CN114507893B - Electrolyte for high-hardness wear-resistant micro-arc oxidation coating on tantalum alloy surface and preparation method thereof - Google Patents
Electrolyte for high-hardness wear-resistant micro-arc oxidation coating on tantalum alloy surface and preparation method thereof Download PDFInfo
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- 235000006481 Colocasia esculenta Nutrition 0.000 claims description 3
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- 229910052782 aluminium Inorganic materials 0.000 description 4
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Abstract
The invention belongs to the technical field of alloy surface treatment, and provides a high-hardness wear-resistant micro-arc oxidation coating electrolyte for a tantalum alloy surface and a preparation method thereof, which are used for effectively improving the hardness and wear resistance of a micro-arc oxidation coating. According to the invention, the hard phase decomposer is added into the electrolyte, and the hard phase decomposer is utilized to decompose at high temperature to obtain hard phase particles which are then integrated into the coating, so that the hardness of the micro-arc oxidation coating is improved, and the tribological property of the coating is improved; meanwhile, the preparation method for obtaining the micro-arc oxidation coating based on the electric parameter matching design of the electrolyte adopts a sectional pressurizing mode to gradually increase the oxidation voltage, so as to adjust the micro-arc oxidation reaction intensity, control the growth rate of the tantalum alloy micro-arc oxidation coating, avoid the coating from generating a large number of microcracks due to overgrowth and damage the structure and compactness of the coating; the micro-arc oxidation coating prepared finally has the advantages of small surface porosity, less cracks, compact structure, coating hardness higher than 800HV, and the dry friction coefficient between the coating and the WC ball is reduced from 0.75 to 0.3-0.4.
Description
Technical Field
The invention belongs to the technical field of alloy surface treatment, relates to a tantalum alloy surface treatment technology, and particularly provides a high-hardness wear-resistant micro-arc oxidation coating electrolyte for a tantalum alloy surface and a preparation method thereof.
Background
Tantalum is a rare refractory metal among the nonferrous metals, with a melting point of 2996 ℃ next to tungsten and rhenium metals. Tantalum has very stable chemical property at normal temperature and only reacts with hydrofluoric acid and acid solution containing fluoride ions. The tantalum alloy has excellent properties such as high density, high strength, high temperature resistance, corrosion resistance and the like, and is widely applied to the fields such as aerospace engines, chemical corrosion, atomic energy industry and the like, particularly high temperature corrosion and the like, and the severe and complex environments thereof; however, the hardness of tantalum alloys is relatively low, about 330HV, limiting the use of tantalum alloys in a wearing environment. When the tantalum alloy is applied as a connecting piece, relative friction movement is inevitably generated between the tantalum alloy and an assembling contact material; the prior literature also mentions that the phenomenon of high friction coefficient exists between the tantalum alloy and the assembly material, the surface states of the tantalum alloy and the assembly workpiece are directly influenced, serious friction and abrasion are generated, and the problems of energy waste, shortened service life and the like are further caused.
In order to improve the service effect, the tantalum alloy is subjected to surface modification treatment and then put into use; the surface coating technique can be used to improve the tribological properties of the tantalum alloy surface, achieving low friction of the tantalum alloy part with adjacent parts. Current tantalum alloy surface treatment techniques include electroplating, vapor deposition, micro-arc oxidation, and the like; the tantalum alloy has excellent corrosion resistance, difficult treatment before electroplating and lower plating binding force; the vapor deposition process is complex and the cost is high; the micro-arc oxidation process mainly relies on the matching adjustment of electrolyte and electric parameters, and under the action of instantaneous high temperature and high pressure generated by arc discharge, a modified ceramic coating which takes matrix metal oxide as a main component and is assisted by electrolyte component grows on the surfaces of valve metals such as aluminum, magnesium, titanium and the like and alloys thereof; the micro-arc oxidation can perform in-situ ceramic transformation on tantalum and the alloy thereof, the process is simpler, and the coating has high hardness and good wear resistance, corrosion resistance and insulation performance.
At present, the coating surface prepared on the surface of the tantalum alloy by the common micro-arc oxidation technology is rough and porous, has a large number of microcracks under the action of residual thermal stress, influences the bonding force between the coating and a matrix, reduces the surface hardness of the coating, and shows a high friction coefficient in the friction process, so that the application of the tantalum alloy micro-arc oxidation coating in a wearing environment is greatly limited. The thickness, hardness and other properties of the micro-arc oxidation coating are affected by energy parameters, matrix alloy elements, solution characteristics and other factors, while the composition and the proportion of the electrolyte are critical to the influence of the surface morphology and the coating performance of the micro-arc oxidation coating.
Disclosure of Invention
Aiming at a plurality of problems existing in the prior art, the invention provides a tantalum alloy surface high-hardness wear-resistant micro-arc oxidation coating electrolyte and a tantalum alloy surface high-hardness wear-resistant micro-arc oxidation coating preparation method based on the electrolyte; according to the invention, the water-soluble hard phase decomposer is introduced into the electrolyte, and the hard phase decomposer is utilized to decompose in the high Wen Weihu oxidation process to generate hard phase particles and is blended into the micro-arc oxidation coating by means of the configuration of the electrolyte and the electric parameters, so that the hardness and the wear resistance of the micro-arc oxidation coating are effectively improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
an electrolyte for a high-hardness wear-resistant micro-arc oxidation coating on a tantalum alloy surface, which comprises the following components: main film forming agent, pH regulator and additive, wherein the main film forming agent is Na 3 PO 4 The pH regulator is NaOH; characterized in that the additive comprises: the film layer thickening agent, the arc inhibitor and the hard phase decomposer, wherein the hard phase decomposer is one or more of soluble aluminum salt, titanium salt, zirconium salt and fluorine salt which can be decomposed into hard phase particles.
Further, the concentration of the main film forming agent is 5-30 g/L, the concentration of the pH regulator is 5-10 g/L, the concentration of the film thickening agent is 1-10 g/L, the concentration of the arc inhibitor is 1-10 g/L, and the concentration of the hard phase decomposer is 5-30 g/L; the solvent is water.
Further, the aluminum salt is NaAlO 2 、KAlO 2 The titanium salt is Na 2 TiO 3 、K 2 TiO 3 The zirconium salt is Na 2 ZrO 3 、K 2 ZrO 3 The fluoride salt is Na 2 TiF 6 、K 2 TiF 6 、(NH 4 ) 2 TiF 6 。
Further toThe film layer thickening agent is NaF, KF, na 2 One or more of S.
Further, the arc inhibitor is disodium ethylenediamine tetraacetate (EDTA-2 Na) or hexamethylenetetramine (C) 6 H 12 N 4 ) Glycerol (C) 3 H 8 O 3 ) One or more of the following.
A preparation method of a high-hardness wear-resistant micro-arc oxidation coating on the surface of a tantalum alloy is characterized by comprising the following steps: preparing the electrolyte of the high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy, placing the electrolyte in a stainless steel electrolytic tank, and setting electric parameters: and adopting a constant-voltage bipolar working mode, wherein the voltage is 100-550V, the discharge frequency is 400-1000 Hz, the positive and negative duty ratio is 10-50%, the oxidation time is 10-60 min, controlling the temperature of the electrolyte to be lower than 40 ℃, connecting a tantalum alloy sample to a conducting rod, immersing the tantalum alloy sample in the electrolyte to serve as an anode, and carrying out micro-arc oxidation treatment by using a stainless steel electrolytic tank as a cathode to obtain the high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy.
Further, the micro-arc oxidation treatment is performed in a sectional pressurizing mode: after micro-arc oxidation arcing, taking 10V as a rising step, rising step by step for 1-5 times on the basis of initial voltage until reaching target voltage, and oxidizing for 5-15 min under each voltage; it should be noted that: setting the voltage value in the electric parameter as the target voltage, and determining the initial voltage after the target voltage and the step-up times are determined.
The beneficial effects of the invention are as follows:
the invention provides a tantalum alloy surface high-hardness wear-resistant micro-arc oxidation coating electrolyte and a tantalum alloy surface high-hardness wear-resistant micro-arc oxidation coating preparation method based on the electrolyte, and the method has the following advantages:
1) According to the invention, the hard phase decomposer is added into the electrolyte, and the hard phase decomposer is utilized to decompose at high temperature to obtain hard phase particles which are then integrated into the coating, so that the hardness of the micro-arc oxidation coating is improved, and the tribological property of the coating is improved; for example, naAlO 2 Reacts with the micro-arc oxidation product on the surface of the tantalum alloy at high temperature to obtain hard phase AlTaO 3 Composite oxide and Al 2 O 3 KAlO is adopted 2 The same effect is achieved; in addition, compared with the method that hard phase particles are directly added into the electrolyte, the method can avoid the problem of uneven coating caused by particle aggregation and sedimentation by utilizing the corresponding salt thermal decomposition of the hard phase particles to generate the hard phase;
2) The method adopts a mode of adding a specified voltage and increasing the voltage in a sectional way to gradually increase the oxidation voltage, so as to adjust the micro-arc oxidation reaction intensity, control the growth rate of the tantalum alloy micro-arc oxidation coating, avoid the coating from generating a large number of microcracks due to overgrowth and damage the structure and compactness of the coating;
3) The micro-arc oxidation coating prepared by the method has the advantages of small surface porosity, less cracks, compact structure, coating hardness higher than 800HV, and the dry friction coefficient between the coating and the WC ball is reduced from 0.75 to 0.3-0.4;
4) The high-hardness wear-resistant coating of the tantalum alloy prepared by the method is very uniform, tightly combined with the matrix, simple in preparation method, mild in reaction condition and low in cost, and the method is beneficial to expanding the application of the tantalum alloy in a wear environment.
Drawings
Fig. 1 is a SEM photograph of the surface morphology of the high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy prepared in example 1.
Fig. 2 is a SEM photograph of the cross-sectional morphology of the high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy prepared in example 1.
FIG. 3 is a sectional morphology XRD phase composition diagram of a high-hardness wear-resistant micro-arc oxidation coating on the surface of a tantalum alloy prepared in example 1.
Detailed Description
The following examples of the present invention are described in detail, and are implemented on the premise of the technical proposal of the present invention, and detailed implementation manners and specific operation procedures are given, but the protection scope of the present invention is not limited to the following examples.
Example 1
The embodiment provides an electrolyte and a preparation method of a high-hardness wear-resistant micro-arc oxidation coating on the surface of a tantalum alloy based on the electrolyte, and the preparation method comprises the following specific steps:
step 1. Sample pretreatment (pre-cleaning): tantalum alloy (TaW 12) sheet samples of 20mm x 22mm x 2mm were carefully sanded sequentially with No. 320, no. 600, no. 1000, no. 2000 sandpaper to remove cutting marks and oxide films on and around the surface; sequentially cleaning the surfaces of the surfaces for 10-20 min in alcohol and distilled water respectively by using an ultrasonic cleaner so as to remove stains on the surfaces; finally, drying with cold air for standby;
step 2, preparing electrolyte: the reagents were weighed according to the following solute concentrations, and then dissolved in 5L of high-purity water (double distilled water) in order of 20g/L Na 3 PO 4 2g/L NaOH, 1g/L NaF, 2g/L EDTA-2Na, 20g/L NaAlO 2 Stirring to promote the uniform dispersion and full dissolution of the solute, and transferring the solute into a micro-arc oxidation stainless steel electrolytic tank after the solute is completely dissolved;
step 3, setting electric parameters: adopting a constant-voltage bipolar working mode, wherein the discharge frequency is 500Hz, the positive and negative duty ratio is 30%, setting the voltage to 460V, oxidizing for 5min, and then increasing the voltage to 470V and oxidizing for 10min;
step 4, micro-arc oxidation: starting circulating cooling water, controlling the temperature of the electrolyte to be lower than 40 ℃, connecting a tantalum alloy sample to a conducting rod through an aluminum wire, immersing the tantalum alloy sample in the electrolyte to serve as an anode, and starting a bidirectional pulse power supply to perform micro-arc oxidation treatment by using a stainless steel electrolytic tank as a cathode;
step 5, post-treatment: and (3) flushing the coating sample subjected to the micro-arc oxidation treatment by using distilled water, removing electrolyte remained on the surface, and drying by using cold air to obtain the high-hardness wear-resistant micro-arc oxidation coating on the tantalum alloy surface.
The high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy prepared by the embodiment is tested, the SEM (scanning electron microscope) picture of the surface appearance is shown in figure 1, the SEM picture of the section appearance is shown in figure 2, the XRD phase composition diagram of the section appearance is shown in figure 3, and the micro-arc oxidation surface coating is very uniform, has no microcrack, has no air hole and has no exposed alloy, so that the micro-arc oxidation coating has ideal effect; as can be seen from FIG. 2, the micro-arc oxidation coating is thinner (about 20 um), has uniform thickness, good adhesion effect, high compactness, high strength, small surface porosity, no crack and compact structure; from FIG. 3, it can be seen that micro-arc oxidation coating is generatedTrace of AlTaO 3 Composite oxide and trace amount of Al 2 O 3 It is the formation of these two species that gives tantalum alloy surfaces with high hardness and wear resistance.
The thickness of the high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy obtained in the embodiment is about 21 mu m, the hardness reaches 1200HV, and the dry friction coefficient between the tantalum alloy and the WC ball under 4N load is 0.32.
Example 2
The embodiment provides an electrolyte and a preparation method of a high-hardness wear-resistant micro-arc oxidation coating on the surface of a tantalum alloy based on the electrolyte, and the preparation method comprises the following specific steps:
step 1. Sample pretreatment (pre-cleaning): tantalum alloy (TaW 12) sheet samples of 20mm x 22mm x 2mm were carefully sanded sequentially with No. 320, no. 600, no. 1000, no. 2000 sandpaper to remove cutting marks and oxide films on and around the surface; sequentially cleaning the surfaces of the surfaces for 10-20 min in alcohol and distilled water respectively by using an ultrasonic cleaner so as to remove stains on the surfaces; finally, drying with cold air for standby;
step 2, preparing electrolyte: the reagents were weighed according to the following solute concentrations, and then dissolved in 5L of high-purity water (double distilled water) in order of 20g/L Na 3 PO 4 2g/L NaOH, 1g/L NaF, 2g/L EDTA-2Na, 20g/L NaAlO 2 Stirring to promote the uniform dispersion and full dissolution of the solute, and transferring the solute into a micro-arc oxidation stainless steel electrolytic tank after the solute is completely dissolved;
step 3, setting electric parameters: adopting a constant-voltage bipolar working mode, wherein the discharge frequency is 500Hz, the positive and negative duty ratio is 10%, setting the voltage to 460V, oxidizing for 5min, and then increasing the voltage to 470V and oxidizing for 10min; increasing the voltage to 480V and oxidizing for 10min;
step 4, micro-arc oxidation: starting circulating cooling water, controlling the temperature of the electrolyte to be lower than 40 ℃, connecting a tantalum alloy sample to a conducting rod through an aluminum wire, immersing the tantalum alloy sample in the electrolyte to serve as an anode, and starting a bidirectional pulse power supply to perform micro-arc oxidation treatment by using a stainless steel electrolytic tank as a cathode;
step 5, post-treatment: and (3) flushing the coating sample subjected to the micro-arc oxidation treatment by using distilled water, removing electrolyte remained on the surface, and drying by using cold air to obtain the high-hardness wear-resistant micro-arc oxidation coating on the tantalum alloy surface. The high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy has the similar effect as in the embodiment 1.
The high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy obtained in the embodiment has a thinner thickness, is about 15 mu m, has a hardness of about 900HV, and has a dry friction coefficient with WC balls of 0.35 under a 4N load.
Example 3
The embodiment provides an electrolyte and a preparation method of a high-hardness wear-resistant micro-arc oxidation coating on the surface of a tantalum alloy based on the electrolyte, and the preparation method comprises the following specific steps:
step 1. Sample pretreatment (pre-cleaning): tantalum alloy (TaW 12) sheet samples of 20mm x 22mm x 2mm were carefully sanded sequentially with No. 320, no. 600, no. 1000, no. 2000 sandpaper to remove cutting marks and oxide films on and around the surface; sequentially cleaning the surfaces of the surfaces for 10-20 min in alcohol and distilled water respectively by using an ultrasonic cleaner so as to remove stains on the surfaces; finally, drying with cold air for standby;
step 2, preparing electrolyte: the reagents were weighed according to the following solute concentrations, and dissolved in 5L of high-purity water (double distilled water) in order of 10g/L Na 3 PO 4 2g/L NaOH, 1g/L NaF, 2g/L EDTA-2Na, 10g/L NaAlO 2 Stirring to promote the uniform dispersion and full dissolution of the solute, and transferring the solute into a micro-arc oxidation stainless steel electrolytic tank after the solute is completely dissolved;
step 3, setting electric parameters: adopting a constant-voltage bipolar working mode, wherein the discharge frequency is 500Hz, the positive and negative duty ratio is 50%, setting the designated voltage as 460V, and increasing the voltage to 470V for 10min after oxidizing the 460V for 5min; then the voltage is increased to 480V and oxidized for 10min; then the voltage is increased to 490V and oxidized for 10min; finally, the voltage is increased to 500V and oxidized for 10min;
step 4, micro-arc oxidation: starting circulating cooling water, controlling the temperature of the electrolyte to be lower than 40 ℃, connecting a tantalum alloy sample to a conducting rod through an aluminum wire, immersing the tantalum alloy sample in the electrolyte to serve as an anode, and starting a bidirectional pulse power supply to perform micro-arc oxidation treatment by using a stainless steel electrolytic tank as a cathode;
step 5, post-treatment: and (3) flushing the coating sample subjected to the micro-arc oxidation treatment by using distilled water, removing electrolyte remained on the surface, and drying by using cold air to obtain the high-hardness wear-resistant micro-arc oxidation coating on the tantalum alloy surface. The high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy still has the similar effect as in the embodiment 1.
The high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy obtained in the embodiment has the thickness of about 23 mu m, the hardness of about 860HV and the dry friction coefficient between the tantalum alloy and the WC ball under the 4N load of 0.30.
While the invention has been described in terms of specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the equivalent or similar purpose, unless expressly stated otherwise; all of the features disclosed, or all of the steps in a method or process, except for mutually exclusive features and/or steps, may be combined in any manner.
Claims (2)
1. A preparation method of a high-hardness wear-resistant micro-arc oxidation coating on the surface of a tantalum alloy is characterized by comprising the following steps: preparing high-hardness wear-resistant micro-arc oxidation coating electrolyte on the surface of the tantalum alloy, placing the electrolyte in a stainless steel electrolytic tank, and setting electric parameters: adopting a constant-voltage bipolar working mode, wherein the voltage is 100-550V, the discharge frequency is 400-1000 Hz, the positive and negative duty ratio is 10-50%, the oxidation time is 10-60 min, the temperature of electrolyte is controlled to be lower than 40 ℃, connecting a tantalum alloy sample to a conducting rod, immersing the tantalum alloy sample in the electrolyte to serve as an anode, and carrying out micro-arc oxidation treatment by using a stainless steel electrolytic tank as a cathode to obtain a high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy;
the high-hardness wear-resistant micro-arc oxidation coating electrolyte for the tantalum alloy surface comprises the following components: main film forming agent, pH regulator and additive, wherein the main film forming agent is Na 3 PO 4 The pH regulator is NaOH; the additive comprises: the film layer thickening agent, the arc inhibitor and the hard phase decomposer, wherein the hard phase decomposer is soluble aluminum salt which can be decomposed into hard phase particles, and the aluminum salt is NaAlO 2 、KAlO 2 The method comprises the steps of carrying out a first treatment on the surface of the The film layer thickening agent is NaF, KF, na 2 S, wherein the arc inhibitor is ethylenediamine tetraOne or more of disodium acetate, hexamethylenetetramine and glycerol;
the main film forming agent has a concentration of 5-30 g/L, the pH regulator has a concentration of 5-10 g/L, the film thickening agent has a concentration of 1-10 g/L, the arc inhibitor has a concentration of 1-10 g/L, the hard phase decomposer has a concentration of 5-30 g/L, and the solvent is water.
2. The method for preparing the high-hardness wear-resistant micro-arc oxidation coating on the surface of the tantalum alloy according to claim 1, wherein the micro-arc oxidation treatment is carried out in a sectional pressurizing mode: after micro-arc oxidation arcing, the step is carried out by taking 10V as a step-up step, the step-up is carried out for 1-5 times on the basis of initial voltage until reaching target voltage, and oxidation is carried out for 5-15 min under each voltage.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2046156C1 (en) * | 1992-05-21 | 1995-10-20 | Институт химии Дальневосточного отделения РАН | Electrolyte for deposition of coatings onto valve metals |
| WO2007090433A2 (en) * | 2006-02-09 | 2007-08-16 | Plus Orthopedics Ag | Purified oxides with novel morphologies formed from ti-alloys |
| CN102758234A (en) * | 2012-07-26 | 2012-10-31 | 西北工业大学 | Method for preparing aluminum alloy anti-corrosion layer and electrolyte used in method |
| CN103526262A (en) * | 2013-10-17 | 2014-01-22 | 赵全明 | Method for performing surface modification on tantalum and tantalum alloy and electrolyte used in method |
| RU2543659C1 (en) * | 2013-09-02 | 2015-03-10 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" | Method for production of composite metal-ceramic coating at valve metals and their alloys |
| CN104928742A (en) * | 2015-06-12 | 2015-09-23 | 中国科学院金属研究所 | MAX phase ceramic and composite material surface modification processing method thereof |
| CN109518254A (en) * | 2018-11-27 | 2019-03-26 | 中国船舶重工集团公司第七二五研究所 | A kind of microarc oxidation solution, titanium alloy high rigidity micro-arc oxidation films and preparation and application |
| CN109680266A (en) * | 2019-02-22 | 2019-04-26 | 吉林大学 | A kind of bioactive ceramic coating and preparation method thereof preparing tantalum atom doping in titanium alloy surface |
| CN110424038A (en) * | 2019-07-02 | 2019-11-08 | 山东农业工程学院 | Micro-arc oxidation electrolyte, differential arc oxidation film layer and the preparation method and application thereof |
-
2022
- 2022-01-14 CN CN202210040712.0A patent/CN114507893B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2046156C1 (en) * | 1992-05-21 | 1995-10-20 | Институт химии Дальневосточного отделения РАН | Electrolyte for deposition of coatings onto valve metals |
| WO2007090433A2 (en) * | 2006-02-09 | 2007-08-16 | Plus Orthopedics Ag | Purified oxides with novel morphologies formed from ti-alloys |
| CN102758234A (en) * | 2012-07-26 | 2012-10-31 | 西北工业大学 | Method for preparing aluminum alloy anti-corrosion layer and electrolyte used in method |
| RU2543659C1 (en) * | 2013-09-02 | 2015-03-10 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" | Method for production of composite metal-ceramic coating at valve metals and their alloys |
| CN103526262A (en) * | 2013-10-17 | 2014-01-22 | 赵全明 | Method for performing surface modification on tantalum and tantalum alloy and electrolyte used in method |
| CN104928742A (en) * | 2015-06-12 | 2015-09-23 | 中国科学院金属研究所 | MAX phase ceramic and composite material surface modification processing method thereof |
| CN109518254A (en) * | 2018-11-27 | 2019-03-26 | 中国船舶重工集团公司第七二五研究所 | A kind of microarc oxidation solution, titanium alloy high rigidity micro-arc oxidation films and preparation and application |
| CN109680266A (en) * | 2019-02-22 | 2019-04-26 | 吉林大学 | A kind of bioactive ceramic coating and preparation method thereof preparing tantalum atom doping in titanium alloy surface |
| CN110424038A (en) * | 2019-07-02 | 2019-11-08 | 山东农业工程学院 | Micro-arc oxidation electrolyte, differential arc oxidation film layer and the preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| A Decade of Progress on MAO-Treated Tantalum Surfaces: Advances and Contributions for Biomedical Applications;Luísa Fialho等;《nanomaterials》(第12期);1-35 * |
| 从钼矿中提取铼的工艺改进及研究进展;范小祥;刘玲;;中国钼业(第06期);29-31 * |
| 放电电压对钽表面微弧氧化陶瓷层抗氧化性能影响的研究;杨海彧;李争显;张雯;;材料导报(第S2期);450-452,478 * |
| 杨培霞等.《现代电化学表面处理专论》.哈尔滨工业大学出版社,2016,第168-173页. * |
| 钽表面微弧氧化陶瓷层的抗氧化性能;杨海彧等;《腐蚀与防护》;第36卷(第6期);563-568 * |
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