CN101899631A - Method for modifying high-wettability coating on surface of metal-based compound material reinforcement - Google Patents

Method for modifying high-wettability coating on surface of metal-based compound material reinforcement Download PDF

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Publication number
CN101899631A
CN101899631A CN 201010242048 CN201010242048A CN101899631A CN 101899631 A CN101899631 A CN 101899631A CN 201010242048 CN201010242048 CN 201010242048 CN 201010242048 A CN201010242048 A CN 201010242048A CN 101899631 A CN101899631 A CN 101899631A
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coating
metal
magnesium
reinforcement
pure magnesium
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CN101899631B (en
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王文广
谢禹钧
张国福
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Liaoning Shihua University
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Liaoning Shihua University
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Abstract

The invention discloses a method for modifying a high-wettability coating on the surface of a metal-based compound material reinforcement. The method comprises the following steps of: 1, by a common coating preparation method, forming a metal oxide coating, of which reducibility is lower than that of magnesium, on the surface of the reinforcement; 2, and placing the reinforcement coated with the metal oxide coating and pure magnesium in a vacuum furnace in a way of placing the pure magnesium on the bottom of the furnace and placing the reinforcement above the pure magnesium, vacuum-pumping the furnace, keeping the vacuum degree below 10Pa, heating the furnace to 600 to700 DEG C, and keeping the temperature for 5 to 60 minutes so as to allow the magnesium steam and the metal oxide coating on the surface of the reinforcement to undergo an oxidation-reduction reaction to generate a compound layer formed by an inner layer made of compounds and an outer layer made of reduced metal. The method has the advantages of simple and controllable process, low equipment requirements, low cost, wide application range, high mechanical and physical properties and the like.

Description

A kind of metal-base composites strengthens method for modifying high-wettability coating on surface
One, technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of metal-base composites and strengthen method for modifying high-wettability coating on surface.
Two, background technology
Material is the basic substance and the guide of social progress.Material property has been proposed more and more higher, more and more tighter and increasing requirement.In many aspects, traditional single-material more and more can not satisfy actual needs.Matrix material is a kind of multiphase solid material that is formed by two or more physics combinations of substances different with chemical property.Matrix material can be through design, promptly by raw-material selection, each moiety being distributed and the assurance of processing condition etc., makes the complementation of stock blend material advantage, thereby has presented outstanding over-all properties.Wherein, metal-base composites has high specific tenacity, specific modulus, high temperature resistant, wear-resistant and excellent physicals and mechanical properties such as thermal expansivity is little, good heat conductivity, more and more come into one's own, become the key areas of various countries' research in new high-tech exploitation.
In order to obtain the metal-base composites of excellent performance and dealing with various requirements, need a suitable interface, make to strengthen between body and the metallic matrix to have good physical chemistry and the consistency on the mechanics.Matrix is bad to the wettability that strengthens body in most of metal-base composites, and problem such as can cause the Composite Preparation difficulty, subsurface defect is many and interface bond strength is low must manage to improve.In addition, surface reaction in various degree all takes place in most metal-base composites in preparation process.Serious surface reaction will cause the damage that strengthens body and form the fragility interface and equate, and will be extremely harmful.In order to control the formation at surface reaction and inhibition fragility interface, must be optimized design to the interface, and adopt relative measures.Wherein, carrying out coating modified to the enhancing surface is practical way.Chang Yong method had sol-gel method, electrochemical plating, chemistry and physical deposition method, magnetron sputtering method, pulsed laser deposition etc. in the past.But these methods all have its shortcoming.
It is simple that sol-gel method has technology, with low cost, can carry out advantages such as coating modified in porous or complex-shaped material surface, but sol-gel method only has the additive method incomparable advantage aspect oxide coating.And oxide coating can not thoroughly solve the bad problem of wettability." Ceramics International " the 34th volume magazine " the Improvement of interface between Al and short carbon fibers by α-Al that published in 2008 2O 3Coatings deposited by sol-gel technology " in (1787-179 page or leaf) literary composition people such as Tang utilize sol-gel method in the short carbon fiber surface-coated the thick α-Al of 200-250nm 2O 3Coating.Though this aluminum oxide coating layer has suppressed interfacial brittle phase Al greatly 4C 3Generation, but according to " Scripta Materialia " the 48th volume magazine " Wetting of (0001) α-Al that published in 2003 2O 3Single crystals by molten Al " in (779-784 page or leaf) literary composition people such as Shen to molten aluminum and α-Al 2O 3What (0001) contact angle of face was done studies show that, Al/Al under 700 ℃, 800 ℃ conditions 2O 3Between contact angle be about 110 °.As everyone knows, be considered to non-wetted during greater than 90 ° when contact angle.Therefore, people such as Tang utilize the vacuum infiltration method, have prepared the short carbon fiber reinforced aluminum matrix composites under the pressure condition of 730 ℃ and 7MPa.Bigger preparation pressure not only can improve into the product cost, also can cause the distortion of precast body, and then reduces the mechanical property of material.Therefore, though can avoid taking place surface reaction, can't well solve the problem of interface wet ability at the carbon fiber surface covering aluminum oxide coating.
Though electrochemical plating have been proven technique, can not carry out coating modified at the internal surface of porous materials.In addition, in the process of preparation metal-base composites, the electroplated metal coating tends to be dissolved among the metallic matrix.This causes strengthening body and directly contacts formation fragility phase with metallic matrix.For example: metallic coatings such as carbon fiber surface electro-coppering, nickel.In the preparation process of matrix material, though metallic coating can improve the wettability that strengthens between body and the molten aluminum matrix greatly, coating is dissolved in aluminum substrate very soon, and then is generating fragility phase Al at the interface 2Cu and Al 3Ni has reduced the mechanical property of material.In addition, metals such as copper, nickel have damaging action to carbon fiber under certain conditions, make the application of this type coating be subjected to certain restriction.
Methods such as chemistry and physical deposition, magnetron sputtering, pulsed laser deposition, generally the internal surface that all is not suitable in porous materials carries out coating modified.In addition, the cost height also is an importance of its application of restriction.
Three, summary of the invention
The purpose of this invention is to provide a kind of metal-base composites and strengthen method for modifying high-wettability coating on surface, this method of modifying can overcome many deficiencies of the prior art effectively.
For achieving the above object, the technical solution used in the present invention is: this method comprises the steps:
1. utilize conventional coating production to apply and go back the coating of metal oxides that property is lower than magnesium in the enhancing surface;
2. the enhancing body and the pure magnesium of coated metal oxide coating are put into vacuum oven, pure magnesium places furnace bottom, strengthen body and place pure magnesium top, vacuumize, keep vacuum tightness to be lower than 10Pa, be warming up to 600-700 ℃, be incubated 5-60 minute, make magnesium vapor and increase surface coating of metal oxides generation oxidation-reduction reaction, the formation reaction layer gets final product.
The step 1. coating production of described routine comprises sol-gel method, magnetron sputtering method, pulsed laser deposition, chemical Vapor deposition process.
By set-up procedure 1. coated metal oxide coat-thickness and step 2. in the thickness of temperature and soaking time may command responding layer, the controllable thickness of this responding layer is built in 20-200nm.
The inventive method is the coating of metal oxides by the ordinary method preparation to be carried out magnesium vapor handle, and is twice-modified to realize, has following advantage:
(1) present method technology simple controllable, low for equipment requirements is with low cost, and can carry out coating modifiedly at porous or complex-shaped material internal surface, and the scope of application is extensive.
(2) composite bed that constitutes of the skin formed of the internal layer mainly formed by compounds such as magnesium oxide or spinels of the responding layer of Sheng Chenging and reduced metal, this composite bed tightly is wrapped in the enhancing body, wherein internal layer can effectively suppress to strengthen the Elements Diffusion between body and the metallic matrix, the generation of control surface reaction; The outer wettability that can improve greatly between molten metal matrix and the enhancing body reduces material internal defect in the metal-base composites preparation process, has reduced metal-base composites and has prepared required minimum pressure, improves the mechanics and the physicals of matrix material.
(3) by control native oxide coat-thickness, utilize the metal to metal matrix of magnesium steam reduction to carry out the adjustment of element trace, can further improve the microtexture of matrices of composite material, improve the mechanical property of matrix material.
Four, embodiment
Embodiment 1: carbon fiber strengthens the metal titanium compound coating surface modification of body
1. water and nitric acid dissolve in Virahol.Do not stopping under the stirring condition, the solution of preparation is dropwise joined in the isopropyl titanate.The ratio of isopropyl titanate, Virahol, water, nitric acid is 1: 6: 0.9: 0.6.Obtain TiO through stirring in continuous 3 hours 2Colloidal sol.
2. carbon fiber is placed on and removes glue thermal treatment under the vacuum condition.Thermal treatment temp is 400 ℃, and is incubated 30 minutes, and stove is cold then.
3. putting into TiO except that the carbon fiber behind the glue 2In the colloidal sol, after 15 minutes, take out carbon fiber with the ultrasonic oscillator vibration.
4. surface-coated TiO 2The carbon fiber of coating and pure magnesium are put in the vacuum oven, and pure magnesium is placed the bottom of vacuum oven, strengthen on the stainless (steel) wire that body places pure magnesium top, and cover cover plate, are evacuated down to below the 10Pa.For obtaining fine and close TiO at carbon fiber surface 2Coating is warmed up to 450 ℃ with the speed of 3 ℃ of per minutes, and is incubated 30 minutes.And then be warming up to 700 ℃, and be incubated 10 minutes, make magnesium vapor and increase surface coating of metal oxides generation oxidation-reduction reaction, formation reaction layer.
5. the heating power supply of turning off vacuum oven keeps vacuum, and stove is cold.
6. take out the carbon fiber that magnesium vapor is handled, finish applying TiO 2The carbon fiber of coating strengthens the modification of body; Reaction layer thickness is 20-50nm.
After metal titanium compound coating surface modification, utilize the tensile strength of the homemade continuous fibre enhancing of the 45vol.% magnesium base composite material of vacuum pressure-free impregnation method preparation can reach 980MPa.
Embodiment 2: carbon fiber strengthens the metal zirconium compound coating surface modification of body
1. Yttrium trinitrate and oxygen chloric acid zirconium were joined in the deionized water in 5: 95 in molar ratio, after stirring with magnetic stirrer, obtain 5%Y 2O 3Stablize ZrO 2The sol-gel precursor solution.Anionite-exchange resin is slowly added to 5%Y 2O 3Stablize ZrO 2In the sol-gel precursor solution, make pH value and be 3 5%Y 2O 3Stablize ZrO 2Sol-gel.
2. carbon fiber is placed on and removes glue thermal treatment under the vacuum condition.Thermal treatment temp is 400 ℃, and is incubated 30 minutes, and stove is cold then.
3. putting into 5%Y except that the carbon fiber behind the glue 2O 3Stablize ZrO 2In the sol-gel, after 15 minutes, take out carbon fiber with the ultrasonic oscillator vibration.
4. surface-coated 5%Y 2O 3Stablize ZrO 2The carbon fiber of coating is put in the vacuum oven, vacuumizes.For obtaining fine and close 5%Y at carbon fiber surface 2O 3Stablize ZrO 2Coating is warmed up to 750 ℃ with the speed of 3 ℃ of per minutes, and is incubated 30 minutes, and stove is cold subsequently.
5. the 5%Y after the thermal treatment 2O 3Stablize ZrO 2Carbon fiber and pure magnesium that coating applies are put in the vacuum oven, and pure magnesium is placed the bottom of vacuum oven, strengthen body and place on the stainless (steel) wire above the pure magnesium, and cover cover plate, are evacuated down to below the 10Pa.Be warming up to 600 ℃ then, and be incubated 30 minutes, make magnesium vapor and increase surface coating of metal oxides generation oxidation-reduction reaction, the formation reaction layer gets final product.
6. the heating power supply of turning off vacuum oven keeps vacuum, and stove is cold.
7. take out the carbon fiber that magnesium vapor is handled, the carbon fiber of finishing the coating of metal zirconium compound coating strengthens the modification of body, and reaction layer thickness is 20-50nm.
After metal zirconium compound coating surface modification, utilize the tensile strength of the homemade continuous fibre enhancing of the 45vol.% magnesium base composite material of vacuum pressure-free impregnation method preparation can reach 1080MPa.

Claims (3)

1. a metal-base composites strengthens method for modifying high-wettability coating on surface, comprises the steps:
1. utilize conventional coating production to apply and go back the coating of metal oxides that property is lower than magnesium in the enhancing surface;
2. the enhancing body and the pure magnesium of coated metal oxide coating are put into vacuum oven, pure magnesium places furnace bottom, strengthen body and place pure magnesium top, vacuumize, keep vacuum tightness to be lower than 10Pa, be warming up to 600-700 ℃, be incubated 5-60 minute, make magnesium vapor and increase surface coating of metal oxides generation oxidation-reduction reaction, the formation reaction layer gets final product.
2. a kind of metal-base composites according to claim 1 strengthens method for modifying high-wettability coating on surface, and it is characterized in that: the step 1. coating production of described routine comprises sol-gel method, magnetron sputtering method, pulsed laser deposition, chemical Vapor deposition process.
3. a kind of metal-base composites according to claim 1 and 2 strengthens method for modifying high-wettability coating on surface, it is characterized in that: the skin that internal layer that described responding layer is made up of compound and reduced metal are formed constitutes, and its controllable thickness is built in 20-200nm.
CN 201010242048 2010-07-26 2010-07-26 Method for modifying high-wettability coating on surface of metal-based compound material reinforcement Expired - Fee Related CN101899631B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111168038A (en) * 2020-03-09 2020-05-19 西南交通大学 Preparation device and method of carbon-copper composite material
CN113667858A (en) * 2021-08-13 2021-11-19 新余学院 Preparation method of spinel-coated nano-alumina reinforced aluminum-based composite material in situ

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2219006A (en) * 1988-05-26 1989-11-29 Rolls Royce Plc Coated fibre for use in a metal matrix
CN1045049A (en) * 1988-02-22 1990-09-05 蒂玛夫公司 A kind of method that between material product and foundry goods, obtains metallurgical, bond
CN101357520A (en) * 2007-07-30 2009-02-04 比亚迪股份有限公司 Magnesium alloy composite material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045049A (en) * 1988-02-22 1990-09-05 蒂玛夫公司 A kind of method that between material product and foundry goods, obtains metallurgical, bond
GB2219006A (en) * 1988-05-26 1989-11-29 Rolls Royce Plc Coated fibre for use in a metal matrix
CN101357520A (en) * 2007-07-30 2009-02-04 比亚迪股份有限公司 Magnesium alloy composite material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111168038A (en) * 2020-03-09 2020-05-19 西南交通大学 Preparation device and method of carbon-copper composite material
CN113667858A (en) * 2021-08-13 2021-11-19 新余学院 Preparation method of spinel-coated nano-alumina reinforced aluminum-based composite material in situ
CN113667858B (en) * 2021-08-13 2022-01-28 新余学院 Preparation method of spinel-coated nano-alumina reinforced aluminum-based composite material in situ

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