CN105256307B - The cold spraying preparation method of the corrosion-resistant aluminium base of Mg alloy surface or zinc-aluminium Base Metal coating - Google Patents
The cold spraying preparation method of the corrosion-resistant aluminium base of Mg alloy surface or zinc-aluminium Base Metal coating Download PDFInfo
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- CN105256307B CN105256307B CN201510746123.4A CN201510746123A CN105256307B CN 105256307 B CN105256307 B CN 105256307B CN 201510746123 A CN201510746123 A CN 201510746123A CN 105256307 B CN105256307 B CN 105256307B
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
Abstract
The invention discloses a kind of corrosion-resistant aluminium base of Mg alloy surface or the cold spraying preparation methods of zinc-aluminium Base Metal coating, belong to material surface engineering technolog and mechanical manufacturing field, include the following steps：1) aluminium base or zinc-aluminium based metal powder are mixed with hard metal powders, the mixed-powder for cold spraying is made；2) cold spray process is used, by spraying mixed-powder on pretreated magnesium alloy substrate, corrosion-resistant aluminium base or zinc-aluminium Base Metal coating is made in magnesium alloy matrix surface.This method is without significantly improving particle rapidity and depositing temperature, it is easy to operate, there is more superior electric conductivity, thermal conductivity through lithosomic body made from the method for the present invention, higher corrosion-resistant, wear-resistant and higher mechanical property, thus can be widely applied to prepare highly conductive, high heat conduction, highly corrosion resistant, high wear resistance coating or strong mechanical performance workpiece.
Description
Technical field
The invention belongs to material surface engineering technologs and mechanical manufacturing field, and in particular to a kind of Mg alloy surface is corrosion-resistant
The cold spraying preparation method of aluminium base or zinc-aluminium Base Metal coating.
Background technology
Magnesium alloy has many excellent performances as structural metallic materials：Low (the 1.8g/cm of density3), only the 2/ of aluminium
3, the 1/4 of iron；Specific strength and specific stiffness are big；Damping performance is good, can bear the shock loading bigger than aluminium alloy, be suitable for bearing
The part of high vibration；Matter is soft, Cutting free processing etc..These advantages of magnesium alloy make it in aerospace, auto industry, electronics
The fields such as communication have obtained more application, possess extraordinary foreground.But as structural material, the poor corrosion stability of magnesium alloy
Its use in a variety of contexts can be limited.
Currently, mostly use surface reforming layer to improve the corrosion resistance of magnesium alloy, as chemical composition coating, anodized,
Various coatings and coating, laser modified technology etc..Chemical composition coating is used as japanning bottom extensively, but studies have shown that chemistry turns
Corrosion rate can only be slowed down by changing film, not can effectively prevent corrosion, and often contain heavy metal ion in plating solution, preparation process is to ring
It causes centainly to pollute in border；Anodizing is a kind of new surface treatment technologies of rising in recent years, can be obtained it is wear-resistant, have one
Determine the coating of corrosion resistance, but the brittleness of anode oxide film is larger, porous, it is difficult to obtain uniform oxidation film；Magnesium alloy
The coat of metal generally uses electro-plating method, but since the current potential of magnesium is extremely low, it is not easy to Direct precipitation corrosion resistant metal, and lead in plating solution
Often contain cyanide, there are larger pollutions to environment；Using thermal spraying in Mg alloy surface deposited metal coating, such as thermal spraying
Aluminized coating is prepared, but in thermal spray process, strong reaction can occur for Mg alloy surface, and Mg alloy surface is made to be aoxidized, raw
At the oxidation film that corrosion resistance is very poor.In recent years, laser modified technology is widely used, but magnesium alloy is in laser treatment
When oxidation, evaporation easily occurs and generates vaporization, stomata and the problems such as thermal stress.To sum up, existing to improve corrosion stability of magnesium alloy
Method still has more problem.
Cold spraying is a kind of high-speed impact by micro-meter scale particle under solid conditions, by particle and basal body interface or
Particle and plastic deformation violent at deposited particles sub-interface and deposit the technology to form coating.Lower technological temperature is (low
In the fusing point of sprayed on material) can to avoid spraying process in metallic oxidation and crystal grain grow up, while also avoiding to magnesium
Alloy substrate causes heat affecting, therefore cold spraying is to prepare the potential effective of high performance corrosion-proof metal coating in Mg alloy surface
Method.Due to not generating the waste liquid rich in heavy metal ion in production, relative to electrochemical method, cold spraying is a kind of phase
To the green preparation technology of coating of environmental protection.
The compactness of coating is that the most important factor of integrated member corrosion resistance is influenced in addition to material attribute itself.Cold spray
The compactness of coating layer depends on the size of cold spraying particle amount of plastic deformation during Collision deposition：Amount of plastic deformation is got over
Greatly, the consistency of coating is higher, and corrosion resistance is better.Current stage, the method for improving cold spraying particle deflection mainly have two
Kind：
1) kinetic energy when improving particle rapidity and then increasing particle encounter；
2) improving the temperature of particle makes particle that significant softening occur.
For cold spraying Al alloy particles because its density is low, momentum is low with energy, and high velocity impact densification mutual when depositing is turned into
With weak, the compactness of coating is relatively low.In general, by further increasing substantially particle rapidity to improve coating compactness.But it is aobvious
The speed for writing raising particle is usually required using expensive helium as gas (about 50 times of nitrogen) is accelerated, and cost is high, limit
Industrial volume production is made.The temperature for significantly improving particle will be the metal transfer softening of these low melting points, and then be deposited on spray
Rifle inner wall, causes spray gun to block, spraying process poor controllability, it is difficult to which continuous spray produces.
Therefore, how inexpensive realization Mg alloy surface aluminium base and significantly improving for zinc-aluminium base corrosion-resistant finishes is current
Important technological problems to be resolved.
Invention content
In order to overcome the problems of the above-mentioned prior art, the purpose of the present invention is to provide a kind of Mg alloy surface corrosion resistants
Aluminium base or the cold spraying preparation method of zinc-aluminium Base Metal coating are lost, this method is easy to operate, low for equipment requirements, through party's legal system
The coating obtained has excellent corrosion resistance.
The present invention is to be achieved through the following technical solutions：
The cold spraying preparation method of a kind of corrosion-resistant aluminium base of Mg alloy surface or zinc-aluminium Base Metal coating, including following step
Suddenly：
1) aluminium base or zinc-aluminium based metal powder are mixed with hard-particle powder, the mixed-powder for cold spraying is made；
2) cold spray process is used, mixed-powder is sprayed on passing through pretreated magnesium alloy substrate, in magnesium alloy substrate
Corrosion-resistant aluminium base or zinc-aluminium Base Metal coating is made in surface.
The grain size of the aluminium base or zinc-aluminium based metal powder is 20~50 μm.
The grain size of the hard-particle powder is 150~500 μm.
The hard-particle powder accounts for the 20%~80% of mixed-powder total volume.
It is that magnesium alloy substrate is subjected to acetone ultrasonic cleaning and sand blasted surface roughening treatment by pretreated magnesium alloy base
After be made.
Used working gas is nitrogen when spraying.
When spraying, gas pressure is set as 0.8~4.0MPa；Gas temperature is 150~500 DEG C.
The hard-particle powder is metal, alloy or ceramic particle.
Compared with prior art, the present invention has technique effect beneficial below：
The cold spraying preparation method of the corrosion-resistant aluminium base of Mg alloy surface disclosed by the invention or zinc-aluminium Base Metal coating, with aluminium
Base or the mixed-powder of zinc-aluminium based metal powder and hard-particle powder are as spray powders, using cold spraying by pre-
Prepares coating on the magnesium alloy substrate of processing, hard bulky grain is to having deposited aluminium base or Zinc and Aluminum Base Coating in the mixed-powder of spraying
(in mixed-powder hard particles due to grain size it is larger so speed is slow, will not deposit, so deposition only will spray
Aluminium base and zinc-aluminium base particle.The shock of aluminium base and the deposition and hard particles of zinc-aluminium base particle occurs in spraying process simultaneously
And rebound, hard particles can only hit previously deposited aluminium base and Zinc and Aluminum Base Coating without pair also generating shadow in the particle of flight
It rings.) effect of impact so that the deposited firm cold welding of particle possible hole together and in seal coat in coating,
Coating cannot be penetrated from coating surface and reaches coating and corrosion base from basal body interface to obtain liquid or gaseous corrosive medium
Body magnesium alloy.Compared with coating of the same race prepared by conventional cold spraying method, the advantage of the method for the present invention is fairly obvious：
First, the coating for preparing aluminium base and zinc-aluminium Base Metal is adopted this method without perforation hole, completely isolated can be corroded
Medium, therefore show excellent corrosion resistance.
Second, hard-particle powder makes the collision deformation of magnesium alloy substrate to form two kinds of materials at coating/basal body interface
The bond strength of coating and matrix is greatly improved in the interfacial structure being mutually locked, and ensure that the length using process floating coat
Phase stability.
Third, cold spraying aluminium base, the Zinc and Aluminum Base Coating of Mg alloy surface will not only reduce the fatigue life of matrix, instead
Generated residual compressive stress, can effectively improve the crack extesion resistance of matrix when due to particle shock Mg alloy surface matrix
Power significantly improves the fatigue life of matrix.
4th, the present invention is without expensive helium as acceleration gas.Meanwhile accelerating the temperature and pressure of gas equal
It is relatively low, it therefore, can be realized by Portable type cold spraying equipment, increased considerably the flexibility of construction, while coating
Manufacturing cost is relatively low.
The method of the present invention realizes Mg alloy surface densification aluminium base or prepared by the low cost of zinc-aluminium Base Metal coating.Therefore,
It has broad application prospects in Corrosion Behaviors of Magnesium Alloys protection field.
Further, hard-particle powder can be metal, alloy and ceramic particle in dusty spray, only need hardness notable
More than the material sprayed, therefore the plastic deformation occurred in knockout process focuses primarily upon sprayed on material, and then hole is made to disappear
It loses.Hard-particle powder have larger grain size (>150 μm), keep its impact velocity relatively low, cold spraying is less than under spraying conditions
The critical speed of deposition and collision when hardly deposit, can coating material caused by avoid being deposited due to hard particles at
Divide and changes.
Description of the drawings
Fig. 1 is the pattern of aluminium powder and hard particles (316 stainless steel particles)；(a) it is aluminium powder；(b) it is 316 stainless steel hard
Particle；
Fig. 2 is the section structure of the 1100Al coatings of conventional cold spraying and the method for the present invention preparation under the conditions of identical parameters；
(a) it is conventional method；(b) it is the method for the present invention；
Fig. 3 is different sample corrosion potential versus time curves in 3.5%NaCl solution
Fig. 4 is the polarization curve of different samples in 3.5%NaCl solution；
Fig. 5 is conventional cold spraying and 1100Al coating/magnesium alloy basal body interface structures prepared by the method for the present invention；(a) it is
Conventional method；(b) it is the method for the present invention.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, it should be noted that these implementations
Example is the present invention preferably particle, is used for it will be understood by those skilled in the art that the present invention, but the invention is not limited in these realities
Apply example.
The cold spraying preparation method of the corrosion-resistant aluminium base of Mg alloy surface disclosed by the invention or zinc-aluminium Base Metal coating, passes through
Following steps are implemented：
First, by the big grain size of 5-70 μm of aluminium base or zinc-aluminium based metal powder and certain proportion (10%-50%) (>150
μm) hard metal powders mixing, using this kind of mixed-powder as cold spraying dusty spray.
Secondly, using cold spraying on magnesium alloy substrate after pretreatment prepares coating.Pass through hard in dusty spray
Bulky grain makes in coating deposited particle pass through cold welding and closes particle to having deposited the effect of impact of aluminium base or Zinc and Aluminum Base Coating
Between hole and formed without perforation hole dense coating, with conventional cold spraying method prepare coating of the same race compared with, using this
Coating prepared by kind method has excellent corrosion resistance due to without perforation hole.
Embodiment 1
Using granularity between 10-50 μm of 1100Al powder as sprayed on material, with granularity between 200-300 microns 316
Stainless steel particles are as hard particles.The hardness of 1100Al and 316 stainless steel hard is respectively about 25HV and 274HV.Such as Fig. 1 institutes
Show, (a) is aluminium powder；(b) it is 316 stainless steel hard particles；1100Al powder is spherical and ellipsoid shape, 316 stainless steel hard
Particle is spherical shapes.Using the hard particles of 40vol.% and 1100Al powder mechanical mixtures as dusty spray.With AZ31 magnesium
Alloy carries out acetone ultrasonic cleaning and sand blasted surface roughening treatment before spraying as basis material to matrix.With nitrogen as work
Make gas, gas pressure and gas temperature are respectively set as 2.0MPa and 200 DEG C.Control sample is to be adopted under identical spray parameters
The coating prepared with pure 1100Al powder.
The section structure of coating is as shown in Figure 2.By (a) in Fig. 2 it can be found that using the preparation of single 1100Al powder
There are a large amount of holes, image analysis result to show in coating, and coating porosity is up to 13.3%.In contrast to this, referring to Fig. 2
In (b), the Al coat insides deposited using mixed-powder do not find apparent hole, and image analysis result shows the porosity of coating
Only 0.3%.It can be seen that compared with conventional cold spray process, cold spraying method using the present invention can significantly reduce aluminium
The porosity of based alloy coating.The 1100Al of 1100Al coatings, the method for the present invention preparation prepared by 1100Al bulks, conventional method
Corrosion potential of the four kinds of samples of coating and magnesium alloy substrate in 3.5%NaCl solution changes over time curve and polarization is bent
Line difference is as shown in Figures 3 and 4.As can be seen that 1100Al coatings prepared by conventional method are since there are a large amount of hole, corrosion
Medium can reach magnesium alloy matrix surface by these holes, therefore, the self-corrosion of 1100Al coatings prepared by conventional method
Current potential is moved closer to magnesium alloy substrate, does not have protective effect.And the Al coating structures for improving cold spraying method preparation are fine and close,
It can be effectively isolated contact of the corrosive medium with magnesium alloy substrate, corrosion potential and industrial pure Al bulk are almost the same, resistance to
Corrosive nature is extremely excellent.
After hard particles are added in powder, the bond strength of pure Al coatings increases substantially 51MPa by 24MPa.Such as Fig. 5
In (a), shown in (b), this is mainly due to hard particles to make coating form two kinds with matrix the collision deformation effect of matrix
Interlaced, the sealed interfacial structure of metal, thus the bond strength of matrix and coating has been greatly enhanced.
Embodiment 2
Using granularity between 15-50 μm of Zn5%Al powder as sprayed on material, with granularity between 150-300 microns 430
Stainless steel particles are as hard particles.Using the hard particles of 50vol.% and pure Al powder mechanical mixture as dusty spray.With
AZ31 magnesium alloys carry out acetone ultrasonic cleaning and sand blasted surface roughening treatment before spraying as basis material to matrix.With nitrogen
As working gas, gas pressure and gas temperature are respectively set as 1.8MPa and 250 DEG C.Test result shows that use is single
There are a large amount of holes, image analysis result to show in coating prepared by Zn5%Al powder, and coating porosity is up to 10.7%.It adopts
The Zn5%Al coat insides deposited with mixed-powder do not find that apparent hole, image analysis result show the porosity of coating only
It is 0.4%.Electrochemical results show the corrosion potential and AZ31 magnesium alloys of Zn5%Al coatings prepared by conventional method
Matrix moves closer to, and does not have protective effect.And the Al coating structures for improving cold spraying method preparation are fine and close, can be effectively isolated
Contact of the corrosive medium with magnesium alloy substrate, corrosion potential and ZnAl bulks are almost the same, and corrosion resistance is extremely excellent.
In conclusion the present invention under the premise of low cost, realizes that the high combination of Mg alloy surface cold spraying deposition preparation is strong
The coating surface of having no way of of degree is penetrated through to fine and close aluminium base, the Zinc and Aluminum Base Coating of the perforation hole of coating/basal body interface.The invention is magnesium
Alloy corrosion protection provides a kind of new corrosion-resistant finishes preparation method.
Claims (3)
1. the cold spraying preparation method of a kind of corrosion-resistant aluminium base of Mg alloy surface or zinc-aluminium Base Metal coating, which is characterized in that packet
Include following steps：
1) aluminium base or zinc-aluminium based metal powder are mixed with hard-particle powder, the mixed-powder for cold spraying is made；Aluminium base
Or the grain size of zinc-aluminium based metal powder is 20~50 μm；The hard-particle powder account for mixed-powder total volume 40%~
50%；The grain size of hard-particle powder is 150~500 μm；
2) cold spray process is used, mixed-powder is sprayed on passing through pretreated magnesium alloy substrate, in magnesium alloy matrix surface
Corrosion-resistant aluminium base or zinc-aluminium Base Metal coating is made；
It is made after pretreated magnesium alloy base is that magnesium alloy substrate is carried out acetone ultrasonic cleaning and sand blasted surface roughening treatment
；When spraying, gas pressure is set as 0.8~4.0MPa；Gas temperature is 150~500 DEG C.
2. the cold spraying preparation side of the corrosion-resistant aluminium base of Mg alloy surface according to claim 1 or zinc-aluminium Base Metal coating
Method, which is characterized in that used working gas is nitrogen when spraying.
3. the cold spraying preparation side of the corrosion-resistant aluminium base of Mg alloy surface according to claim 1 or zinc-aluminium Base Metal coating
Method, which is characterized in that the hard-particle powder is metal, alloy or ceramic particle.
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| CN201510746123.4A CN105256307B (en) | 2015-11-05 | 2015-11-05 | The cold spraying preparation method of the corrosion-resistant aluminium base of Mg alloy surface or zinc-aluminium Base Metal coating |
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| CN107675163A (en) * | 2017-11-14 | 2018-02-09 | 北京科技大学 | The method that the pure zinc of Mg alloy surface/Zinc alloy coated is prepared based on cold spray technique |
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| CN109487261B (en) * | 2018-12-28 | 2021-02-12 | 广东工业大学 | Method for quickly electrodepositing coating on surface of magnesium alloy |
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| CN110976893B (en) * | 2019-12-27 | 2022-05-20 | 深圳市欣天科技股份有限公司 | Preparation method of composite metal layer on surface of ceramic substrate |
| CN111926322A (en) * | 2020-06-24 | 2020-11-13 | 广东省新材料研究所 | Repairing method of magnesium-aluminum alloy structural part |
| CN113106437B (en) * | 2021-03-23 | 2022-10-14 | 武汉大学 | Ni-Mo-Al for molten chloride corrosion prevention 2 O 3 Metal coating and preparation method thereof |
| CN113088956B (en) * | 2021-04-14 | 2022-09-20 | 广东工业大学 | Cold spraying-based corrosion-resistant composite coating and preparation method and application thereof |
| CN113293345A (en) * | 2021-05-14 | 2021-08-24 | 东莞美景科技有限公司 | Plate and production method thereof |
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| CN115055677B (en) * | 2022-08-17 | 2022-11-01 | 潍坊谷合传动技术有限公司 | Method for preparing zinc-aluminum corrosion-resistant coating by cold spraying |
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| CN104894554B (en) * | 2015-04-10 | 2018-10-30 | 西安交通大学 | A kind of preparation method and application of high-compactness cold spraying metal/metal base lithosomic body |
| CN104988492A (en) * | 2015-07-22 | 2015-10-21 | 中国兵器科学研究院宁波分院 | Preparation method of corrosion resistant coating layer on surface of magnesium alloy component |
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