containing gas is heated to a temperature of 500 to 850°

C. prior to being supplied to the reactor.

90. Material in accordance with claim 89, wherein the said material is tungsten monocarbide WC alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

91. Material in accordance with claim 89, wherein the said material is tungsten semicarbide W₂C alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

92. Material in accordance with claim 89, wherein the said material is tungsten subcarbide W₃C alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

93. Material in accordance with claim 89, wherein the said material is tungsten subcarbide W₁₂C alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %.

94. Material in accordance with claim 89, wherein the said material additionally contains fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %.

95. Material for wear, erosion and corrosion resistant coatings comprising a mixture of at least two tungsten carbides alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt % and optionally with fluorocarbon compositions with carbon content up to 15 wt % and fluorine content up to 0.5 wt %, wherein the material is deposited on a heated substrate by way of chemical vapour deposition in a chemical vapour deposition reactor using a mixture of gases including tungsten hexafluoride, hydrogen, a carbon-containing gas and, optionally, an inert gas, and wherein the carbon-containing gas is heated to a temperature of 500 to 850°

C. prior to being supplied to the reactor.

101. Process for producing tungsten carbides in a chemical vapour deposition reactor by chemical vapour deposition on a heated substrate using a mixture of gases including tungsten hexafluoride, hydrogen, a carbon-containing gas and, optionally, an inert gas, wherein the carbon-containing gas is thermally activated before being supplied to the reactor by heating to a temperature of 500-850°

C., and wherein fluorine is alloyed with the tungsten carbides in amounts ranging from 0.0005 to 0.5 wt %.

102. Process in accordance with claim 101, wherein the said carbon-containing gas is propane.

103. Process in accordance with claim 101, wherein the process is performed at a pressure of 2-150 kPa, a substrate temperature of 400-900°

C., a ratio of carbon-containing gas to hydrogen of 0.2-1.7 and a ratio of tungsten hexafluoride to hydrogen of 0.02-0.12.

104. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 1.0-1.5 and a ratio of tungsten hexafluoride to hydrogen of 0.08-0.10, and wherein the carbon-containing gas is heated to a temperature of 750-850°

C. before being supplied to the reactor, and wherein tungsten monocarbide WC is obtained.

105. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.75-0.90 and a ratio of tungsten hexafluoride to hydrogen of 0.06-0.08, and wherein the carbon-containing gas is heated to a temperature of 600-750°

C. before being supplied to the reactor, and wherein tungsten semicarbide W₂C is obtained.

106. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.60-0.65 and a ratio of tungsten hexafluoride to hydrogen of 0.05-0.55, and wherein the carbon-containing gas is heated to a temperature of 560-720°

C. before being supplied to the reactor, and wherein tungsten subcarbide W₃C is obtained.

107. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.35-0.45 and a ratio of tungsten hexafluoride to hydrogen of 0.040-0.045, and wherein the carbon-containing gas is heated to a temperature of 500-700°

C. before being supplied to the reactor, and wherein tungsten subcarbide W₁₂C is obtained.

108. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.90-1.00 and a ratio of tungsten hexafluoride to hydrogen of 0.07-0.09, and wherein the carbon-containing gas is heated to a temperature of 670-790°

C. before being supplied to the reactor, and wherein a mixture of the carbides WC and W₂C is obtained.

109. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.70-0.75 and a ratio of tungsten hexafluoride to hydrogen of 0.055-0.060, and wherein the carbon-containing gas is heated to a temperature of 580-730°

C. before being supplied to the reactor, and wherein a mixture of the carbides W₂C and W₃C is obtained.

110. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.60-0.65 and a ratio of tungsten hexafluoride to hydrogen of 0.045-0.060, and wherein the carbon-containing gas is heated to a temperature of 570-700°

C. before being supplied to the reactor, and wherein a mixture of the carbides W₂C and W₁₂C is obtained.

111. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.45-0.60 and a ratio of tungsten hexafluoride to hydrogen of 0.045-0.050, and wherein the carbon-containing gas is heated to a temperature of 550-680°

C. before being supplied to the reactor, and wherein a mixture of the carbides W₃C and W₁₂C is obtained.

112. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.65-0.70 and a ratio of tungsten hexafluoride to hydrogen of 0.045-0.060, and wherein the carbon-containing gas is heated to a temperature of 570-710°

C. before being supplied to the reactor, and wherein a mixture of the carbides W₂C, W₃C and W₁₂C is obtained.

113. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.70-0.90 and a ratio of tungsten hexafluoride to hydrogen of 0.08-0.09, and wherein the carbon-containing gas is heated to a temperature of 600-720°

C. before being supplied to the reactor, and wherein a mixture of the carbide WC and tungsten is obtained.

114. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.70-0.90 and a ratio of tungsten hexafluoride to hydrogen of 0.08-0.09, and wherein the carbon-containing gas is heated to a temperature 600-720°

C. before being supplied to the reactor, and wherein a mixture of the carbides W₂C and tungsten is obtained.

115. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.60-0.65 and a ratio of tungsten hexafluoride to hydrogen of 0.055-0.070, and wherein the carbon-containing gas is heated to a temperature of 560-700°

C. before being supplied to the reactor, and wherein a mixture of the carbide W₃C and tungsten is obtained.

116. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.20-0.35 and a ratio of tungsten hexafluoride to hydrogen of 0.045-0.070, and wherein the carbon-containing gas is heated to a temperature of 500-680°

C. before being supplied to the reactor, and wherein a mixture of the carbide W₁₂C and tungsten is obtained.

117. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 0.35-0.60 and a ratio of tungsten hexafluoride to hydrogen of 0.05-0.07, and wherein the carbon-containing gas is heated to a temperature of 500-680°

C. before being supplied to the reactor, and wherein a mixture of the carbides W₃C, W₁₂C and tungsten is obtained.

118. Process in accordance with claim 103, wherein the process is performed at a ratio of carbon-containing gas to hydrogen of 1.50-1.70 and a ratio of tungsten hexafluoride to hydrogen of 0.10-0.12, and wherein the carbon-containing gas is heated to a temperature of 750-850°

C. before being supplied to the reactor, and wherein a mixture of the carbide WC and carbon is obtained.

119. Material for wear, erosion and corrosion resistant coatings, the material including tungsten carbide alloyed with fluorine in amounts ranging from 0.0005 to 0.5 wt %, and having a microhardness of at least 3100 kg/mm².

120. Material as claimed in claim 119, having a microhardness of at least 3400 kg/mm².

121. Material as claimed in claim 119, having a microhardness of at least 3500 kg/mm².