CN113293349B - High-wear-resistance hard alloy and coating thereof - Google Patents
High-wear-resistance hard alloy and coating thereof Download PDFInfo
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- CN113293349B CN113293349B CN202110559810.0A CN202110559810A CN113293349B CN 113293349 B CN113293349 B CN 113293349B CN 202110559810 A CN202110559810 A CN 202110559810A CN 113293349 B CN113293349 B CN 113293349B
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
Abstract
The invention relates to the technical field of hard alloy, in particular to high-wear-resistance hard alloy and a coating thereof 1 The surface layer is an AlCrYN coating; through the cooperation of the coating and the hard alloy matrix, the overall wear resistance of the material is greatly improved, good hardness and oxidation resistance are kept, the service life of the hard alloy is prolonged, and the cost is reduced.
Description
Technical Field
The invention relates to the technical field of hard alloy, in particular to high-wear-resistance hard alloy and a coating thereof.
Background
The hard alloy is a sintered material consisting of hard refractory metal carbide phase and bonding metal phase, has the characteristics of high hardness, high strength, high elastic modulus, good wear resistance and corrosion resistance and the like, and is widely applied to various cutting tools, mining tools, wear-resistant and corrosion-resistant parts and the like.
Generally, a coating is plated on the surface of the hard alloy, and the coating of the hard alloy has high wear resistance and excellent oxidation resistance, so that the comprehensive performance of the hard alloy is improved, the processing quality is improved, and the processing cost is reduced. The AlCrN coating has excellent high-temperature oxidation resistance and better toughness, and is a common coating material for cutting tools.
However, with the development of cutting tools, mining tools, and the like, higher requirements are put forward on the existing AlCrN coating, such as improvement of machining precision, prolongation of the service life of a cutter, reduction of machining cost, and the like.
For example, patent CN 107130221A discloses a multilayer gradient rare earth composite coating of cemented carbide, which comprises: the hard alloy is a base material and comprises a TiCrN, tiAlN, tiBN, tiSiN coating and a rare earth coating, wherein the coating is a multi-layer gradient composite coating, and the rare earth coating is coated on the surface of the hard alloy and between the TiCrN, tiAlN, tiBN and TiSiN coating. The coating comprises TiCrN, tiAlN, tiBN and TiSiN in sequence from inside to outside, the thicknesses of the TiCrN, tiAlN, tiBN and TiSiN coatings are 3-5 mu m, 6-12 mu m, 7-15 mu m and 10-30 mu m respectively, and the mass ratio of the TiCCrN to the TiA1N to the TiBN to the TiSiN coatings is 0.5-1.0.
However, the coating in the scheme is various, the combination of the coatings has certain problems, the whole structure is complex, and the method is not suitable for popularization and application.
Furthermore, the prior modification method only focuses on the coating, and neglects the matching with the hard alloy matrix.
Disclosure of Invention
In view of the above problems, the present invention provides a highly wear-resistant hard alloy coating comprising a two-layer structure consisting of a bonding layer and a surface layer, the bonding layer being AlCrVM 1 And the surface layer is an AlCrYN coating.
Said M 1 Is one or more of lanthanide series metal elements including La, ce, pr and Nd.
Wherein, alCrVM 1 The thickness of the N coating and the AlCrYN coating is 0.5-3 mu m, preferably 1-2 mu m respectively;
AlCrVM 1 in the N coating, al, cr, V and M 1 3-6;
in the AlCrYN coating, the atomic ratio of Al to Cr to Y is 4-6.
The bonding layer is plated on the surface of the hard alloy.
Further, the invention provides a hard alloy which is WC-Co-M 2 Hard alloy.
Said M 2 Is one or more of lanthanide series metal elements including La, ce, pr and Nd.
Among the cemented carbides, WC-Co-M 2 The mass ratio of (1) is 84-96.
The preparation method of the hard alloy comprises the following steps:
(1) Cleaning the surface of the hard alloy, soaking the hard alloy in acetone, then ultrasonically cleaning, and then carrying out ion etching;
(2) Vitamin (vitamin)Keeping the internal temperature of the ion plating equipment at 400-500 ℃, introducing nitrogen, and sequentially starting AlCrVM 1 The coating is plated on the surface of the hard alloy by using an N target and an AlCrYN target;
wherein, controlling AlCrVM 1 The thickness of the N coating and the AlCrYN coating is 0.5-3 mu m, preferably 1-2 mu m respectively;
AlCrVM 1 in the N coating, al, cr, V and M 1 3-6;
in the AlCrYN coating, the atomic ratio of Al to Cr to Y is (4-6).
Compared with the prior art, the high wear-resistant coating has the following beneficial effects:
(1) The invention not only focuses on the coating, but also focuses on the matching of the coating and the hard alloy matrix while improving the coating, and can greatly improve the overall wear resistance of the material by only slightly improving the hard alloy, simultaneously keep good hardness and oxidation resistance, prolong the service life of the hard alloy and reduce the cost.
(2) The lanthanide series metal element has special atomic structure, special optical, electric, magnetic and nuclear performance and high chemical activity, and can further improve the compactness of the coating and raise the comprehensive performance of the hard alloy.
(3) The lanthanide series metal elements are expensive, the multilayer structure is adopted, the special performance of the lanthanide series metal elements can be utilized to the maximum degree, the coating and the hard alloy matrix can be modified, the cost can be saved, the cost of the hard alloy obtained by the method is controlled, the performance is excellent, the preparation process is simple, and the method can be directly applied to industrial production.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a high-wear-resistance hard alloy coating, which comprises a double-layer structure and consists of a bonding layer and a surface layer, wherein the bonding layer is AlCrVM 1 And the surface layer is an AlCrYN coating.
Said M 1 Is one or more of lanthanide series metal elements including La, ce, pr and Nd.
Wherein, alCrVM 1 The thickness of the N coating and the AlCrYN coating is 0.5-3 mu m, preferably 1-2 mu m respectively;
AlCrVM 1 in the N coating, al, cr, V and M 1 3-6;
in the AlCrYN coating, the atomic ratio of Al to Cr to Y is (4-6).
Further, the invention provides a hard alloy which is WC-Co-M 2 Hard alloy.
The bonding layer is plated on the surface of the hard alloy.
Said M 2 Is one or more of lanthanide series metal elements including La, ce, pr and Nd.
Among the hard alloys, WC-Co-M 2 The mass ratio of (1) is 84-96.
The preparation method of the hard alloy comprises the following steps:
(1) Cleaning the surface of the hard alloy, soaking the hard alloy in acetone, then ultrasonically cleaning, and then carrying out ion etching;
(2) Maintaining the internal temperature of the ion plating equipment at 400-500 ℃, introducing nitrogen, and sequentially starting AlCrVM 1 N target and AlCrYN target, coating the hard alloy surface with the coating;
wherein, controlling AlCrVM 1 The thickness of the N coating and the AlCrYN coating is 0.5-3 mu m, preferably 1-2 mu m respectively;
AlCrVM 1 in the N coating, al, cr, V and M 1 3-6;
in the AlCrYN coating, the atomic ratio of Al to Cr to Y is 4-6.
Example 1
A high-wear-resistance hard alloy coating comprises a double-layer structure and is composed of a bonding layer and a surface layer, wherein the bonding layer is an AlCrVLaN coating, and the surface layer is an AlCrYN coating.
The bonding layer is plated on the surface of the hard alloy.
The preparation method of the hard alloy comprises the following steps:
(1) Cleaning the surface of the hard alloy, soaking the hard alloy in acetone, then ultrasonically cleaning, and then carrying out ion etching;
the hard alloy is WC-Co-La hard alloy;
in the hard alloy, the mass ratio of WC-Co-La is 90.
(2) Maintaining the internal temperature of the ion plating equipment at 450 ℃, introducing nitrogen, sequentially starting an AlCrVLaN target and an AlCrYN target, and plating a coating on the surface of the hard alloy;
wherein the thickness of the AlCrVLaN coating and the AlCrYN coating is controlled to be 1.6 mu m;
in the AlCrVLaN coating, the atomic ratio of Al to Cr to V to La is (4.5);
in the AlCrYN coating, the atomic ratio of Al to Cr to Y is 5.
Example 2
A high wear-resistant hard alloy coating comprises a double-layer structure and is composed of a bonding layer and a surface layer, wherein the bonding layer is an AlCrVCeN coating, and the surface layer is an AlCrYN coating.
The bonding layer is plated on the surface of the hard alloy.
The preparation method of the hard alloy comprises the following steps:
(1) Cleaning the surface of the hard alloy, soaking the hard alloy in acetone, then ultrasonically cleaning, and then carrying out ion etching;
the hard alloy is WC-Co-Ce hard alloy;
in the hard alloy, the mass ratio of WC-Co-Ce is 90.
(2) Maintaining the internal temperature of the ion plating equipment at 450 ℃, introducing nitrogen, sequentially starting an AlCrVCeN target and an AlCrYN target, and plating a coating on the surface of the hard alloy;
wherein the thickness of the AlCrVCeN coating and the AlCrYN coating is controlled to be 1.6 mu m;
in the AlCrVCeN coating, the atomic ratio of Al to Cr to V to Ce is (4.5);
in the AlCrYN coating, the atomic ratio of Al to Cr to Y is 5.
Comparative example 1
A highly wear resistant coating for cemented carbide comprising a single layer structure, which layer is an AlCrVN coating.
The layer is plated directly on the cemented carbide surface.
The preparation method of the hard alloy comprises the following steps:
(1) Cleaning the surface of the hard alloy, soaking the hard alloy in acetone, then ultrasonically cleaning, and then carrying out ion etching;
the hard alloy is WC-Co-La hard alloy;
in the hard alloy, the mass ratio of WC-Co-La is 90.
(2) Maintaining the internal temperature of the ion plating equipment at 450 ℃, introducing nitrogen, starting an AlCrVN target, and plating a coating on the surface of the hard alloy;
wherein the thickness of the AlCrVN coating is controlled to be 3.2 mu m;
in the AlCrVN coating, the atomic ratio of Al to Cr to V is 4.5.
Comparative example 2
A high-wear-resistance hard alloy coating comprises a double-layer structure and is composed of a bonding layer and a surface layer, wherein the bonding layer is an AlCrVLaN coating, and the surface layer is an AlCrYN coating.
The bonding layer is arranged on the surface of the hard alloy.
The preparation method of the hard alloy comprises the following steps:
(1) Cleaning the surface of the hard alloy, soaking the hard alloy in acetone, then ultrasonically cleaning, and then carrying out ion etching;
the hard alloy is WC-Co hard alloy;
in the hard alloy, the mass ratio of WC-Co is 96.
(2) Maintaining the internal temperature of the ion plating equipment at 450 ℃, introducing nitrogen, sequentially starting an AlCrVLaN target and an AlCrYN target, and plating a coating on the surface of the hard alloy;
wherein the thickness of the AlCrVLaN coating and the AlCrYN coating is controlled to be 1.6 mu m;
in the AlCrVLaN coating, the atomic ratio of Al to Cr to V to La is 4.5;
in the AlCrYN coating, the atomic ratio of Al to Cr to Y is 5.
Testing the obtained hard alloy, wherein the hardness of the hard alloy is tested by using a microhardness tester; the oxidation performance is tested in a muffle furnace for oxidation weight gain, and the mixture is heated for 2 hours at the temperature of 900 ℃ in the air atmosphere; the abrasion loss test was performed in an atmospheric atmosphere using a frictional abrasion tester. The test results are shown in Table 1.
Table 1: hard alloy coating performance test
| Unit of | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | |
| Hardness of | HV | 2466 | 2434 | 2394 | 2410 |
| Oxidation weight gain | mg/cm 2 | 0.51 | 0.53 | 0.58 | 0.51 |
| Amount of wear | mg/h | 0.19 | 0.20 | 0.29 | 0.26 |
From the test results, it can be seen that the addition of lanthanide metal elements to cemented carbide significantly improves the amount of wear of the coating while maintaining hardness and oxidation properties. The probable reason is that the lanthanide metal element has special atomic structure and strong chemical activity, so that the compactness of the coating is improved, the lanthanide metal element is easy to deform, and deformation and micro-hard alloying action exist in the coating and the hard alloy, so that the interface performance of the coating and the hard alloy can be further improved, and the wear resistance of the coating can be improved.
Of course, those skilled in the art will appreciate that the above-described embodiments are merely some, and not all, embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Claims (2)
1. The high wear-resistant hard alloy is characterized in that the surface of the hard alloy is plated with a coating, the coating comprises a double-layer structure and consists of a bonding layer and a surface layer, and the bonding layer is AlCrVM 1 A N coating layer, wherein the surface layer is AlCrYNCoating;
the bonding layer is plated on the surface of the hard alloy;
the hard alloy is WC-Co-M 2 Hard alloy;
among the cemented carbides, WC-Co-M 2 The mass ratio of (1) is 90;
said M 1 、M 2 The same, and is lanthanide metal element La or Ce;
the AlCrVM 1 The thickness of the N coating and the AlCrYN coating is 1.6 mu m;
AlCrVM 1 in the N coating, al, cr, V and M 1 In an atomic ratio of 4.5;
in the AlCrYN coating, the atomic ratio of Al to Cr to Y is 5.
2. The method for preparing the hard alloy according to claim 1, which is characterized by comprising the following steps:
(1) Cleaning the surface of the hard alloy, soaking the hard alloy in acetone, then ultrasonically cleaning, and then carrying out ion etching;
(2) Maintaining the internal temperature of the ion plating equipment at 400-500 ℃, introducing nitrogen, and sequentially starting AlCrVM 1 N target and AlCrYN target, the coating was plated onto the cemented carbide surface.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE518145C2 (en) * | 1997-04-18 | 2002-09-03 | Sandvik Ab | Multilayer coated cutting tool |
| SE0004203D0 (en) * | 2000-11-16 | 2000-11-16 | Haakan Hugosson | A surface coating |
| SE526336C2 (en) * | 2002-07-01 | 2005-08-23 | Seco Tools Ab | Cut with durable refractory coating of MAX phase |
| CN101381836B (en) * | 2008-10-27 | 2010-12-15 | 王铀 | Nano modified WC/Co cemented carbide material and manufacturing method thereof |
| CN102994854B (en) * | 2012-12-11 | 2015-06-17 | 重庆文理学院 | Fine-particle wear-resistant cemented carbide for railway tamping pickaxe and preparation method thereof |
| CN109666906A (en) * | 2019-01-16 | 2019-04-23 | 广东工业大学 | A kind of high-temperature oxidation resistant AlCrYN coating and its preparation method and application |
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Address after: 412005 room 6-b, building 6, power components industrial park, Xinma power independent innovation park, Tianyuan District, Zhuzhou City, Hunan Province Patentee after: Zhuzhou SRP Cemented Carbide Co.,Ltd. Address before: 412005 room 6-b, building 6, power components industrial park, Xinma power independent innovation park, Tianyuan District, Zhuzhou City, Hunan Province Patentee before: Zhuzhou srip cemented carbide Co.,Ltd. |