CN112725754B - Coating material, preparation method and alloy material - Google Patents
Coating material, preparation method and alloy material Download PDFInfo
- Publication number
- CN112725754B CN112725754B CN202011475658.XA CN202011475658A CN112725754B CN 112725754 B CN112725754 B CN 112725754B CN 202011475658 A CN202011475658 A CN 202011475658A CN 112725754 B CN112725754 B CN 112725754B
- Authority
- CN
- China
- Prior art keywords
- layer
- target
- tib
- electrode
- voltage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 238000000576 coating method Methods 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000956 alloy Substances 0.000 title claims abstract description 21
- 229910006281 γ-TiAl Inorganic materials 0.000 claims abstract description 34
- 238000009792 diffusion process Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000007747 plating Methods 0.000 claims abstract description 19
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 104
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 46
- 229910052786 argon Inorganic materials 0.000 claims description 23
- 238000004321 preservation Methods 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000013077 target material Substances 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 239000000919 ceramic Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 73
- 239000010408 film Substances 0.000 description 22
- 239000011159 matrix material Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 10
- 239000002344 surface layer Substances 0.000 description 10
- 238000005275 alloying Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910010038 TiAl Inorganic materials 0.000 description 3
- 229910033181 TiB2 Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- QDMRQDKMCNPQQH-UHFFFAOYSA-N boranylidynetitanium Chemical compound [B].[Ti] QDMRQDKMCNPQQH-UHFFFAOYSA-N 0.000 description 2
- 238000005271 boronizing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- 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
- C23C14/48—Ion implantation
-
- 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
- C23C14/067—Borides
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- 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
- C23C14/54—Controlling or regulating the coating process
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
The invention discloses a coating material, a preparation method and an alloy material. The coating material of the invention consists of a Ti layer and TiBxThe periodic units formed by the layers are sequentially arranged, wherein x is 1-2; the thickness of the Ti layer is 100-500nm, and the TiB layerxThe layer thickness is 100-500 nm; the TiBx coating is prepared by a three-cathode ion diffusion plating method; the arrangement period of the periodic units is 10-50. The invention prepares a nano-level Ti layer and TiB by a three-cathode ion diffusion plating methodxContinuous multilayer film composed of layers, design of multilayer film and preparation of nano-level film to maintain TiB on coating surfacexThe ceramic layer has high hardness, high wear resistance and high-temperature oxidation resistance, the internal stress of the coating is effectively reduced, the toughness of the ceramic layer is improved, the comprehensive mechanical property is excellent, the service life of the gamma-TiAl material with the coating as an aeroengine component material is prolonged, and the application prospect is wide.
Description
Technical Field
The invention relates to a high-temperature wear-resistant material, a preparation method and an alloy, in particular to a coating material, a preparation method and an alloy material.
Background
The titanium alloy is applied to an engine at the core part of an airplane, the use amount of the titanium alloy on the airplane engine can reach 20-30% of the total weight, and the titanium alloy is generally used for manufacturing parts of an air compressor. With the rapid development of aerospace, the original material cannot meet the use requirement of high performance. The realization of the advanced aeroengine with high thrust-weight ratio, high pressure ratio, high turbine front temperature and low oil consumption target not only adopts advanced structural design and accurate strength calculation, but also strongly depends on the light heat-resistant titanium alloy material. It is desirable to provide new materials that are resistant to harsh environments, such as high temperatures, high pressures, and smoke, which require high strength, oxidation resistance, and high wear resistance. At present, materials researchers have carried out a series of research works on new materials with light weight and excellent comprehensive performance, wherein the research on TiAl intermetallic compounds is particularly emphasized.
When the aircraft engine is in a high-speed operation process, the internal components continuously slide and roll, and the components are repeatedly rubbed, loaded and unloaded, so that high-temperature friction is caused, the elasticity of the surface layers of the parts is reduced, and finally the parts are damaged to different degrees. After a long time, the surface layer of the component can generate deformation or cracks due to friction, and even the large fragments of the surface layer can be peeled off and pits can occur if the surface layer is greatly limited, and the normal operation of an engine can be disturbed; on the other hand, in the engine operation process, the internal components are locally plastically deformed under the effect of friction, the component surface layer material is transferred or the surface layer material is adhered to other component surface layers, and the interference range is larger. Therefore, the further application of the gamma-TiAl on the aeroengine is limited by the defects of insufficient wear resistance and poor high-temperature oxidation resistance of the gamma-TiAl.
Because the frictional wear and the high-temperature oxidation are the surface damages of the material, the surface treatment technology is mainly adopted to improve the performance of the gamma-TiAl surface layer, thereby ensuring the normal use of the gamma-TiAl surface layer under the working condition of high-temperature wear. A better method for solving the problems of insufficient wear resistance and poor high-temperature oxidation resistance of the gamma-TiAl is to select a coating with high hardness, high wear resistance and good high-temperature oxidation resistance to protect the gamma-TiAl surface layer. TiB compound formed by reaction of Ti and Bx(x is 1-2) because it has the characteristics of high hardness, high strength, good high-temperature oxidation resistance and the like of ceramic materials, and has the excellent characteristics of good heat conduction and the like of metal materialsTo a wide range of concerns.
In TiBxAmong various preparation methods of the coating, the solid boronizing method has the advantages of simple equipment, convenient operation and strong adaptability, can obtain the in-situ metallurgically bonded boron-titanium compound layer, but has the advantages of thin thickness of the boronized layer, low efficiency, difficult phase control and random growth direction of the boronized layer. Aiming at the problem, the three-cathode ion diffusion plating technology can obtain TiB with adjustable thickness and directionally-oriented growth by adjusting proper process combinationxAnd (4) coating.
The three-cathode ion diffusion plating technology is established on the basis of the double-glow plasma surface alloying technology, and is characterized in that a porous cavity cathode is arranged between two cathodes of a double-glow plasma surface alloying device and is connected with a direct-current power supply. The double glow plasma surface alloying technology is a novel surface modification treatment technology, and has the greatest advantages that a mutual diffusion layer can be formed between a modification layer and a matrix through element diffusion, and the components of the diffusion layer are in gradient distribution, so that the modification layer and the matrix form metallurgical bonding and are firmly bonded with the matrix. In addition, the thickness and the components of the diffusion layer can be controlled by adjusting the process parameters such as voltage, air pressure, heat preservation time and the like, and the bonding force of the modified layer can be effectively improved by the diffusion layer. The alloy layer prepared by the technology has compact and complete surface, no holes, impurities, cracks and the like, can realize the coordination and unification of hardness and toughness between the surface alloy layer and the matrix, can ensure the deformation compatibility of the alloy layer and the matrix even under a harsh service environment, and is not easy to peel off from the matrix, thereby providing long-acting protection.
Because the gamma-TiAl matrix and the TiBxThe ceramic layer has poor compatibility and large linear expansion coefficient difference, so that the internal stress of the coating is large, and the coating is easy to peel off. Therefore, it is necessary to use γ -TiAl matrix and TiBxPreparing an intermediate transition layer between the ceramic layers, and releasing the stress of the coating.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems of poor wear resistance and insufficient high-temperature oxidation resistance of the existing alloy material, the invention provides a coating material consisting of a nano-level multilayer film prepared by a double-glow plasma alloying method. The invention also provides a preparation method of the coating material, an alloy material containing the coating and a preparation method of the alloy material.
The technical scheme is as follows: the coating material consists of Ti layer and TiBxThe periodic units formed by the layers are sequentially arranged, wherein x is 1-2; the thickness of the Ti layer is 100-500nm, and the TiB layerxThe layer thickness is 100-500 nm; the TiBx coating is prepared by a three-cathode ion diffusion plating method; the arrangement period of the periodic units is 10-50.
The invention adopts the three-cathode ion diffusion plating technology to improve the problems of thin thickness of the diffusion layer, low efficiency, difficult phase control, random growth direction of the diffusion layer and the like of the solid boronizing method, and the proper process combination is adjusted to obtain the boron-titanium composite layer with adjustable thickness and directional growth.
The three-cathode ion diffusion plating method comprises the following steps: the method comprises the steps of taking a Ti target and a B target as double sources, keeping a Ti target power supply continuously turned on, periodically switching on and off the B target power supply, and preparing a Ti layer for 2-10 min in each period unit, wherein TiB isxThe preparation time of the layer is 2-10 min.
The preparation process parameters of the Ti layer are as follows: electrode voltage of a workpiece: 500-550V; source voltage: 700-800V; argon pressure: 18-36 Pa; and (3) heat preservation temperature: 700-750 ℃; distance between the Ti target and the workpiece: 20-30 mm; and (3) heat preservation time: 2-10 min;
the TiBxThe preparation process parameters of the layer are as follows: electrode voltage of a workpiece: 500-550V; ti target source voltage: 700-800V; b target source voltage: 850-900V; argon pressure: 18-36 Pa; and (3) heat preservation temperature: 850-900 ℃; b, distance between the target and the workpiece: 10-15 mm; and (3) heat preservation time: 2-10 min.
The preparation method of the coating material comprises the following steps:
(S11) putting the Ti target and the B target into a three-cathode ion diffusion plating device to be used as double sources, vacuumizing to the limit vacuum degree, feeding argon, and starting glow;
(S12) keeping the Ti target electrode power supply continuously turned on, stabilizing the technological parameters, periodically switching on and off the B target electrode power supply, and preparing TiBxLayer, finally obtaining a Ti layer and TiBxThe layers constitute a continuous multilayer film.
The alloy material comprises a titanium-based material and the coating material.
Preferably, the titanium-based material is γ -TiAl.
The alloy material is prepared by the following method:
(S21) sequentially loading gamma-TiAl, a Ti target and a B target into a three-cathode ion diffusion plating device, wherein the Ti target and the B target are used as double sources, and the gamma-TiAl is used as a workpiece electrode;
(S22) vacuumizing to a limit vacuum degree, feeding argon, starting glow, firstly cleaning the target material and the gamma-TiAl, and preparing a Ti layer after cleaning is finished; keeping the Ti target electrode power supply continuously turned on, stabilizing the technological parameters, periodically switching on and off the B target electrode power supply, and preparing TiBxA layer, a Ti layer and TiB are prepared on the surface of the gamma-TiAl layer after 10 to 50 periodsxThe layers constitute a continuous multilayer film.
In the step (S22), the Ti layer is prepared by the following process parameters: electrode voltage of a workpiece: 500-550V; source voltage: 700-800V; argon pressure: 18-36 Pa; and (3) heat preservation temperature: 700-750 ℃; distance between the Ti target and the workpiece: 20-30 mm; and (3) heat preservation time: 2-10 min; the TiBxThe preparation process parameters of the layer are as follows: electrode voltage of a workpiece: 500-550V; ti target source voltage: 700-800V; b target source voltage: 850-900V; argon pressure: 18-36 Pa; and (3) heat preservation temperature: 850-900 ℃; b, distance between the target and the workpiece: 10-15 mm; and (3) heat preservation time: 2-10 min.
TiB prepared by the method of step (S22)xAnd the value range of x is between 1 and 2.
The alloy material comprises the following steps:
(S31) sequentially loading gamma-TiAl, Ti targets and B targets into a furnace chamber of a three-cathode ion diffusion plating device, starting a mechanical pump and cooling water, and vacuumizing to the vacuum degree of below 0.2-0.4 Pa; opening a molecular pump and an argon valve, carrying out cavity gas washing for 2-5 times, and introducing argon to keep the gas pressure of the cavity at 18-36 Pa;
(S32) turning on the Ti target power supply, the workpiece electrode voltage: 500-550V; source voltage: 700-800V; temperature: 700 ℃ and 750 ℃; time: 2-10 min; after the Ti layer is prepared, keeping the voltage of a Ti target electrode and the voltage of a workpiece electrode unchanged, turning on a power supply of a B target electrode, and switching on the voltage of a B target source electrode: 850-900V; temperature: 850-900 ℃; time: 2-10 min; finishing heat preservation, and closing a source electrode power supply of the target B;
(S33) repeating the step (S32) 10-30 times to prepare a Ti layer and TiBxA continuous multilayer film of layers;
(S34) after the last heat preservation is finished, respectively reducing the voltage of the Ti target electrode and the voltage of the B target electrode, respectively preserving the heat of each level of voltage for 3-5 min, closing the power supplies of the Ti target and the B target source electrode, and opening the furnace for sampling when the temperature is reduced to 100-150 ℃.
The preferred preparation method of the alloy material comprises the following steps:
one preferred treatment method of the invention is as follows:
step 1: the target materials are Ti target and B target, and the purity is 99.99%; before the target material is installed, polishing with No. 01 abrasive paper to remove an oxide layer, ultrasonically cleaning in absolute ethyl alcohol, and drying; the matrix material is gamma-TiAl, the matrix is made into a sample with the size of 15mm multiplied by 4mm by utilizing the spark line cutting technology, and then the sample is polished by 0#, 01#, 02#, 03#, 05#, 06#, 07# abrasive paper and then is polished by 3.5 mu m diamond grinding paste. Ultrasonically cleaning the substrate by using an acetone solution, and drying the substrate for later use;
in the invention, argon (with the purity of 99.99%) is selected as the working carrier gas for the glow plasma surface alloying test, and the argon has stronger sputtering capability and high chemical stability and does not react with metal elements.
Step 2: putting a sample into a furnace chamber, opening a mechanical pump and cooling water, and vacuumizing to a vacuum degree of below 0.2-0.4 Pa; opening a molecular pump and an argon valve, carrying out cavity gas washing for 2-5 times, introducing argon to keep the gas pressure of the cavity at 18-36Pa, opening a Ti target electrode power supply, and preheating for 3-5 min;
electrode voltage of a workpiece: 500-550V;
source voltage: 700-800V;
temperature: 750-800 ℃;
time: 2-10 min;
after the preparation of the Ti layer is finished, keeping the voltage of a Ti target electrode and the voltage of a workpiece electrode unchanged, turning on a power supply of a B target electrode, and preheating for 3-5 min;
b target source voltage: 850-900V
Temperature: 850-900 ℃;
time: 2-10 min;
finishing heat preservation, and closing a source electrode power supply of the target B;
and step 3: repeating the operation for 10-50 times to prepare a continuous multilayer film consisting of a nano-level Ti layer-TiBx layer-Ti layer-TiBx layer which are periodically arranged;
and 4, step 4: and after the last heat preservation is finished, respectively reducing the voltage of the Ti target electrode and the voltage of the B target electrode, respectively preserving the heat of each level of voltage for 3-5 min, then closing the power supplies of the Ti target and the B target source electrode, and opening the furnace for sampling when the temperature is reduced to 100-150 ℃.
The nano-scale layer as referred to in the present invention means the thickness of a single Ti layer or TiBx layer.
Has the advantages that: (1) the invention adopts the three-cathode ion diffusion plating technology to prepare the nano-level Ti layer-TiBx layer continuous multilayer film through a small modulation period, and changes the micron-level TiB in the prior artxForm of coating, nano-scale TiBxThe coating not only maintains the high hardness and high strength of the coating, but also the Ti layer and TiB due to the existence of the Ti layerxThe layers are alternately deposited, the internal stress of the coating is effectively reduced by the design of the multilayer film and the improvement of the toughness of the coating, so that the coating is not easy to peel off, and the wear resistance, the high-temperature oxidation resistance and the service life of the base material are improved; (2) the invention selects a Ti layer as an intermediate transition layer, TiBxHas good compatibility with titanium and density similar to that of titanium (the density of titanium is 4.5 g/cm)-3The TiB density is 4.51g/cm-3，TiB2The density was 4.52g/cm-3) The difference in linear expansion coefficient is within 50% (the linear expansion coefficient of titanium is 9X 10)-6The coefficient of linear expansion of the TiB is 8.6 multiplied by 10-6/K，TiB2Linear expansion coefficient of 6.4X 10-6K) and the elastic modulus is 4 to 5 times that of titanium (the elastic modulus of titanium is 115GPa, the elastic modulus of TiB is 550GPa, TiB2530GPa), through a Ti layer as an intermediate transition layer, and through Ti/TiBxDesign of thin film multilayer structureThe toughness of the coating is improved, the coating and the matrix are firmly combined, and the internal stress of the coating is effectively reduced.
Drawings
FIG. 1 is a schematic view of a three-cathode ion diffusion plating apparatus;
FIG. 2 shows Ti/TiBx/Ti/TiBx……Ti/TiBxCoating structure diagram composed of multilayer film.
Detailed Description
Example 1: the three-cathode ion diffusion plating equipment is shown in figure 1, the target materials are a Ti target and a B target, and the purity is 99.99 percent. Before the target material is installed, polishing with No. 01 abrasive paper to remove an oxide layer, ultrasonically cleaning in absolute ethyl alcohol, and drying;
the matrix material is gamma-TiAl, the matrix is made into a sample with the size of 15mm multiplied by 4mm by utilizing the spark line cutting technology, and then the sample is polished by 0#, 01#, 02#, 03#, 05#, 06#, 07# abrasive paper and then is polished by 3.5 mu m diamond grinding paste. Ultrasonically cleaning the substrate by using an acetone solution, and drying the substrate for later use;
argon (with the purity of 99.99%) is selected as working carrier gas for glow plasma surface alloying tests, has strong sputtering capacity and high chemical stability, and does not react with metal elements;
putting a sample into a furnace chamber, opening a mechanical pump and cooling water, and vacuumizing to a vacuum degree of below 0.2-0.4 Pa; opening a molecular pump and an argon valve, carrying out cavity gas washing for 2-5 times, introducing argon to keep the gas pressure of the cavity at 18-36Pa, opening a Ti target electrode power supply, and preheating for 3-5 min;
electrode voltage of a workpiece: 500V;
ti target source voltage: 700V;
temperature: 700-750 ℃;
time: 5 min;
after the preparation of the Ti layer is finished, keeping the voltage of a Ti target electrode and the voltage of a workpiece electrode unchanged, turning on a power supply of a B target electrode, and preheating for 3-5 min;
b target source voltage: 850V;
temperature: 850-900 ℃;
time: 5 min;
finishing heat preservation, and closing a source electrode power supply of the target B;
repeating the above operation 30 times to prepare Ti/TiBx/Ti/TiBx……Ti/TiBxContinuous multilayer film, total 60 layers;
and after the last heat preservation is finished, closing the power supplies of the Ti target and the B target, and opening the furnace for sampling when the temperature is reduced to 100-150 ℃.
The alloy material prepared by the invention is shown in figure 2, the substrate material is gamma-TiAl, and a Ti layer and TiB are sequentially deposited on the surface of the gamma-TiAlxLayer (TiB)xCeramic layer) adjacent to the Ti/TiBxThe mutual diffusion layer is formed between the films through element diffusion, and the combination is firm, namely the Ti/TiB is prepared through periodically switching on and off a B target source power supply and in a small modulation periodx/Ti/TiBx……Ti/TiBxA continuous multilayer film. In the invention, the gamma-TiAl can be replaced by other titanium-based materials.
In the embodiment, Ti/TiB is prepared by adopting three-cathode ion diffusion plating equipmentx/Ti/TiBx……Ti/TiBxMultilayer film, total coating thickness 15 μm, single Ti layer thickness about 250nm, single TiB layerxThe ceramic layer is about 250nm thick. The hardness of the gamma-TiAl matrix is 240-260 HV0.1The coating has high hardness, and the microhardness measurement shows that the hardness of a test sample is 1857.8HV0.1. The friction and wear test of the coating at room temperature is a CET-I type friction and wear tester produced by Lanzhou chemical and physical research institute of Chinese academy of sciences, and the experimental method is a reciprocating friction and wear test. The test parameters are: ZrO is selected as small ball material of friction pair2The sliding speed is 300r/min, the load is 12N, the reciprocating length is 5mm, and the abrasion time is 30 min. The friction and wear test at high temperature is a HT-500 miniature high-temperature friction and wear tester produced by the national institute of materialization of Lanzhou, and adopts a ball disc type wear test method. The test parameters are: the test temperature is 500 ℃, and ZrO is selected as the material of the small ball of the friction pair2The sliding speed is 560r/min, the load is 8N, the test rotating radius is 2mm, and the abrasion time is 30 min. The test principle of the friction and wear test is as follows: during the test, the sample is fixed on the objective table, and the small ball of the friction pair is vertical to the sample. While rubbingA constant vertical pressure P is applied to the secondary pellet and generates a load on the sample. When the sample moves along with the movement of the object stage, the sample and the small ball of the friction pair slide under the action of the vertical pressure P to cause friction and abrasion. The results of the abrasion tests at room temperature (20 ℃) and high temperature (500 ℃) show that: the specific wear rate of the coating at room temperature (20 ℃) is reduced by 83.7 percent compared with gamma-TiAl, and the specific wear rate at high temperature (500 ℃) is reduced by 61.8 percent compared with the gamma-TiAl. The results of the constant temperature oxidation experiments at 750 ℃, 850 ℃ and 950 ℃ show that: after the gamma-TiAl matrix is oxidized for 40 hours at 750 ℃, an oxide film is cracked and peeled off, the oxidation degree is increased at 850 ℃, and the oxide layer is loose and easy to peel off; after the coating is oxidized for 100 hours at the constant temperature of 950 ℃, an oxide film formed on the surface is flat and uniform in thickness, is tightly combined with the coating, has no holes or cracks, is complete in structure, has good adhesion between the oxide film and a substrate, and remarkably improves the oxidation resistance of the gamma-TiAl.
Example 2:
the target materials are Ti target and B target, and the purity is 99.99%. Before the target material is installed, polishing with No. 01 abrasive paper to remove an oxide layer, ultrasonically cleaning in absolute ethyl alcohol, and drying;
the matrix material is gamma-TiAl, the matrix is made into a sample with the size of 15mm multiplied by 4mm by utilizing the spark line cutting technology, and then the sample is polished by 0#, 01#, 02#, 03#, 05#, 06#, 07# abrasive paper and then is polished by 3.5 mu m diamond grinding paste. Ultrasonically cleaning the substrate by using an acetone solution, and drying the substrate for later use;
argon (with the purity of 99.99%) is selected as working carrier gas for glow plasma surface alloying tests, has strong sputtering capacity and high chemical stability, and does not react with metal elements;
putting a sample into a furnace chamber, opening a mechanical pump and cooling water, and vacuumizing to a vacuum degree of below 0.2-0.4 Pa; opening a molecular pump and an argon valve, carrying out cavity gas washing for 2-5 times, introducing argon to keep the gas pressure of the cavity at 18-36Pa, opening a Ti target electrode power supply, and preheating for 3-5 min;
electrode voltage of a workpiece: 550V;
ti target source voltage: 800V;
temperature: 700-750 ℃;
time: 10 min;
after the preparation of the Ti layer is finished, keeping the voltage of a Ti target electrode and the voltage of a workpiece electrode unchanged, turning on a power supply of a B target electrode, and preheating for 3-5 min;
b target source voltage: 900V
Temperature: 850-900 ℃;
time: 10 min;
finishing heat preservation, and closing a source electrode power supply of the target B;
repeating the above operation 20 times to prepare Ti/TiBx/Ti/TiBx……Ti/TiBxA continuous multilayer film, total 40 layers;
and after the last heat preservation is finished, closing the power supplies of the Ti target and the B target, and opening the furnace for sampling when the temperature is reduced to 100-150 ℃.
The invention prepares Ti/TiB by adopting three-cathode ion diffusion plating equipmentx/Ti/TiBx……Ti/TiBxMultilayer film, total coating thickness of 16 μm, thickness of single Ti layer of about 400nm, single TiB layerxThe ceramic layer is about 400nm thick. The hardness of the gamma-TiAl matrix is 240-260 HV0.1The coating has high hardness, and the microhardness measurement shows that the hardness of a test sample is 1835.8HV0.1. The coating was subjected to abrasion tests at room temperature and at elevated temperature according to the method of example 1. The results of the abrasion tests at room temperature (20 ℃) and high temperature (500 ℃) show that: the specific wear rate of the coating at room temperature (20 ℃) is reduced by 80.7 percent compared with gamma-TiAl, and the specific wear rate at high temperature (500 ℃) is reduced by 59.9 percent compared with the gamma-TiAl. The results of the constant temperature oxidation experiments at 750 ℃, 850 ℃ and 950 ℃ show that: after the gamma-TiAl matrix is oxidized for 40 hours at 750 ℃, an oxide film is cracked and peeled off, the oxidation degree is increased at 850 ℃, and the oxide layer is loose and easy to peel off; after the coating is oxidized for 100 hours at the constant temperature of 950 ℃, an oxide film formed on the surface is flat and uniform in thickness, is tightly combined with the coating, has no holes or cracks, is complete in structure, has good adhesion between the oxide film and a substrate, and remarkably improves the oxidation resistance of the gamma-TiAl.
According to the invention, the nano-level Ti/TiBx/Ti/TiBx … … Ti/TiBx multilayer film is prepared by adopting the three-cathode ion diffusion plating equipment, and due to the design of the multilayer structure of the Ti/TiBx film and the improvement of the toughness of the coating, the coating is firmly combined with the substrate, the internal stress of the coating is effectively reduced, and the oxidation resistance of the gamma-TiAl is obviously improved.
Claims (3)
1. The preparation method of the alloy material is characterized in that the alloy material is prepared by the following steps:
(S11) sequentially loading gamma-TiAl, a Ti target and a B target into a three-cathode ion diffusion plating device, wherein the Ti target and the B target are used as double sources, and the gamma-TiAl is used as a workpiece electrode;
(S12) vacuumizing to a limit vacuum degree, feeding argon, starting glow, firstly cleaning the target material and the gamma-TiAl, and preparing a Ti layer after cleaning is finished; keeping the Ti target electrode power supply continuously turned on, stabilizing the technological parameters, periodically switching on and off the B target electrode power supply, and preparing TiBxLayer, x is 1-2; after 10-50 cycles, a Ti layer and TiB are prepared on the surface of the gamma-TiAlxThe layers constitute a continuous multilayer film; the preparation process parameters of the Ti layer are as follows: electrode voltage of a workpiece: 500-550V; source voltage: 700-800V; argon pressure: 18-36 Pa; and (3) heat preservation temperature: 700-750 ℃; distance between the Ti target and the workpiece: 20-30 mm; and (3) heat preservation time: 2-10 min; the TiBxThe preparation process parameters of the layer are as follows: electrode voltage of a workpiece: 500-550V; ti target source voltage: 700-800V; b target source voltage: 850-900V; argon pressure: 18-36 Pa; and (3) heat preservation temperature: 850-900 ℃; b, distance between the target and the workpiece: 10-15 mm; and (3) heat preservation time: 2-10 min.
2. The method for preparing the alloy material according to claim 1, comprising the steps of:
(S21) sequentially loading gamma-TiAl, Ti targets and B targets into a furnace chamber of a three-cathode ion diffusion plating device, starting a mechanical pump and cooling water, and vacuumizing to the vacuum degree of below 0.2-0.4 Pa; opening a molecular pump and an argon valve, carrying out cavity gas washing for 2-5 times, and introducing argon to keep the gas pressure of the cavity at 18-36 Pa;
(S22) turning on the Ti target power supply, the workpiece electrode voltage: 500-550V; source voltage: 700-800V; temperature: 700 ℃ and 750 ℃; time: 2-10 min; after the Ti layer is prepared, keeping the voltage of a Ti target electrode and the voltage of a workpiece electrode unchanged, turning on a power supply of a B target electrode, and switching on the voltage of a B target source electrode: 850-900V; temperature: 850-900 ℃; time: 2-10 min; finishing heat preservation, and closing a source electrode power supply of the target B;
(S23) repeating the step (S22) 10-30 times to prepare a Ti layer and TiBxA continuous multilayer film of layers;
(S24) after the last heat preservation is finished, respectively reducing the voltage of the Ti target electrode and the voltage of the B target electrode, respectively preserving the heat of each level of voltage for 3-5 min, closing the power supplies of the Ti target and the B target source electrode, and opening the furnace for sampling when the temperature is reduced to 100-150 ℃.
3. An alloy material produced by the production method according to claim 1, comprising a titanium-based material and a coating material; the titanium-based material is gamma-TiAl; the coating material consists of a Ti layer and TiBxThe periodic units formed by the layers are sequentially arranged, wherein x is 1-2; the thickness of the Ti layer is 100-500nm, and the TiB layerxThe layer thickness is 100-500 nm; the TiBx coating is prepared by a three-cathode ion diffusion plating method; the arrangement period of the periodic units is 10-50; in each period unit, the preparation time of the Ti layer is 2-10 min, and the TiBxThe preparation time of the layer is 2-10 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011475658.XA CN112725754B (en) | 2020-12-15 | 2020-12-15 | Coating material, preparation method and alloy material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011475658.XA CN112725754B (en) | 2020-12-15 | 2020-12-15 | Coating material, preparation method and alloy material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112725754A CN112725754A (en) | 2021-04-30 |
| CN112725754B true CN112725754B (en) | 2021-12-21 |
Family
ID=75602209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011475658.XA Active CN112725754B (en) | 2020-12-15 | 2020-12-15 | Coating material, preparation method and alloy material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112725754B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481467B (en) * | 2021-06-01 | 2022-07-22 | 北京科技大学 | Method for inhibiting generation of ordered intermetallic compound in phase change process of Al-Ni nano multilayer film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731539A (en) * | 1983-05-26 | 1988-03-15 | Plaur Corporation | Method and apparatus for introducing normally solid material into substrate surfaces |
| CN102580154A (en) * | 2012-02-28 | 2012-07-18 | 淮阴工学院 | Antifriction and toughening metal/ceramic bionic multilayer-film artificial joint |
| CN108118304A (en) * | 2017-12-22 | 2018-06-05 | 富耐克超硬材料股份有限公司 | Nano-composite coating and its preparation process |
-
2020
- 2020-12-15 CN CN202011475658.XA patent/CN112725754B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4731539A (en) * | 1983-05-26 | 1988-03-15 | Plaur Corporation | Method and apparatus for introducing normally solid material into substrate surfaces |
| CN102580154A (en) * | 2012-02-28 | 2012-07-18 | 淮阴工学院 | Antifriction and toughening metal/ceramic bionic multilayer-film artificial joint |
| CN108118304A (en) * | 2017-12-22 | 2018-06-05 | 富耐克超硬材料股份有限公司 | Nano-composite coating and its preparation process |
Non-Patent Citations (2)
| Title |
|---|
| "TC4合金表面辉光离子Mo-B共渗的研究";尹忠奇等;《热加工工艺》;20130930;第42卷(第18期);第106-108页 * |
| "三阴极离子渗镀技术及其在纯钛及钛合金上形成金属碳化物的研究";容幸福;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20041215;第3卷(第4期);第26-29、42页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112725754A (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105839061B (en) | The NiCoCrAlY/ZrO on gamma-TiAl alloy surface2Composite coating and preparation method | |
| CN112981320B (en) | Titanium alloy surface composite coating and preparation method thereof | |
| CN104928638A (en) | AlCrSiN-based multilayer nanometer composite cutter coating layer and preparation method thereof | |
| CN105839049B (en) | A kind of titanium-aluminium alloy surface resistance to high temperature oxidation, wear-resistant AlCrN coatings and preparation method thereof | |
| CN113652659B (en) | Preparation method of high-entropy alloy nitride coating metallurgically bonded with substrate | |
| CN108251797B (en) | TiAlN/CrN multilayer coating for titanium alloy cutting tool and preparation method thereof | |
| CN112323013A (en) | Method for preparing high-film-base-binding-force composite coating on surface of titanium alloy | |
| CN109402564A (en) | A kind of AlCrSiN and AlCrSiON double-layer nanometer composite coating and preparation method thereof | |
| CN111647851B (en) | Zr-B-N nano composite coating with high hardness and high toughness and preparation method thereof | |
| CN103590002A (en) | Preparation method for Al-Cr coating on nickel-based superalloy | |
| CN112725754B (en) | Coating material, preparation method and alloy material | |
| CN107937874B (en) | A method of Pt-Al high-temperature protection coating is prepared on niobium alloy surface | |
| CN112962065B (en) | Nickel-based alloy surface composite structure coating and preparation method thereof | |
| CN107604312A (en) | A kind of surface is piston of the wear-resisting ultra high build coating of (Ti, Al) N multilayer insulations and its preparation method and application | |
| CN106893991A (en) | A kind of Zr B O N nano-composite coating preparation technologies | |
| CN109735799A (en) | A kind of cutting tool surface multi-layer step high temperature wear-resistant coating and preparation method thereof | |
| CN112647040A (en) | Ta-c base multilayer wear-resistant cutter coating and preparation method thereof | |
| CN114086117B (en) | Protective coating for resisting erosion of solid particles and preparation method thereof | |
| CN111235533A (en) | AlCrNbSiTiBC high-temperature self-lubricating composite coating of hard alloy milling cutter and preparation method thereof | |
| CN114000118B (en) | Preparation method of titanium alloy surface hardness gradient distribution layer thickness adjustable nitride layer | |
| CN111471973B (en) | Process for preparing Zr-B-N nano composite coating in reducing atmosphere | |
| CN111647859B (en) | Preparation process of Zr-Ti-B-N nano composite coating in reducing atmosphere | |
| CN111500990B (en) | Zr-Ti-B-N nano composite coating and preparation method thereof | |
| CN112126900B (en) | High-temperature low-friction hard nano multilayer VAlCN/VN-Ag coating, and preparation method and application thereof | |
| CN113186505A (en) | Method for preparing WC coating on surface of gamma-TiAl alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |