CN101899631B - 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 PDFInfo
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- CN101899631B CN101899631B CN 201010242048 CN201010242048A CN101899631B CN 101899631 B CN101899631 B CN 101899631B CN 201010242048 CN201010242048 CN 201010242048 CN 201010242048 A CN201010242048 A CN 201010242048A CN 101899631 B CN101899631 B CN 101899631B
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- coating
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- magnesium
- thomel
- reinforcement
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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
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 increasingly high, 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 pass through design, promptly through raw-material selection, each moity being distributed and the assurance of processing condition etc., makes stock blend material advantage complementary, 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 the most gold metal-matrix composite material, 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 the 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 surface reaction and the formation that suppresses the 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.Method commonly used in the past has sol-gel method, plating method, chemistry and physical deposition method, magnetron sputtering method, pulsed laser deposition etc.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 coatings.And oxide coatings 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
3(0001) research done of the contact angle of face shows 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, under 730 ℃ of pressure conditions with 7MPa, have prepared the short carbon fiber reinforced aluminum matrix composites.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 plating method 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 thomel under certain conditions, make the application of this type coating receive certain restriction.
Methods such as chemistry and physical deposition, magnetron sputtering, pulsed laser deposition, the internal surface that generally 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 realizing above-mentioned purpose, the technical scheme that the present invention adopts is: this method comprises the steps:
1. utilize conventional coating production to strengthen the surface and apply the coating of metal oxides that reductibility is lower than magnesium at thomel;
2. the thomel enhancing body and the pure magnesium of coated metal oxide coating are put into vacuum oven, pure magnesium places furnace bottom, and thomel strengthens body and places 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 strengthen surface coating of metal oxides generation oxidation-reduction reaction, generate mainly the composite bed responding layer that skin that the internal layer be made up of Natural manganese dioxide or spinel compound and reduced metal form constitutes and get final product.
The step 1. coating production of described routine comprises sol-gel method, magnetron sputtering method, pulsed laser deposition, chemical Vapor deposition process.
Through 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 magnesia or spinelles of the conversion zone 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 interfacial reaction; The outer wetability that can improve the motlten metal matrix greatly and strengthen between the 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 physical property of composite.
(3) through 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: thomel strengthens the metal titanium compound coating surface-treated 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. be placed on thomel and remove 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 thomel behind the glue
2In the colloidal sol, after 15 minutes, take out thomel with the ultrasonic oscillator vibration.
4. surface-coated TiO
2The thomel of coating and pure magnesium are put in the vacuum oven, place the bottom of vacuum oven to pure magnesium, 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 PMs, 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 thomel that magnesium vapor is handled, accomplish applying TiO
2The thomel of coating strengthens the modification of body; Reaction layer thickness is 20-50nm.
After metal titanium compound coating surface-treated, 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: thomel strengthens the metal zirconium compound coating surface-treated of body
1. join Yttrium trinitrate and oxygen chloric acid zirconium 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.Slowly add anionite-exchange resin 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. be placed on thomel and remove 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 thomel behind the glue
2O
3Stablize ZrO
2In the sol-gel, after 15 minutes, take out thomel with the ultrasonic oscillator vibration.
4. surface-coated 5%Y
2O
3Stablize ZrO
2The thomel 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 PMs, and is incubated 30 minutes, and stove is cold subsequently.
5. the 5%Y after the thermal treatment
2O
3Stablize ZrO
2Thomel and pure magnesium that coating applies are put in the vacuum oven, place the bottom of vacuum oven to pure magnesium, 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 thomel that magnesium vapor is handled, the thomel of accomplishing 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-treated, 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 strengthen the surface and apply the coating of metal oxides that reductibility is lower than magnesium at thomel;
2. the thomel enhancing body and the pure magnesium of coated metal oxide coating are put into vacuum oven, pure magnesium places furnace bottom, and thomel strengthens body and places 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 strengthen surface coating of metal oxides generation oxidation-reduction reaction, generate mainly the composite bed responding layer that skin that the internal layer be made up of Natural manganese dioxide or spinel compound and reduced metal form constitutes and get 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 Natural manganese dioxide or spinel compound and reduced metal are formed constitutes, and its gauge control is at 20-200nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201010242048 CN101899631B (en) | 2010-07-26 | 2010-07-26 | Method for modifying high-wettability coating on surface of metal-based compound material reinforcement |
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| CN 201010242048 CN101899631B (en) | 2010-07-26 | 2010-07-26 | Method for modifying high-wettability coating on surface of metal-based compound material reinforcement |
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| CN101899631B true CN101899631B (en) | 2012-10-03 |
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| 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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| GB2219006A (en) * | 1988-05-26 | 1989-11-29 | Rolls Royce Plc | Coated fibre for use in a metal matrix |
| CN101357520B (en) * | 2007-07-30 | 2012-10-17 | 比亚迪股份有限公司 | Magnesium alloy composite material and preparation method thereof |
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