CN108914024A - A kind of preparation method of amorphous alloy block materials - Google Patents
A kind of preparation method of amorphous alloy block materials Download PDFInfo
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- CN108914024A CN108914024A CN201810576537.0A CN201810576537A CN108914024A CN 108914024 A CN108914024 A CN 108914024A CN 201810576537 A CN201810576537 A CN 201810576537A CN 108914024 A CN108914024 A CN 108914024A
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- amorphous alloy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/08—Amorphous alloys with aluminium as the major constituent
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
- C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
Abstract
The present invention provides a kind of preparation method of amorphous alloy block materials, the preparation method is using amorphous powdered alloy as raw material, using the decline of amorphous alloy heat temperature raising viscosity, gradually softens and superplastic feature is presented in supercooling liquid phase region, it is fast in conjunction with Particle Acceleration in cold spray process, heating temperature is low, heat affecting is small, material is not susceptible to oxidation and tissue change, thermal stress it is small and finally be in compressive stress state the features such as, by procedure parameter optimal control, the layer-by-layer high velocity impact of particle is made to deposit to form block materials；And the shock of subsequent particle has compacting and densification to lithosomic body has been formed in the size range of several grain thicknesses.With simple process, with short production cycle, processing cost is low, adaptable and prepare the technical advantages such as scantling is unrestricted.
Description
Technical field
The invention belongs to the preparation technical fields of amorphous alloy block materials, and in particular to a kind of amorphous alloy block materials
Preparation method.
Background technique
Different from the crystal structure of conventional alloys material, amorphous alloy atom is in the disorderly arranged presentation glassy state of three-dimensional space
Structure has excellent mechanical property and corrosion resistance.By taking al based amorphous alloy as an example, tensile strength is more than 1000MPa,
It is 2~3 times of traditional aluminum alloy materials, and also there are the characteristics such as light weight, rub resistance be good.This closes 21 century amorphous
Golden material is expected to replace some traditional metal materials in the fields such as Aeronautics and Astronautics and industry, national defence, shows wide application
Prospect.
Critical cooling rate needed for forming amorphous alloy is high, generally 103K/s or more, this proposes its preparation process
Higher requirement is gone out.The method for being generally used to prepare amorphous alloy material mainly has fusion casting and powder metallurgic method.Wherein melt
Casting includes copper mold casting, spray to cast-suction casting method and water quenching etc..But the production efficiency of these methods is lower, and obtained amorphous closes
Golden size is smaller, more demanding to the amorphous formation ability of alloy itself.Powder metallurgical technique is to be atomized amorphous alloy powder
Raw material, be packed into mold by compacting and sintering and etc. amorphous alloy material, but the complex technical process, larger size system is made
Part the problems such as there are crystallization.In short, cooling condition need to be broken through since preparation amorphous alloy needs big cooling velocity and degree of supercooling
Limitation, conventional method prepare larger size block materials difficulty it is big, complex process, the reality for seriously constraining new material is answered
With.
Cold spray technique is a kind of novel green spraying technology to grow up in recent years, it is with compressed gas (nitrogen, helium
Gas or their mixed gas) be used as accelerating medium, drive metallic particles in the solid state with high speed (300~
1200m/s) bumped substrate makes particle that drastic deformation occur and realize layer by layer deposition.It has spraying compared with hot-spraying technique
The low feature of temperature is suitble to the preparation heat-sensitive materials such as amorphous alloy, and lithosomic body is fine and close and oxide content is low, chemical component and
Microstructure can be consistent with raw material；Residual stress inside lithosomic body is low and is compression, and deposition efficiency is high, can make
Standby large scale two dimension coating and three-dimensional block materials.Recent study person has started to select amorphous alloy and the atomization of some systems
Powder material is made, attempts the cold spraying on the material substrates such as carbon steel and prepares amorphous protective coating, but related cold spraying prepares block
The related work of body amorphous alloy material is also rarely reported.
Summary of the invention
To solve the above-mentioned problems, the present invention provides, and the preparation method passes through the iron that cold spraying produces powder by atomization
Base, zirconium base, copper-based or aluminium base amorphous alloy powder are raw material, prepare block amorphous alloy material, the amorphous alloy powder
Particle size range be 5~80 μm, spray the baseplate material used as metals such as common copper alloy, aluminium alloy, carbon steel, stainless steels
Substrate；Spray before substrate coarse sandpaper polishing with obtain suitable surface roughness convenient for particle deposition and by ultrasonic wave it is clear
It washes away except surface and oil contaminant；
Further, the cold spray process is as follows：Substrate is fixed on the three-dimension numerical controlled mobile working platform of X-Y-Z,
Spray gun is fixed on the normal position of workbench, and mobile platform is moved with certain speed when spraying；Or using fixture base
Plate is fixed, by being fixed on the movement of spray gun on mechanical arm, to prepare the block amorphous alloy material of certain size；
Further, cold spraying principle is to be made by the way that amorphous alloy powder is heated to its critical cooling rate
Softening, plasticity, which improves, even to be generated superplasticity and realizes effective deposition of powder granule；
Further, the working gas used in the cold spray process is the mixed of nitrogen, helium or nitrogen and helium
Close gas；
Further, the technological parameter of cold spraying and range are：Spray distance be 5~50mm, rifle outlet pressure be 0.5~
5.0MPa, pre-heated gas temperature are respectively 100~900 DEG C, and substrate rate travel is 60~1000mm/min, and powder feeding rate is about
1~50g/min；
Further, finally prepd bulk amorphous materials in the S3 are carried out using hardness of the nano-probe to coating
Characterization, lithosomic body average hardness is about 3.56GPa；
Further, finally prepd bulk amorphous materials in the S3 are measured using Image-Pro software and is put 400
Under big multiple, the porosity of block amorphous alloy material is about 3%；
Beneficial effects of the present invention are as follows：
1)：Amorphous alloy has the characteristic similar with other glassy structure materials, and viscosity declines as the temperature rises,
Gradually soften；And superplasticity is presented in supercooling liquid phase region；
2)：Using the above-mentioned characteristic of amorphous alloy and cold spray technique is combined, largely reduction prepares scantling
Dependence to alloy Forming ability, the bulk amorphous alloy size prepared far are more than generally conventional method；
3)：Particle Acceleration is fast in cold spray process, heating temperature is low, and heat affecting is small, and material is not susceptible to aoxidize and organize
Variation, thermal stress is small and is finally in compressive stress state, by procedure parameter optimal control, makes the layer-by-layer high velocity impact deposition shape of particle
At block materials；The shock of subsequent particle has compacting and cause to lithosomic body has been formed in the size range of several grain thicknesses
Densification effect；
4)：It is the method for the invention simple process, with short production cycle, at low cost and adaptable.
Detailed description of the invention
Fig. 1 is cold spraying system structural schematic diagram；
In figure label for：(1) gas source, (2) gas control unit, (3) mass flowmenter, (4) powder feeder, (5) spray gun,
(6) thermometric and pressure instrumentation, (7) substrate, (8) numerical control table, NC table, (9) gas heater；
Fig. 2 is the SEM tissue topography of amorphous powder；
Fig. 3 is the part prepared after block amorphous alloy material macro morphology and machining；
Fig. 4 is the XRD test result of starting powder and the bulk amorphous materials using cold spray process preparation；
In figure label for：(10) bulk amorphous materials prepared by original amorphous powder, (11) cold spray process；
Fig. 5 is the SEM pattern of the coatings cross-section prepared using cold spray process.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.On the contrary, the present invention cover it is any be defined by the claims do on the essence and scope of the present invention
Substitution, modification, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to this
It is detailed to describe some specific detail sections in the datail description of invention.It is thin without these for a person skilled in the art
The present invention can also be understood completely in the description of section part.
The present invention will be further explained below with reference to the attached drawings and specific examples, but not as a limitation of the invention.
Most preferred embodiment is enumerated below for of the invention：
As Figure 1-Figure 5, the present invention provides a kind of preparation method of amorphous alloy block materials, and this method is to be atomized system
The amorphous alloys powders such as the iron-based of powder production, zirconium base, copper-based, aluminium base are raw material, prepare amorphous alloy block using cold spray technique
The new method of body material.Since amorphous component molten alloy droplets size is small in atomization process, cooling velocity is fast, the powder after solidification holds
Easily keep non crystalline structure；Simultaneously be to guarantee that the coat inside overwhelming majority is amorphous state and suitable cold spray process and equipment requirement,
Atomized powder is further sieved, selects the amorphous alloy powder of granularity effective size of grain range as spraying raw material.Using
Common metal material such as copper alloy, aluminium alloy, carbon steel, stainless steel etc. is used as substrate, in order to be able to achieve preferable deposition effect,
Appropriate grinding process is carried out to obtain suitable surface roughness to substrate, and carries out ultrasonic cleaning with acetone to remove surface
Greasy dirt etc..The substrate that cleaning finishes is placed on workbench, it is suitable between control per pass by inputting numerical control program
The lithosomic body of certain size area and thickness is formed when distance；Or fix substrate, it is sprayed by being fixed on mechanical arm
The movement of rifle deposits preparation to realize.Spray gun is vertically fixed on above substrate.Spraying process mainly controls technological parameter：Work
Make the mixed gas that gas is nitrogen, helium or nitrogen and helium, spray distance, spray pressure, spraying temperature, substrate or spray
Rifle movement speed, powder feeding rate etc..
Amorphous alloy has the characteristic similar with other glassy structure materials, and viscosity declines as the temperature rises, by
Gradually soften；And superplasticity is presented in supercooling liquid phase region.Using the above-mentioned characteristic of amorphous alloy and cold spray technique is combined, in very great Cheng
Reduction prepares dependence of the scantling to alloy Forming ability on degree, and the bulk amorphous alloy size prepared far is more than generally conventional side
Method, and there is outstanding advantages of simple process, with short production cycle, at low cost and adaptable.
Cold spray apparatus is the cold spraying system of autonomous Design assembling, and system structure is as shown in Figure 1.
By taking aluminium-based amorphous alloy material as an example, using the atomization amorphous powder of Al-Ni-Y system, powder heterogeneous microstructure is as schemed
Shown in 2；Its particle size range is 5~45m.Spraying uses Al6061 substrate, before spraying, need to be carried out using 60 mesh coarse sandpapers to substrate
Polishing, to obtain the deposition that enough surface roughnesses are convenient for particle；It is cleaned in ultrasonic wave after polishing using acetone,
To remove being mingled with greasy dirt for surface etc..
Substrate is fixed on workbench before spraying, workbench is X-Y-Z three-shaft linkage system, and spray gun is fixed on base
The normal position of plate, in the program of action pane input control workbench.Workbench is moved when spraying with certain speed
Dynamic, so that particle deposits to form one coat, one of end of scan rear platform is along the direction perpendicular with passage direction before
Mobile certain width is moved at the same rate further along the opposite direction for spraying passage before to form passage overlap joint, each passage
Overlap joint forms the amorphous coating of larger area repeatedly.On the basis of forming certain area coating, repeatedly sprayed using same manner
It applies, i.e., forms plane SH wave in depositing coating, thus realize the preparation of bulk amorphous materials, the material object of prepared thick coating
Photo is shown in Fig. 3.And it can be carried out subsequent mechanical process.
Specific spraying parameter is as follows：It employs nitrogen as to accelerate and powder feeding carrier gas；Spray distance is 20mm, rifle outlet
Pressure is 3.0MPa, and pre-heated gas temperature is respectively 320 DEG C, and substrate rate travel is 500mm/min, and powder feeding rate is about 12g/
min；Spacing between per pass is 2mm.
XRD analysis test is carried out it is found that inside alloy to the block amorphous alloy sample prepared under above-mentioned technological parameter
Ingredient is almost the same with starting powder, predominantly amorphous microstructure structure.
Claims (5)
1. a kind of preparation method of bulk amorphous materials, which is characterized in that the preparation method passes through cold spraying for powder by atomization
The iron-based of production, zirconium base, copper-based or aluminium base amorphous alloy powder are raw material, prepare block amorphous alloy material, the amorphous
The particle size range of alloy powder is 5~80 μm, sprays the baseplate material that uses as common copper alloy, aluminium alloy, carbon steel, stainless
The metal substrates such as steel；The polishing of substrate coarse sandpaper is before spraying to obtain the deposition and process that suitable surface roughness is convenient for particle
Ultrasonic cleaning removes surface and oil contaminant.
2. the method according to claim 1, wherein the cold spray process is as follows：Substrate is fixed on X-Y-Z
On three-dimension numerical controlled mobile working platform, spray gun is fixed on the normal position of workbench, and mobile platform is with a constant speed when spraying
Degree movement；Or substrate is fixed using fixture, by being fixed on the movement of spray gun on mechanical arm, to prepare a scale
Very little block amorphous alloy material.
3. the method according to claim 1, wherein cold spraying principle is by the way that amorphous alloy powder is heated to
Its critical cooling rate, softens it, and plasticity improves the effective deposition for even generating superplasticity and realizing powder granule.
4. the method according to claim 1, wherein the working gas used in the cold spray process is nitrogen
The mixed gas of gas, helium or nitrogen and helium.
5. according to the method described in claim 2, it is characterized in that, the technological parameter and range of cold spraying are：Spray distance is 5
~50mm, rifle outlet pressure are 0.5~5.0MPa, and pre-heated gas temperature is respectively 100~900 DEG C, and substrate rate travel is 60
~1000mm/min, powder feeding rate are about 1~50g/min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115125471A (en) * | 2022-06-29 | 2022-09-30 | 武汉苏泊尔炊具有限公司 | Method for manufacturing amorphous non-stick material and method for manufacturing amorphous non-stick coating |
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| US20160122557A1 (en) * | 2013-06-12 | 2016-05-05 | United Technologies Corporation | Corrosion resistant hydrophobic coatings and methods of production thereof |
| US9609874B1 (en) * | 2016-07-21 | 2017-04-04 | Kuwait Institute For Scientific Research | Metallic glassy alloy powders for antibacterial coating |
| CN107338433A (en) * | 2017-07-11 | 2017-11-10 | 西安建筑科技大学 | A kind of preparation method of Mg alloy surface amorphous alloy coating |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059218A (en) * | 2010-12-14 | 2011-05-18 | 北京科技大学 | Method and device for preparing polymer-based composite material surface metallization coating |
| US20160122557A1 (en) * | 2013-06-12 | 2016-05-05 | United Technologies Corporation | Corrosion resistant hydrophobic coatings and methods of production thereof |
| US9609874B1 (en) * | 2016-07-21 | 2017-04-04 | Kuwait Institute For Scientific Research | Metallic glassy alloy powders for antibacterial coating |
| CN107338433A (en) * | 2017-07-11 | 2017-11-10 | 西安建筑科技大学 | A kind of preparation method of Mg alloy surface amorphous alloy coating |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115125471A (en) * | 2022-06-29 | 2022-09-30 | 武汉苏泊尔炊具有限公司 | Method for manufacturing amorphous non-stick material and method for manufacturing amorphous non-stick coating |
| CN115125471B (en) * | 2022-06-29 | 2023-05-16 | 武汉苏泊尔炊具有限公司 | Method for producing amorphous non-stick material and method for producing amorphous non-stick coating |
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