CN106637081A - Method for improving high-temperature-oxidation resistance of TC4 titanium alloy - Google Patents

Method for improving high-temperature-oxidation resistance of TC4 titanium alloy Download PDF

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Publication number
CN106637081A
CN106637081A CN201611102573.0A CN201611102573A CN106637081A CN 106637081 A CN106637081 A CN 106637081A CN 201611102573 A CN201611102573 A CN 201611102573A CN 106637081 A CN106637081 A CN 106637081A
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China
Prior art keywords
titanium alloy
alloy
temperature
oxidation
square
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Pending
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CN201611102573.0A
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Chinese (zh)
Inventor
冯长杰
蒋利民
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Nanchang Hangkong University
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Nanchang Hangkong University
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Priority to CN201611102573.0A priority Critical patent/CN106637081A/en
Publication of CN106637081A publication Critical patent/CN106637081A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—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
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C23C14/5853—Oxidation
    • 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
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • 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
    • 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
    • C25D11/04—Anodisation of aluminium or alloys based thereon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Provided is a method for improving high-temperature-oxidation resistance of TC4 titanium alloy. The method includes the steps that an aluminum coating with the thickness being 2-3 micrometers is deposited on the surface of the TC4 alloy through an arc ion plating technology and an aluminum target with the purity of more than 99.9wt%, and then the TC4 alloy with the aluminum coating on the surface is used as an anode at the room temperature and placed in a 100g/L sodium silicate solution so as to be subjected to micro-arc oxidation treatment for 20 minutes through a square-wave pulse power supply with the frequency of 1200 Hz and the duty ratio of 60%, wherein the square-wave pulse current density is 15 A/dm2, and during micro-arc oxidation, 304 stainless steel with the surface area 2-3 times that of the TC4 alloy is used as the cathode. An oxidized film mainly containing aluminum oxide and silicon oxide is produced on the surface of the TC4 titanium alloy, the oxidized film is high in bonding performance with the base body, namely the TC4 titanium alloy, and thus the oxidation temperature to which the TC4 titanium alloy can resist in air is increased to 800 DEG C from 500 DEGC. By means of the method, the high-temperature-oxidation resistance of the TC4 titanium alloy is remarkably improved, and the method is simple and can be widely applied.

Description

A kind of method of raising TC4 titanium alloy high temperature oxidation resistances
Technical field
The present invention relates to a kind of method of raising TC4 titanium alloy high temperature oxidation resistances.
Background technology
Arc ion plating (aip) is a kind of wide variety of surface protection coating technology, fast with sedimentation rate, film layer with The outstanding advantages such as matrix excellent bonding performance, the compactness height of coating, can prepare various coatings, as with good wear performance High rigidity titanium nitride coating, the aluminized coating with good atmospheric corrosion resistance etc., are industrially widely used.Differential arc oxidization technique is It is a kind of that directly in the new surface treatment technologies of the non-ferrous metal surface growth in situ ceramic membrane such as aluminium, magnesium, titanium, processing procedure is simple, It is environmental friendly, after process the advantages of film layer superior performance.
TC4 titanium alloys have excellent corrosion resistance, little density, high specific strength and preferable toughness and weldability etc. Number of advantages, in departments such as Aero-Space, petrochemical industry, shipbuilding, automobile, medicine extensively application is obtained for, but TC4 titaniums are closed Golden antioxygenic property is weaker, typically can be only applied to 500oIn the environment of below C, long-term work environment temperature is typically smaller than 400oC。
The content of the invention
Object of the present invention is to provide a kind of method for significantly improving TC4 titanium alloy resistance to high temperature oxidation, can make TC4 titaniums Alloy oxidation resistance temperature is by 500oC brings up to 800oC。
The present invention is achieved like this, and is first more than using arc ion plating (aip) and purity in TC4 alloy surfaces The aluminium target of 99.9wt.%, the aluminized coating after its surface deposition 2-3 micron, the main technologic parameters of arc ion plating aluminized coating For：Argon flow amount：200mL/min, target is direct：100mm, arc current 100A, substrate bias -200V, sedimentation time 2- 3min。
Then surface is carried into the TC4 alloys of aluminized coating as anode under room temperature, is placed on the sodium silicate solution of 100g/L In, usage frequency is 1200Hz, and dutycycle is that 60% square-wave pulse mao power source is processed 20 minutes, square wave pulsed current Density is 15A/dm2, used as negative electrode, its surface area is 2-3 times of TC4 alloys to 304 stainless steels during differential arc oxidation.
The solution have the advantages that：Oxygen of the present invention in the production of TC4 titanium alloy surfaces based on aluminum oxide and silica Change film, and high with matrix TC4 titanium alloys binding ability, make in TC4 titanium alloy air oxidation resistance temperature by 500oC brings up to 800oC.Invention significantly improves the high temperature oxidation resistance of TC4 titanium alloys, and side is simple, can extensively apply.
Description of the drawings
Fig. 1 TC4 titanium alloys are 500oThe macro morphology figure after 100h is aoxidized in C air.
500 after Fig. 2 TC4 titanium alloys are processed by the inventionoThe macro morphology figure after 100h is aoxidized in C air.
Fig. 3 TC4 titanium alloys are 800oThe macro morphology figure after 100h is aoxidized in C air.
800 after Fig. 4 TC4 titanium alloys are processed by the inventionoThe macro morphology figure after 100h is aoxidized in C air.
Specific embodiment
The present invention is elaborated with reference to embodiment and accompanying drawing：
Embodiment 1
In TC4 alloy surfaces aluminium target first using arc ion plating (aip) and purity more than 99.9wt.%, in its surface deposition The aluminized coating of 2.1 microns of thickness.TC4 specimen sizes are 20mm × 30mm × 2mm, thick through 1200# sand paper before arc ion plating Mill, removes the oxide skin on surface, and 3min is cleaned in ultrasonic cleaner with ethanol, and then electricity consumption dries up standby.Electric arc The main technologic parameters of Ion-Plated with Aluminum coating are：Argon flow amount：200mL/min, target diameter：100mm, arc current 100A, Substrate bias -200V, sedimentation time 2min.
Then surface is carried into the TC4 alloys of aluminized coating as anode under room temperature, is placed on the sodium silicate solution of 100g/L In, usage frequency is 1200Hz, and dutycycle is that 60% square-wave pulse mao power source is processed 20 minutes, square wave pulsed current Density is 15A/dm2, used as negative electrode, its surface area is 2-3 times of TC4 alloys to 304 stainless steels during differential arc oxidation.
Embodiment 2
In TC4 alloy surfaces aluminium target first using arc ion plating (aip) and purity more than 99.9wt.%, in its surface deposition The aluminized coating of 2.4 microns of thickness.TC4 specimen sizes are 20mm × 30mm × 2mm, thick through 1200# sand paper before arc ion plating Mill, removes the oxide skin on surface, and 3min is cleaned in ultrasonic cleaner with ethanol, and then electricity consumption dries up standby.Electric arc The main technologic parameters of Ion-Plated with Aluminum coating are：Argon flow amount：200mL/min, target diameter：100mm, arc current 100A, Substrate bias -200V, sedimentation time 2.5min.
Then surface is carried into the TC4 alloys of aluminized coating as anode under room temperature, is placed on the sodium silicate solution of 100g/L In, usage frequency is 1200Hz, and dutycycle is that 60% square-wave pulse mao power source is processed 20 minutes, square wave pulsed current Density is 15A/dm2, used as negative electrode, its surface area is 2-3 times of TC4 alloys to 304 stainless steels during differential arc oxidation.
Embodiment 3
In TC4 alloy surfaces aluminium target first using arc ion plating (aip) and purity more than 99.9wt.%, in its surface deposition The aluminized coating of 2.9 microns of thickness.TC4 specimen sizes are 20mm × 30mm × 2mm, thick through 1200# sand paper before arc ion plating Mill, removes the oxide skin on surface, and 3min is cleaned in ultrasonic cleaner with ethanol, and then electricity consumption dries up standby.Electric arc The main technologic parameters of Ion-Plated with Aluminum coating are：Argon flow amount：200mL/min, target diameter：100mm, arc current 100A, Substrate bias -200V, sedimentation time 3min.
Then surface is carried into the TC4 alloys of aluminized coating as anode under room temperature, is placed on the sodium silicate solution of 100g/L In, usage frequency is 1200Hz, and dutycycle is that 60% square-wave pulse mao power source is processed 20 minutes, square wave pulsed current Density is 15A/dm2, used as negative electrode, its surface area is 2-3 times of TC4 alloys to 304 stainless steels during differential arc oxidation.

Claims (1)

1. a kind of method of raising TC4 titanium alloy high temperature oxidation resistances, methods described for first using arc ion plating (aip) and Aluminium target of the purity more than 99.9wt.%, first deposits the thick aluminized coating of 2-3 microns, then by table under room temperature in TC4 alloy surfaces Used as anode, in being placed on the sodium silicate solution of 100g/L, usage frequency is 1200Hz to TC4 alloys of the face with aluminized coating, is accounted for Sky is processed 20 minutes than the square-wave pulse power source differential arc oxidation for 60%, and square wave pulsed current density is 15A/dm2, differential arc oxidation When 304 stainless steels as negative electrode, its surface area is 2-3 times of TC4 alloys.
CN201611102573.0A 2016-12-05 2016-12-05 Method for improving high-temperature-oxidation resistance of TC4 titanium alloy Pending CN106637081A (en)

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Application Number Priority Date Filing Date Title
CN201611102573.0A CN106637081A (en) 2016-12-05 2016-12-05 Method for improving high-temperature-oxidation resistance of TC4 titanium alloy

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112301400A (en) * 2020-11-04 2021-02-02 西安赛福斯材料防护有限责任公司 Preparation method of hard protection micro-arc oxidation film layer on surface of titanium alloy ball valve

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
卜彤等: "多弧离子镀铝工艺对TC4钛合金微弧氧化膜结构及性能的影响", 《企业技术开发》 *
陆峰等: "《航空材料环境试验及表面防护技术》", 31 December 2012, 北京：国防工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112301400A (en) * 2020-11-04 2021-02-02 西安赛福斯材料防护有限责任公司 Preparation method of hard protection micro-arc oxidation film layer on surface of titanium alloy ball valve
CN112301400B (en) * 2020-11-04 2023-06-20 西安赛福斯材料防护有限责任公司 Preparation method of hard protection micro-arc oxidation film layer on surface of titanium alloy ball valve

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