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CN113088960A - Titanium alloy flexible package wear-resistant coating and preparation method thereof - Google Patents

Titanium alloy flexible package wear-resistant coating and preparation method thereof Download PDF

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CN113088960A
CN113088960A CN202110346189.XA CN202110346189A CN113088960A CN 113088960 A CN113088960 A CN 113088960A CN 202110346189 A CN202110346189 A CN 202110346189A CN 113088960 A CN113088960 A CN 113088960A
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coating
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titanium alloy
wear
cladding
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CN113088960B (en
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林成
彭贤民
李飞
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Liaoning Shihua University
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00Coating starting from inorganic powder
    • C23C24/08Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides

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Abstract

本发明公开了一种钛合金软包装耐磨涂层及其制备方法,解决钛合金的耐磨性问题。该涂层的成分为初生Si和(α+Si)共晶组织,涂层‑基体结合界面组织成分为Ti‑Al系金属间化合物。该涂层具有良好的耐磨性能,从涂层表面到基体在硬度上呈现出由软包装的特点,涂层部分硬度低于钛合金基体,但其耐磨性却较钛合金基体大幅提高。本发明采用等离子焊接和同步送粉熔覆技术制备涂层,该工艺方法易实现,工艺过程可控制,工艺成型质量高。

Figure 202110346189

The invention discloses a wear-resistant coating for a titanium alloy flexible package and a preparation method thereof, and solves the problem of wear resistance of the titanium alloy. The composition of the coating is primary Si and (α+Si) eutectic structure, and the composition of coating-substrate bonding interface is Ti-Al intermetallic compound. The coating has good wear resistance, and the hardness from the coating surface to the substrate shows the characteristics of soft packaging. The hardness of the coating part is lower than that of the titanium alloy substrate, but its wear resistance is greatly improved than that of the titanium alloy substrate. The invention adopts the plasma welding and synchronous powder feeding and cladding technology to prepare the coating, the process method is easy to realize, the process process can be controlled, and the process forming quality is high.

Figure 202110346189

Description

Titanium alloy flexible package wear-resistant coating and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of titanium alloy wear-resistant coatings, and particularly relates to a titanium alloy flexible package wear-resistant coating and a preparation method thereof.
Background
The titanium alloy is an important structural material, the density (4.5 g/cm 3) of titanium is lower than that of steel, and the requirement of aerospace products on light materials is met; the strength (500-1400 MPa) of the titanium alloy is far higher than that of Al and Mg alloys, the titanium alloy has high-temperature resistance and low-temperature performance, and the titanium alloy can work for a long time under the conditions of high temperature of 550 ℃ and low temperature of-250 ℃, and is called as modern metal, space metal and the like. Titanium and titanium alloys are widely used in the industrial sectors of aerospace, aviation, petroleum, chemical industry and the like due to their excellent comprehensive properties of small specific gravity, high specific strength, corrosion resistance, high temperature resistance, no magnetism, weldability and the like. The titanium alloy has poor wear resistance, which limits the wide application of the titanium alloy under the conditions of plowing wear and abrasive wear. In general, titanium alloys undergo severe abrasive wear under normal temperature dry friction conditions. Therefore, the preparation of the wear-resistant coating on the surface of the titanium alloy by using the surface modification technology becomes one of the research hotspots in the field of titanium alloy surface strengthening, and is a technical problem which is always desired to be solved in the field.
Disclosure of Invention
The invention aims to provide a titanium alloy flexible package wear-resistant coating, which solves the problem of poor wear resistance of titanium alloy in the prior art. The coating is composed of primary Si and (alpha + Si) eutectic structures, and the coating-matrix combined interface is composed of Ti-Al series intermetallic compounds. The coating has good wear resistance, the hardness of the coating from the surface of the coating to the substrate is changed from low to high, the hardness of the coating is lower than that of the titanium alloy substrate, but the wear resistance of the coating is greatly improved compared with that of the titanium alloy substrate.
The invention also aims to provide a preparation method of the titanium alloy flexible package wear-resistant coating, which adopts plasma welding and synchronous powder feeding cladding technology, and has the advantages of easy realization, controllable process and high process forming quality.
The technical scheme of the invention is as follows:
a flexible package wear-resistant coating of titanium alloy comprises a primary Si and (alpha + Si) eutectic structure as coating components, and a coating-substrate combination interface structure comprising a primary Si structure and a Ti-Al series intermetallic compound.
The coating and the matrix are completely in metallurgical transition combination, the surface microhardness of the cladding coating is 90-120HV, and the friction and wear resistance is 3-10 times that of the matrix; the hardness of the coating-substrate interface area is 360-700 HV.
A preparation method of a titanium alloy flexible package wear-resistant coating comprises the following steps: selecting Al-Si alloy powder, carrying out plasma welding cladding on a titanium alloy matrix by adopting a plasma welding machine and a synchronous powder feeder, wherein the welding current is 60A-75A, the powder feeding gas flow is 3.2-3.81 atm Nl/min, and carrying out plasma welding cladding on the titanium alloy matrix to form a coating.
The Al-Si alloy powder is subjected to synchronous powder feeding, welding and cladding, wherein the mass fraction of the Si powder is 15-35%.
The Al-Si alloy powder is prepared from 100-120-mesh Al powder and Si powder by fully grinding for 120 minutes by a planetary ball mill.
The design idea of the invention is as follows:
as known from a Ti-Al binary phase diagram, the addition of Al element can reduce the melting point of Ti and increase the beta transition temperature, thereby playing a strengthening role. When the addition amount of Al is small, Al element exists in alpha phase in a replacement mode at room temperature, and when the addition amount of Al exceeds the solubility limit, Ti-Al intermetallic compounds appear in the coating, and the Ti-Al intermetallic compounds have the advantages of small density, high strength, high hardness and the like.
The titanium alloy Al-Si flexible package wear-resistant coating has good bonding strength by combining with Al element, and a Ti-Al intermetallic compound exists at the interface of the coating and the matrix at room temperature, so that local high hardness is shown, and the protection of the titanium alloy matrix under the action of friction and abrasion is enhanced.
Si element in the titanium alloy Al-Si flexible package wear-resistant coating can improve the strength, reduce the thermal expansion coefficient of the coating and be used as a main alloy element for improving the wear resistance. A large number of primary Si particles in the coating play a role in bearing and reducing the abrasion to alpha-Al in the coating, so that the alpha-Al in the coating is prevented from being ploughed and rubbed by dual microprotrusions, and the abrasion rate is further reduced.
The plasma welding cladding technology has high molten pool center temperature, can carry out surface cladding of various ceramic, high-melting point, wear-resisting and heat-resisting materials, and has the advantages of low porosity of the coating, higher bonding strength between the coating and the matrix, easily controlled coating characteristics and size, smooth and flat coating, accurately controlled thickness and less content of oxide and impurities of the coating.
In practical engineering applications, the plasma arc under argon protection will allow a certain amount of oxygen to enter the weld pool due to the practical engineering conditions, and the partThe oxygen element can be Al after the welding seam is formed2O3Are present in the coating, likewise having a beneficial effect on the wear resistance of the coating.
The invention has the advantages that:
1. the coating designed by the invention is very effective in wear-resistant protection of the titanium alloy.
2. The coating is prepared by adopting plasma welding cladding and synchronous powder feeding processes, the metal powder component is Al-Si alloy powder, and the target coating can be prepared on the surface of the titanium alloy substrate subjected to decontamination treatment. The coating components are easy to control and the operability is strong. The powder is heated in the process of spraying out, and is protected by argon and ion gas, so that the uniformity of a cladding layer is better, and the defects of air holes are less.
3. The coating has an obvious tissue composition transition area between the coating and the titanium alloy substrate, the main component is Ti-Al series intermetallic compound, and the coating has the characteristics of high hardness, strong bonding force with substrate atoms, greatly improved wear resistance and the like.
4. The coating provided by the invention improves the wear resistance of the surface of the titanium alloy, and simultaneously continues the advantage of light weight.
5. The invention has lower cost.
Drawings
FIG. 1 is a diagram of the interface morphology of the coating after plasma welding cladding preparation.
FIG. 2 is a graph of the volumetric wear rate per unit time for a frictional wear test on a single sample.
FIG. 3 is a graph showing the trend of microhardness of the cross section of the coating.
Detailed Description
In a specific embodiment, the TC4 titanium alloy Al-Si flexible package wear-resistant coating and the preparation method thereof select Al-Si alloy powder, and a planetary rapid grinding machine is selected for mixing the Al powder and the Si powder, wherein the granularity range of the Al powder and the Si powder is 100-mesh and 120-mesh, the powder mixing rotation speed is 120r/min, and the powder mixing time is 120 min; carrying out plasma welding cladding on a titanium alloy substrate by adopting a plasma welding machine and a synchronous powder feeder, wherein the welding current is 60A-75A, the powder feeding flow is 3.2-3.81 atm Nl/min, the rotating speed of the powder feeder is 12-18r/min, the argon flow is 1.3-1.7L/min, the ion flow is 0.8-1.21 atm Nl/min, and an Al-Si wear-resistant coating is prepared by welding cladding on the titanium alloy substrate, and the thickness of the wear-resistant coating is 0-5 mm; the coating is organized into a primary Si and (alpha + Si) eutectic structure, and the interface bonding layer of the coating and the substrate is a Ti-Al series intermetallic compound. Si is uniformly distributed in the coating, and the mass percentage of Si element in the coating is 15-35 wt%. The coating has the advantages of low porosity, low alloy linear shrinkage, low thermal expansion coefficient, good compatibility with a matrix, good bonding force, better wear resistance and coating stability, and can well solve the problem of wear resistance of the titanium alloy.
The coating and the substrate completely show metallurgical bonding, the microhardness of the surface of the cladding layer is lower and is about 90-120HV, and the coating still shows good friction and wear resistance which is 3-10 times that of the titanium alloy substrate; the coating-matrix interface area shows higher hardness, the highest microhardness can reach more than 700HV, and extremely strong friction and wear resistance is obtained in the area.
In the invention, the plasma welding equipment is a multifunctional plasma welding machine which is DML-V02BD produced by Shanghai Duoliao industry Co.
In the invention, the titanium alloy matrix is a Ti6Al4V matrix.
In order to make the technical solution and advantages of the present invention more clear, the following detailed description is given with reference to specific embodiments.
Example 1
Al-15Si alloy powder with the granularity of 100 meshes is filled into a synchronous powder feeder of a plasma welding machine, a welding cladding coating is carried out on the surface of TC4 titanium alloy by the plasma welding machine in a plasma continuous welding mode, the welding current is 65A, and the powder feeding airflow is 3.51 atm Nl/min. If a plurality of welding processes are carried out, the slag removal treatment is carried out on the finished cladding layer before the next cladding layer is welded, so that the surface of the cladding layer is smooth and clean. When welding cladding is carried out, the superposition of the next cladding layer and the previous cladding layer is not less than 1/2. Thus preparing the target Al-Si flexible package wear-resistant coating.
As shown in figure 1, the coating is divided into primary Si and (alpha + Si) eutectic structures, and metallurgical bonding is presented between the coating and the substrate. The primary silicon is uniformly distributed in the coating and is used as the support of the alpha-Al soft phase to play a role in wear resistance. Under the condition of low content ratio of Si alloy powder, eutectic structures are not obvious, and the coating shows good wear resistance. A single sample is taken for carrying out a plurality of times of friction and wear tests under the test conditions of dry friction and plowing wear. The material Q235 steel was chosen as the friction pair material according to the known coating structure composition. The result shows that the wear resistance of the TC4 titanium alloy Al-Si flexible packaging wear-resistant coating is 3-10 times that of the matrix TC4 titanium alloy; and the transition region of the coating and the matrix has higher wear resistance, so that the wear resistance of the surface of the TC4 titanium alloy is greatly improved, and the metallurgical bonding transition region provides effective protection for the titanium alloy matrix, as shown in FIG. 2. The technological parameters are the optimal cladding technological parameters of the invention.
Example 2
Al-25Si alloy powder with the granularity of 100 meshes is filled into a synchronous powder feeder of a plasma welding machine, a welding cladding coating is carried out on the surface of TC4 titanium alloy by the plasma welding machine in a plasma continuous welding mode, the welding current is 60A, the powder feeding flow is 3.51 atm Nl/min, the target Al-Si flexible packaging wear-resistant coating is prepared, and silicon is uniformly distributed in the coating.
The TC4 titanium alloy Al-Si flexible packaging wear-resistant coating disclosed by the invention is shown in figure 3, and microhardness analysis is carried out on the cross section of the coating. In the coating layer, α -Al is a main component of the coating layer, and the hardness is 60-100HV, while the reason why the texture high hardness is exhibited in the transition region is that Ti-Al based intermetallic compounds, which are generated in the interface bonding region between the coating layer and the substrate, have a characteristic of high hardness.
Example 3
Al-15Si alloy powder with the granularity of 100 meshes is filled into a synchronous powder feeder of a plasma welding machine, a welding cladding coating is carried out on the surface of TC4 titanium alloy by the plasma welding machine in a plasma continuous welding mode, the welding current is 60A, the powder feeding flow is 3.51 atm Nl/min, the target Al-Si flexible packaging wear-resistant coating is prepared, and silicon is uniformly distributed in the coating. As a result, the wear resistance of the coating was found to be 3 times that of the titanium alloy of the substrate TC 4.
Example 4
Al-35Si alloy powder with the granularity of 120 meshes is filled into a synchronous powder feeder of a plasma welding machine, a welding cladding coating is carried out on the surface of TC4 titanium alloy by the plasma welding machine in a plasma continuous welding mode, the welding current is 75A, and the powder feeding airflow is 3.81 atm Nl/min, so that the target Al-Si flexible packaging wear-resistant coating is prepared. The cladding current obtains the maximum value of the process parameters and is matched with Al-Si alloy powder with high Si content, and the wear resistance of the obtained cladding layer is reduced to a certain extent compared with the wear resistance of the coating obtained by the optimal process parameters. Cladding is carried out under the upper limit current value, so that a molten pool has better fluidity, Si element sinks to the bottom of the molten pool more in the cladding process to be solidified and crystallized, the content of the Si element on the surface of the coating is reduced, further the primary silicon structure is reduced, further the wear resistance of the coating is reduced, and the wear resistance of the coating is still far higher than that of a titanium alloy matrix.
Example 5
Al-15Si alloy powder with the granularity of 100 meshes is filled into a synchronous powder feeder of a plasma welding machine, a welding cladding coating is carried out on the surface of TC4 titanium alloy by the plasma welding machine in a plasma continuous welding mode, the welding current is 60A, the powder feeding flow is 3.21 atm Nl/min, and the target Al-Si flexible packaging wear-resistant coating is prepared. When the low-current and low-content alloy powder is used for cladding, the flow rate of the powder feeding gas is correspondingly reduced for matching, and the wear resistance of the coating obtained by the process is reduced to a certain extent compared with that of the coating with the optimal process parameters in the embodiment 1, but better wear resistance is still obtained. The lower welding heat input is beneficial to the structure grain refinement of the cladding coating. Although the primary Si structure obtained by the process is reduced, most Si elements participate in Al-Si eutectic reaction to form a eutectic beta-Si structure, the eutectic beta-Si structure is very beneficial to improving the wear resistance, and the eutectic beta-Si structure distributed on the alpha-Al soft matrix can enhance the stability of the coating and serve as the support of the soft matrix, so that the good wear resistance is further shown.
Example 6
Selecting Al-Si alloy powder, and selecting a planetary rapid grinding machine to mix Al powder and Si powder, wherein the granularity of the Al powder and the Si powder is 120 meshes, the powder mixing rotation speed is 120r/min, and the powder mixing time is 120 min; carrying out plasma welding cladding on a titanium alloy substrate by adopting a plasma welding machine and a synchronous powder feeder, wherein the welding current is 65A, the powder feeding flow is 3.51 atm Nl/min, the rotating speed of the powder feeder is 12r/min, the argon flow is 1.3L/min, and the ionic flow is 0.81atm Nl/min, and an Al-Si wear-resistant coating is prepared on the titanium alloy substrate by welding cladding, and the thickness of the wear-resistant coating is 1 mm; the coating is organized into a primary Si and (alpha + Si) eutectic structure, and the interface bonding layer of the coating and the substrate is a Ti-Al series intermetallic compound. Si is uniformly distributed in the coating, and the mass percentage of Si element in the coating is 20 wt%. The coating and the substrate completely show metallurgical bonding, the microhardness of the surface of the cladding layer is lower and is about 90-120HV, and the coating still shows good friction and wear resistance which is 3-10 times that of the titanium alloy substrate; the coating-matrix interface area shows higher hardness, the highest microhardness can reach more than 700HV, and extremely strong friction and wear resistance is obtained in the area.
Example 7
Selecting Al-Si alloy powder, and selecting a planetary rapid grinding machine to mix Al powder and Si powder, wherein the granularity of the Al powder and the Si powder is 100 meshes, the powder mixing rotation speed is 120r/min, and the powder mixing time is 120 min; carrying out plasma welding cladding by adopting a plasma welding machine and a synchronous powder feeder, wherein the welding current is 65A, the powder feeding flow is 3.71 atm Nl/min, the rotating speed of the powder feeder is 18r/min, the argon flow is 1.7L/min, the ionic gas flow is 1.21atm Nl/min, and an Al-Si wear-resistant coating is prepared on the titanium alloy substrate by welding cladding, and the thickness of the wear-resistant coating is 1 mm; the coating is organized into a primary Si and (alpha + Si) eutectic structure, and the interface bonding layer of the coating and the substrate is a Ti-Al series intermetallic compound. Si is uniformly distributed in the coating, and the mass percentage of Si element in the coating is 15 wt%. The coating and the substrate completely show metallurgical bonding, the microhardness of the surface of the cladding layer is lower and is about 90-120HV, and the coating still shows good friction and wear resistance which is 3-10 times that of the titanium alloy substrate; the coating-matrix interface area shows higher hardness, the highest microhardness can reach more than 700HV, and extremely strong friction and wear resistance is obtained in the area.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (7)

1.一种钛合金软包装耐磨涂层,其特征在于:涂层的组织成分为初生Si组织和(α+Si)共晶组织,涂层与基体结合界面组织成分为初生Si组织和Ti-Al系金属间化合物。1. A wear-resistant coating for flexible packaging of titanium alloys, characterized in that: the organizational components of the coating are primary Si structure and (α+Si) eutectic structure, and the combined interface structure components of the coating and the substrate are primary Si structure and Ti- Al-based intermetallic compounds. 2.根据权利要求1所述的一种钛合金软包装耐磨涂层,其特征在于:所述涂层与基体完全呈现冶金过渡结合,熔覆涂层表面显微硬度为90-120HV,耐摩擦磨损性能是基体的3-10倍;涂层-基体界面区域硬度为360-700HV。2. A kind of wear-resistant coating for titanium alloy flexible packaging according to claim 1, characterized in that: the coating and the substrate completely present a metallurgical transition bond, the surface microhardness of the cladding coating is 90-120HV, and the friction resistance is 90-120HV. The wear performance is 3-10 times that of the substrate; the hardness of the coating-substrate interface area is 360-700HV. 3.制备权利要求1所述的一种钛合金软包装耐磨涂层的方法,其特征在于包括下述步骤:选用Al-Si合金粉末,采用等离子焊机与同步送粉器进行等离子焊接熔覆,焊接电流为60A-75A,送粉气流量为3.2-3.8 1atm Nl/min,对钛合金基体进行等离子焊接熔覆,形成涂层。3. the method for preparing a kind of titanium alloy flexible packaging wear-resistant coating according to claim 1 is characterized in that comprising the following steps: select Al-Si alloy powder for selection, adopt plasma welding machine and synchronous powder feeder to carry out plasma welding cladding , the welding current is 60A-75A, the powder feeding gas flow is 3.2-3.8 1atm Nl/min, and the titanium alloy substrate is plasma welded and clad to form a coating. 4.根据权利要求4所述的一种钛合金软包装耐磨涂层的制备方法,其特征在于:所述的Al-Si合金粉末进行同步送粉焊接熔覆,其中Si粉的质量分数占比为15%-35%。4 . The method for preparing a wear-resistant coating for titanium alloy flexible packaging according to claim 4 , wherein the Al-Si alloy powder is synchronously fed by powder feeding for welding and cladding, wherein the mass fraction of the Si powder accounts for 4 . 15%-35%. 5.根据权利要求4所述的一种钛合金软包装耐磨涂层的制备方法,其特征在于:所述的Al-Si合金粉末选用100-120目的Al粉与Si粉,采用行星式球磨机经过120分钟充分研磨,混粉转速120r/min,得到Al-Si合金粉末。5. the preparation method of a kind of titanium alloy flexible packaging wear-resistant coating according to claim 4, is characterized in that: described Al-Si alloy powder selects 100-120 purpose Al powder and Si powder, adopts planetary ball mill to pass through The powder was fully ground for 120 minutes, and the powder mixing speed was 120 r/min to obtain Al-Si alloy powder. 6.根据权利要求4所述的一种钛合金软包装耐磨涂层的制备方法,其特征在于:所述的等离子焊机与同步送粉器中,送粉器转速为12-18r/min,氩气的流量为1.3-1.7L/min,离子气流量为0.8-1.2 1atm Nl/min。6. The method for preparing a wear-resistant coating for titanium alloy flexible packaging according to claim 4, characterized in that: in the plasma welding machine and the synchronous powder feeder, the rotating speed of the powder feeder is 12-18r/min, The flow rate of argon gas is 1.3-1.7L/min, and the flow rate of ion gas is 0.8-1.2 1atm Nl/min. 7.根据权利要求4所述的一种钛合金软包装耐磨涂层的制备方法,其特征在于:所述的等离子焊接熔覆步骤,若进行多道焊工艺则下一道熔覆层进行焊接之前对已完成的熔覆层进行清渣处理,保证涂层表面光洁;进行焊接熔覆时,下一道熔覆层与上一道熔覆层重合不小于1/2。7. the preparation method of a kind of titanium alloy flexible packaging wear-resistant coating according to claim 4, it is characterized in that: described plasma welding cladding step, if carry out multi-pass welding process, before the next cladding layer is welded The completed cladding layer shall be cleaned by slag treatment to ensure that the surface of the coating is smooth and clean; during welding and cladding, the overlap between the next cladding layer and the previous cladding layer shall not be less than 1/2.
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CN114645272A (en) * 2022-04-07 2022-06-21 南通德邦新材料科技有限公司 Plasma alloy powder cladding equipment
CN115786905A (en) * 2022-11-16 2023-03-14 辽宁石油化工大学 A wear-resistant coating of Al-Si-V-Nb titanium alloy containing an oxygen-free region and its preparation method
CN115821188A (en) * 2022-12-21 2023-03-21 重庆宗申发动机制造有限公司 Titanium alloy with coating and preparation method thereof

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