CN107663618A - Zirconium-base amorphous alloy aluminum or aluminum alloy composite and dyeing zirconium-base amorphous alloy aluminum or aluminum alloy composite and preparation method - Google Patents
Zirconium-base amorphous alloy aluminum or aluminum alloy composite and dyeing zirconium-base amorphous alloy aluminum or aluminum alloy composite and preparation method Download PDFInfo
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- CN107663618A CN107663618A CN201610613156.6A CN201610613156A CN107663618A CN 107663618 A CN107663618 A CN 107663618A CN 201610613156 A CN201610613156 A CN 201610613156A CN 107663618 A CN107663618 A CN 107663618A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
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- 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
- C25D11/18—After-treatment, e.g. pore-sealing
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- 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
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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Abstract
The present invention relates to the field of compound material of zirconium-base amorphous alloy and aluminum or aluminum alloy, discloses a kind of zirconium-base amorphous alloy aluminum or aluminum alloy composite and dyeing zirconium-base amorphous alloy aluminum or aluminum alloy composite its preparation method.Method includes：(1) under vacuum or argon gas atmosphere, will at least one piece of zirconium-base amorphous alloy and at least one piece of aluminum or aluminum alloy is put together, hot pressing temperature is heated to 10~50 DEG C/min of heating rate since normal temperature；(2) under the hot pressing temperature, the zirconium-base amorphous alloy and the aluminum or aluminum alloy are pressurizeed, the strain rate for making the zirconium-base amorphous alloy and the aluminum or aluminum alloy is 0.1%/s~1%/s；Pressing time is 50~500s；(3) 100~500s of pressurize is carried out under the pressure reached at the end of step (2) described pressurization, then cools down to obtain zirconium-base amorphous alloy aluminum or aluminum alloy composite.This method is simple and easy, and obtained composite bond strength is big.
Description
Technical field
The present invention relates to zirconium-base amorphous alloy and Al alloy composite preparation field, in particular it relates to which a kind of zirconium base is non-
Peritectic alloy-aluminum or aluminum alloy composite material and preparation method thereof, the zirconium-base amorphous alloy that this method obtains-aluminum or aluminum alloy composite wood
Material, and the dyeing zirconium base that the preparation method of dyeing zirconium-base amorphous alloy-aluminum or aluminum alloy composite and this method obtain are non-
Peritectic alloy-aluminum or aluminum alloy composite.
Background technology
Non-crystaline amorphous metal has the characteristic of high intensity, high abrasion and highly corrosion resistant, such as zirconium-base amorphous alloy, in high-end 3C Product
Upper application has very big potentiality.
Aluminium alloy is often applied to 3C Product by the shell or parts as 3C Product, therefore by non-crystaline amorphous metal at present,
Compound with aluminium alloy turns into key.
CN103993314A discloses a kind of surface treatment method of non-crystaline amorphous metal, including 1) cold spraying：Dividing peritectic alloy
Surface one layer of aluminum metal layer or aluminium alloy layer are sprayed by the method for cold spraying, obtain semi-finished product；2) anodized：Will
The aluminum metal layer or aluminium alloy layer of the semi-finished product carry out anodization, form aluminum metal layer or the aluminium alloy layer surface
Aluminum oxide film, obtain finished product.Wherein the thickness of aluminum metal layer or aluminium alloy layer is 5~100 μm.
CN103029368A discloses a kind of Composite metal shell, including aluminium alloy outer layer, and outside the aluminium alloy
The zirconium-base amorphous alloy internal layer of die cast in layer.Wherein, the thickness of zirconium-base amorphous alloy internal layer is 0.3~0.6mm, aluminium alloy
The thickness of outer layer is 0.9~3.6mm.Corresponding preparation method step includes：(1) casing blank that aluminum alloy base material is formed is put
In in vacuum mold die cavity and locked mode；(2) zirconium-base amorphous alloy is heated under vacuum being molten into melt, Ran Houyong
Die casting machine fills the melt to mold cavity at 550~650 DEG C, until forming zirconium-base amorphous alloy structure, so
The demoulding obtains product after pressurize 15s~25s afterwards.The aluminium that this method is easily damaged due to the high temperature of melt in mold cavity closes
Gold.
CN102921926A discloses a kind of complex of aluminum or aluminum alloy and non-crystaline amorphous metal, including aluminum or aluminum alloy base
Body and injection are incorporated into the non-crystaline amorphous metal body of aluminum or aluminum alloy matrix surface, are characterised by, the aluminum or aluminum alloy matrix passes through sun
Pole oxidation processes make its surface form a pellumina, and the pellumina surface is closed formed with some nano-pores, the amorphous
Gold is incorporated into surface of the pellumina formed with some nano-pores.Its disclosed method is：Aluminum or aluminum alloy is provided
Matrix；Anodized is carried out to aluminum or aluminum alloy matrix, the aluminum or aluminum alloy matrix surface is formed a pellumina, and
The pellumina surface is formed with some nano-pores；The aluminum or aluminum alloy matrix is preheated；Aluminium or aluminium after will be preheated
Alloy substrate is placed in injecting molding die, and amorphous alloy material is injected in into aluminum or aluminum alloy matrix surface forms non-crystaline amorphous metal
Body, is made the complex, 5 DEG C of the glass transition temperature ﹢ and non-crystaline amorphous metal of the temperature of the non-crystaline amorphous metal between non-crystaline amorphous metal
Between -10 DEG C of crystallization temperature.
By spraying means, either material surface handles or re-formed non-crystaline amorphous metal body to prior art, is prepared with realizing
The composite of non-crystaline amorphous metal and aluminum or aluminum alloy.Obtained zirconium-base amorphous alloy and the composite of aluminum or aluminum alloy, it is impossible to
Sandwich construction is provided；Can not aluminum or aluminum alloy layer it is thicker, it is aluminum or aluminum alloy thin layer to be only capable of.Prior art processes are complicated and not
Easy industrializing implementation.And prior art can not obtain the thicker aluminium alloy layer of thickness on non-crystaline amorphous metal, such as spraying is only
Relatively thin aluminium alloy covered can occur, it is impossible to which realization reaches thicker thickness.
It can be seen that the, it is necessary to method of the more easy suitable composite for preparing non-crystaline amorphous metal and aluminum or aluminum alloy.
The content of the invention
The invention aims to solve how to prepare to answer with multilayer zirconium-base amorphous alloy, multilayer aluminum or aluminum alloy
Close, and the composite that aluminum or aluminum alloy layer is thicker, there is provided a kind of zirconium-base amorphous alloy-aluminum or aluminum alloy composite and dye
Color zirconium-base amorphous alloy-aluminum or aluminum alloy composite and preparation method.
To achieve these goals, the present invention provides a kind of zirconium-base amorphous alloy-aluminum or aluminum alloy composite of preparing
Method, including：(1), will at least one piece of zirconium-base amorphous alloy and at least one piece of aluminum or aluminum alloy under vacuum or argon gas atmosphere
Put together, hot pressing temperature is heated to 10~50 DEG C/min of heating rate since normal temperature；The hot pressing temperature meets：Institute
State the supercooling of glass transition temperature+(0.3~0.8) × zirconium-base amorphous alloy of hot pressing temperature=zirconium-base amorphous alloy
Liquid phase sector width；(2) under the hot pressing temperature, the zirconium-base amorphous alloy and the aluminum or aluminum alloy is pressurizeed, made
The strain rate of the zirconium-base amorphous alloy and the aluminum or aluminum alloy is 0.1%/s~1%/s；Pressing time be 50~
500s；(3) 100~500s of pressurize is carried out under the pressure reached at the end of step (2) described pressurization, then cools down to obtain zirconium base non-
Peritectic alloy-aluminum or aluminum alloy composite；Wherein, the supercooled liquid phase sector width is the gamma transition of the zirconium-base amorphous alloy
Temperature difference between the crystallization temperature of temperature and the zirconium-base amorphous alloy；The strain rate is the unit under the pressurization
The overall dimensional contraction percentage of the zirconium-base amorphous alloy and the aluminum or aluminum alloy in time.
Present invention also offers zirconium-base amorphous alloy-aluminum or aluminum alloy composite made from a kind of method of the invention.
Present invention also offers a kind of colouring method of zirconium-base amorphous alloy of the invention-aluminum or aluminum alloy composite,
Including：(I) zirconium-base amorphous alloy-aluminum or aluminum alloy composite is subjected to anodic oxidation；Anodic oxidation solution is concentration
160~200g/L sulfuric acid solution, anodic oxidation voltage are 14~16V, and anodizing temperature is 19~20 DEG C, during anodic oxidation
Between be 30~45min；(II) product that step (I) obtains is put into coloring agent, contaminated at 35~50 DEG C of dyeing temperature
5~15min of color, then fully cleaned using clear water；(III) product that step (III) obtains is put into pore-sealing liquid, in sealing of hole
3~8min of sealing of hole is carried out at 90~100 DEG C of temperature；(IV) product that step (IV) obtains is subjected to drying 5 at 90~120 DEG C
~15min.
Zirconium-base amorphous alloy-aluminum or aluminum alloy is dyed as made from the colouring method of the present invention present invention also offers a kind of
Composite.
Pass through above-mentioned technical proposal, can by simplicity process realize production have multilayer zirconium-base amorphous alloy with
The composite of multilayer aluminum or aluminum alloy, and have high bond strength between zirconium-base amorphous alloy layer and aluminum or aluminum alloy layer.And
And in the composite prepared, can have thicker zirconium-base amorphous alloy layer, aluminum or aluminum alloy layer.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the schematic diagram of the composite with multilayer zirconium-base amorphous alloy and multilayer aluminum or aluminum alloy.
Description of reference numerals
1st, aluminum or aluminum alloy layer 2, zirconium-base amorphous alloy layer
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of method for preparing zirconium-base amorphous alloy-aluminum or aluminum alloy composite, including：(1) true
Under empty or argon gas atmosphere, will at least one piece of zirconium-base amorphous alloy and at least one piece of aluminum or aluminum alloy is put together, from normal temperature
Start to be heated to hot pressing temperature with 10~50 DEG C/min of heating rate；The hot pressing temperature meets：The hot pressing temperature=described
The supercooled liquid phase sector width of the glass transition temperature of zirconium-base amorphous alloy+(0.3~0.8) × zirconium-base amorphous alloy；(2) exist
Under the hot pressing temperature, the zirconium-base amorphous alloy and the aluminum or aluminum alloy are pressurizeed, make the zirconium-base amorphous alloy
Strain rate with the aluminum or aluminum alloy is 0.1%/s~1%/s；Pressing time is 50~500s；(3) in step (2) institute
State and carry out 100~500s of pressurize under the pressure that reaches at the end of pressurization, then cool down to obtain zirconium-base amorphous alloy-aluminum or aluminum alloy multiple
Condensation material；Wherein, the supercooled liquid phase sector width be the zirconium-base amorphous alloy glass transition temperature with it is described zirconium-base amorphous
Temperature difference between the crystallization temperature of alloy；The strain rate be under the pressurization, it is described zirconium-base amorphous in the unit interval
The overall dimensional contraction percentage of alloy and the aluminum or aluminum alloy.
In the present invention, the strain rate can be by measuring the zirconium-base amorphous alloy and the aluminum or aluminum alloy
It is overall on the action direction for the pressure born, the contraction change of size determines.Stressed thing can also be applied by control
Displacement of the body on pressure action direction, bearing displacement and the entirety of the zirconium-base amorphous alloy and the aluminum or aluminum alloy
Pressure action direction on original dimension (when being not affected by pressure) percentage within above range.
In the present invention, when setting the hot pressing temperature, it is multiplied with the supercooled liquid phase sector width of the zirconium-base amorphous alloy
Coefficient range is 0.3~0.8.When the coefficient is less than 0.3, the zirconium-base amorphous alloy is in the harder stage, is not easy to add
Work；When the coefficient is more than 0.8, the risk of the zirconium-base amorphous alloy crystallization in process be present.
The method of the present invention can be realized by hot pressing prepares answering for multilayer zirconium-base amorphous alloy and multilayer aluminum or aluminum alloy
Condensation material.
In the present invention, the vacuum pressure of step (1) is less than ﹣ 0.1MPa.
According to the present invention, the zirconium-base amorphous alloy can be not particularly limited, and can be zirconium commonly used in the art
Base noncrystal alloy, under preferable case, the composition of the zirconium-base amorphous alloy can contain 30~65 weight %Zr, 25~45 weights
Measure %Cu, 5~18 weight %Al, 2~13 weight %Ni, 0~4 weight %Fe, 0~4 weight %Mg and 0~4 weight %Nb.Tool
Body, such as Zr48Cu33Al10Ni9、Zr50Cu23Al10Ni7、Zr37Cu35Al13Ni15。
In the method for the present invention, the temperature conditionss for carrying out hot pressing are set according to some temperature parameters of the zirconium-base amorphous alloy
It is fixed.It can be tested by DSC, determine glass transition temperature, the crystallization temperature of the zirconium-base amorphous alloy, and calculated relative
The supercooled liquid phase sector width answered.
Such as certain zirconium-base amorphous material, its glass transition temperature is measured as 440 DEG C, and crystallization temperature is 500 DEG C, corresponding
Supercooled liquid phase sector width be 60 DEG C, then in step (1), hot pressing temperature meet：440 DEG C+(0.3~0.8) × 60 DEG C=458
~488 DEG C.Hot pressing temperature can typically be set as 460 DEG C.
In the present invention, the thickness of the zirconium-base amorphous alloy can not limited, such as more than 0 and can be below 2cm.
According to the present invention, there is no particular limitation for the aluminium alloy, can be aluminium alloy commonly used in the art, preferably
In the case of, the composition of the aluminum or aluminum alloy contains 85~100 weight %Al, 0~1 weight %Si, 0~1 weight %Fe, 0~3
Weight %Cu, 0~2 weight %Mn, 0~2.5 weight %Mg, 0~0.5 weight %Cr, 0~1 weight %Ni, 0~1 weight %Zn
With 0~0.5 weight %Ti.Can the aluminium alloy be 6 commercially available line aluminium alloys.Specifically, such as aluminium alloy 6061, aluminium alloy
6063。
According to the present invention it is possible to the thickness of the aluminum or aluminum alloy is unrestricted, and under preferable case, the aluminum or aluminum alloy
Thickness can be more than 0 and be below 2cm.
In the method and step (1) of the present invention, the normal temperature can be 15~40 DEG C.
In the method for the present invention, when carrying out step (1), do not pressurize.Hot press pair can be used since step (2)
The zirconium-base amorphous alloy applies pressure with the overall of the aluminum or aluminum alloy.Can be by the zirconium-base amorphous alloy and the aluminium
Or aluminium alloy is placed in hot pressing die, such as stacking is placed, and applying pressure makes the zirconium-base amorphous alloy be closed with the aluminium or aluminium
Gold is realized compound.Whether described to apply stressed size suitable, can be closed according to the zirconium-base amorphous alloy and the aluminium or aluminium
The entirety of gold is in the case where bearing pressure, and the deformation of generation is controlled, such as controlled strain speed.In the present invention, the strain rate
It is on the basis of the overall size of the zirconium-base amorphous alloy and the aluminum or aluminum alloy.
According to the present invention, method of the invention can realize the zirconium-base amorphous alloy of composite multi-layer, aluminum or aluminum alloy.It is preferred that
In the case of, the composite contains zirconium-base amorphous alloy described in polylith and during aluminum or aluminum alloy, the zirconium base is non-described in polylith
Alternately laminated mode is taken to be in contact between peritectic alloy and the aluminum or aluminum alloy.As shown in Figure 1.
In the case of, according to the invention it is preferred to, before step (1), the aluminum or aluminum alloy is subjected to surface degreasing, step
Including：
(a) aluminum or aluminum alloy is inserted in the wax removing agent that concentration is 40~60g/L, in the bar that temperature is 50~65 DEG C
2~4min is soaked under part, taking-up is fully cleaned using clear water；
(b) product for obtaining step (b) is put into the cleaning agent that concentration is 40~60g/L, is 50~65 DEG C in temperature
Under conditions of soak 2~4min, further take out and fully cleaned using clear water.
In the present invention, the wax removing agent can be conventional use of wax removing agent, can be used for example as cleaning agent for commercially available
Hydrocarbon solvent E7000；The cleaning agent can be conventional use of cleaning agent, can be commercially available such as aqueous cleaning agent
ED-38C。
Present invention also offers zirconium-base amorphous alloy-aluminum or aluminum alloy composite made from a kind of method of the invention.
The composite contains at least one zirconium-base amorphous alloy layer and at least one in the case of, according to the invention it is preferred to
Aluminum or aluminum alloy layer；Stacking is alternateed between the zirconium-base amorphous alloy layer and the aluminum or aluminum alloy layer.
The present invention can not limit on the thickness of obtained composite, can by the zirconium-base amorphous alloy layer,
The respective thickness of aluminum or aluminum alloy layer, and the compound number of plies determine.
According to the present invention, there is good bond strength in the composite, between different layers, it is described under preferable case
Bond strength between zirconium-base amorphous alloy layer and aluminium lamination or aluminium alloy layer that composite contains is 20~100MPa.
Present invention also offers a kind of colouring method of zirconium-base amorphous alloy of the invention-aluminum or aluminum alloy composite,
Including：(I) zirconium-base amorphous alloy-aluminum or aluminum alloy composite is subjected to anodic oxidation；Anodic oxidation solution is concentration
160~200g/L sulfuric acid solution, anodic oxidation voltage are 14~16V, and anodizing temperature is 19~20 DEG C, during anodic oxidation
Between be 30~45min；(II) product that step (I) obtains is put into coloring agent, contaminated at 35~50 DEG C of dyeing temperature
5~15min of color, then fully cleaned using clear water；(III) product that step (III) obtains is put into pore-sealing liquid, in sealing of hole
3~8min of sealing of hole is carried out at 90~100 DEG C of temperature；(IV) product that step (IV) obtains is subjected to drying 5 at 90~120 DEG C
~15min.
In the present invention, the pore-sealing liquid can be the pore-sealing liquid that commercial grade is Top Seal DX-500.The coloring agent
Can be the coloring agent of the commercially available padding that can be used for aluminum or aluminum alloy, such as wild dyestuff difficult to understand；Color can be according to need
Determine, it is commercially available.
Zirconium-base amorphous alloy-aluminum or aluminum alloy is dyed as made from the colouring method of the present invention present invention also offers a kind of
Composite.
In the present invention, the pressure being related to is gauge pressure.
The present invention will be described in detail by way of examples below.
In following examples, the glass transition temperature of zirconium-base amorphous alloy, crystallization temperature are according to GB/T13464-2008's
Material heat endurance thermal analysis test method determines.
By by composite, in contact engaging and separating force experimental machine, (Dongguan City milligram surveys the limited public affairs of instrument to the bond strength of composite
The 1220SAR of department) on, zirconium-base amorphous alloy layer is fixed respectively and aluminum or aluminum alloy layer carries out pulling capacity test and determined.
Embodiment 1
This example demonstrates that prepare method and the zirconium-base amorphous alloy-aluminium conjunction of zirconium-base amorphous alloy-Al alloy composite
The colouring method of metal/composite material.
(1) zirconium-base amorphous alloy-Al alloy composite.Zirconium-base amorphous alloy (Zr48Cu33Al10Ni9).Carry out DSC surveys
Examination, it is 420 DEG C to draw glass transition temperature, and crystallization temperature is 500 DEG C, and corresponding supercooled liquid phase sector width is 80 DEG C；Setting
Hot pressing temperature is 450 DEG C.Cut the cuboid that the zirconium-base amorphous alloy is 100mm × 100mm × 15mm (length × width × height)；
Aluminium alloy (6061, be cut into the cuboid of 100mm × 100mm × 15mm (length × width × height)) is inserted into concentration is
In 50g/L wax removing agent (cleaning agent E7000), 4min is soaked under temperature 60 C, taking-up is fully cleaned using clear water；Then put
Enter in the cleaning agent (aqueous cleaning agent ED-38C) that concentration is 50g/L, 4min is soaked under temperature 60 C, remove aluminum alloy surface
Grease, taking-up fully cleaned using clear water；
Between two blocks of aluminium alloys after zirconium-base amorphous alloy is positioned over except grease, it is put into together in hot pressing die.First will
Vacuumized in mould, vacuum pressure is ﹣ 0.01MPa.Since 30 DEG C, heated with 20 DEG C/min of heating rate, reach heat
Press 450 DEG C of temperature.After reaching the temperature, pressurizeed, strain rate 0.5%/s, pressing time 120s；Terminated with pressurization
When the pressure that reaches carry out pressurize 180s after cool down, obtain zirconium-base amorphous alloy-Al alloy composite M-1.
The gross thickness for measuring M-1 is 25mm, and wherein zirconium-base amorphous alloy thickness degree is 10mm, and aluminium alloy layer thickness is
15mm。
M-1 is combined strength test, is as a result 75MPa.
(2) zirconium-base amorphous alloy-Al alloy composite dyeing.Zirconium-base amorphous alloy-Al alloy composite M-1 is entered
Row anodized, anodic oxidation solution be 180g/L sulfuric acid solution, anodic oxidation voltage 15V, anodizing temperature
For 19 DEG C, anodizing time 40min；
M-1 after anodized is put into coloring agent (difficult to understand wild dyestuff-red), carried out at 45 DEG C of dyeing temperature
6min is dyed, taking-up is fully cleaned using clear water.
M-1 after dyeing processing is positioned in Top Seal DX-500, and sealing of hole 6min is carried out at 95 DEG C of sealing of hole temperature.
M-1 after sealing of hole is taken out and dries 10min at 120 DEG C.
Obtain dyeing zirconium-base amorphous alloy-Al alloy composite N-1.
Embodiment 2
This example demonstrates that prepare the method and zirconium-base amorphous alloy-aluminium composite wood of zirconium-base amorphous alloy-aluminium composite material
The colouring method of material.
(1) zirconium-base amorphous alloy-Al alloy composite.Zirconium-base amorphous alloy (Zr50Cu23Al10Ni7), carry out DSC surveys
Examination, it is 440 DEG C to draw glass transition temperature, and crystallization temperature is 520 DEG C and corresponding supercooled liquid phase sector width is 80 DEG C；If
Rule hot pressing temperature is 480 DEG C.It is 200mm × 200mm × 20mm to cut the zirconium-base amorphous alloy.(length × width × height) it is rectangular
Body；
It is removing for 60g/L that aluminium (cuboid for being cut into 200mm × 200mm × 30mm (length × width × height)) is inserted into concentration
In cerate, 3min is soaked under temperature 50 C, taking-up is fully cleaned using clear water；Then the cleaning agent that concentration is 40g/L is inserted
In, 2min is soaked at 65 DEG C of temperature, removes the grease of aluminium surface, taking-up is fully cleaned using clear water；
Between three blocks of aluminium after two pieces of zirconium-base amorphous alloys are positioned over except grease (zirconium-base amorphous alloy interlocks with aluminium), one
Rise and be put into hot pressing die.Argon gas protection will be first filled with mould, since 20 DEG C, is added with 30 DEG C/min of heating rate
Heat, reach 480 DEG C of hot pressing temperature.After reaching the temperature, pressurizeed, strain rate 0.3%/s, pressing time 200s；
The pressure reached at the end of with pressurization cools down after carrying out pressurize 380s, obtains zirconium-base amorphous alloy-aluminium composite material M-2.
The gross thickness for measuring M-2 is 46mm., wherein zirconium-base amorphous alloy thickness degree is 16mm, aluminum layer thickness 30mm.
M-2 is combined strength test, is as a result 66MPa
(2) zirconium-base amorphous alloy-aluminium composite material dyeing.Zirconium-base amorphous alloy-aluminium composite material M-2 is subjected to anodic oxygen
Change is handled, and anodic oxidation solution is 160g/L sulfuric acid solution.Anodic oxidation voltage is 15V, and anodizing temperature is 19 DEG C, sun
Pole oxidization time is 45min；
M-2 after anodized is put into coloring agent, dyeing 15min is carried out at 35 DEG C of dyeing temperature, is taken out
Fully cleaned using clear water.
M-2 after dyeing processing is positioned in Top Seal DX-500, and sealing of hole 3min is carried out at 90 DEG C of sealing of hole temperature.
M-2 after sealing of hole is taken out and dries 15min at 100 DEG C.
Obtain dyeing zirconium-base amorphous alloy-aluminium composite material N-2.
Embodiment 3
This example demonstrates that prepare method and the zirconium-base amorphous alloy-aluminium conjunction of zirconium-base amorphous alloy-Al alloy composite
The colouring method of metal/composite material.
(1) zirconium-base amorphous alloy-Al alloy composite.Zirconium-base amorphous alloy (Zr37Cu35Al13Ni15), carry out DSC surveys
Examination, it is 380 DEG C to draw glass transition temperature, and crystallization temperature is 470 DEG C and corresponding supercooled liquid phase sector width is 90 DEG C；If
Hot pressing temperature is determined for 430 DEG C.Cut the cuboid that the zirconium-base amorphous alloy is 150 × 250 × 10mm (length × width × height)；
It is 40g/L that aluminium alloy 6063 (cuboid for being cut into 150 × 250 × 10mm (length × width × height)) is inserted into concentration
Wax removing agent in, 2min is soaked at 65 DEG C of temperature, taking-up is fully cleaned using clear water；Then it is the clear of 60g/L to insert concentration
In lotion, 3min is soaked under temperature 50 C, removes the grease of aluminum alloy surface, taking-up is fully cleaned using clear water；
Between four blocks of aluminium alloys after three pieces of zirconium-base amorphous alloys are positioned over except grease (as shown in Figure 1), it is put into together
In hot pressing die.Argon gas protection will be first filled with mould, since 40 DEG C, is heated, reached with 10 DEG C/min of heating rate
430 DEG C of hot pressing temperature.After reaching the temperature, pressurizeed, strain rate 0.2%/s, pressing time 300s；With the knot that pressurizes
The pressure reached during beam cools down after carrying out pressurize 480s, obtains zirconium-base amorphous alloy-Al alloy composite M-3.
The gross thickness for measuring M-3 is 47mm., wherein zirconium-base amorphous alloy thickness degree is 7mm, and aluminium alloy layer thickness is
40mm。
M-2 is combined strength test, is as a result 80MPa.
(2) zirconium-base amorphous alloy-Al alloy composite dyeing.Zirconium-base amorphous alloy-Al alloy composite M-2 is entered
Row anodized, anodic oxidation solution be 180g/L sulfuric acid solution, anodic oxidation voltage 14V, anodizing temperature
For 20 DEG C, anodizing time 30min；
M-3 after anodized is put into coloring agent, carries out dyeing 6min at 40 DEG C of dyeing temperature, taking-up makes
Fully cleaned with clear water.
M-3 after dyeing processing is positioned in Top Seal DX-500, and sealing of hole 6min is carried out at 95 DEG C of sealing of hole temperature.
M-3 after sealing of hole is taken out and dries 5min at 110 DEG C.
Obtain dyeing zirconium-base amorphous alloy-Al alloy composite N-3.
As can be seen from the above embodiments, method of the invention can be prepared containing zirconium-base amorphous alloy layer and the conjunction of aluminium or aluminium
The thicker composite of layer gold thickness, and there is good bond strength.
Method provided by the invention uses the form of hot pressing, simple to operation, beneficial to industrializing implementation.
Claims (10)
1. a kind of method for preparing zirconium-base amorphous alloy-aluminum or aluminum alloy composite, including：
(1), will at least one piece of zirconium-base amorphous alloy and at least one piece of aluminum or aluminum alloy is placed under vacuum or argon gas atmosphere
Together, hot pressing temperature is heated to 10~50 DEG C/min of heating rate since normal temperature；The hot pressing temperature meets：
The glass transition temperature of the hot pressing temperature=zirconium-base amorphous alloy+(0.3~the 0.8) × zirconium-base amorphous alloy
Supercooled liquid phase sector width；
(2) under the hot pressing temperature, the zirconium-base amorphous alloy and the aluminum or aluminum alloy are pressurizeed, make the zirconium base
The strain rate of non-crystaline amorphous metal and the aluminum or aluminum alloy is 0.1%/s~1%/s；Pressing time is 50~500s；
(3) 100~500s of pressurize is carried out under the pressure reached at the end of step (2) described pressurization, then cools down to obtain zirconium base non-
Peritectic alloy-aluminum or aluminum alloy composite；
Wherein, the supercooled liquid phase sector width is the glass transition temperature of the zirconium-base amorphous alloy and the zirconium-base amorphous alloy
Crystallization temperature between temperature difference；The strain rate is the zirconium-base amorphous alloy in the unit interval under the pressurization
With the overall dimensional contraction percentage of the aluminum or aluminum alloy.
2. according to the method for claim 1, wherein, the composition of the zirconium-base amorphous alloy contain 30~65 weight %Zr,
25~45 weight %Cu, 5~18 weight %Al, 2~13 weight %Ni, 0~4 weight %Fe, 0~4 weight %Mg and 0~4 weight
Measure %Nb.
3. method according to claim 1 or 2, wherein, the composition of the aluminum or aluminum alloy contains 85~100 weight %
Al, 0~1 weight %Si, 0~1 weight %Fe, 0~3 weight %Cu, 0~2 weight %Mn, 0~2.5 weight %Mg, 0~0.5
Weight %Cr, 0~1 weight %Ni, 0~1 weight %Zn and 0~0.5 weight %Ti.
4. according to the method described in any one in claim 1-3, wherein, it is non-that the composite contains zirconium base described in polylith
Peritectic alloy described in polylith between the zirconium-base amorphous alloy and the aluminum or aluminum alloy with during aluminum or aluminum alloy, taking alternately laminated
Mode be in contact.
5. according to the method described in any one in claim 1-4, wherein, before step (1), by the aluminum or aluminum alloy
Surface degreasing is carried out, step includes：
(a) aluminum or aluminum alloy is inserted in the wax removing agent that concentration is 40~60g/L, under conditions of temperature is 50~65 DEG C
2~4min is soaked, taking-up is fully cleaned using clear water；
(b) product for obtaining step (b) is put into the cleaning agent that concentration is 40~60g/L, in the bar that temperature is 50~65 DEG C
2~4min is soaked under part, further takes out and is fully cleaned using clear water.
6. zirconium-base amorphous alloy-aluminum or aluminum alloy made from a kind of method in 1-5 as claim described in any one is compound
Material.
7. composite according to claim 6, wherein, the composite contains at least one zirconium-base amorphous alloy layer
With at least one aluminum or aluminum alloy layer；Stacking is alternateed between the zirconium-base amorphous alloy layer and the aluminum or aluminum alloy layer.
8. according to claim 6 or 7, wherein, in the composite, the zirconium-base amorphous alloy layer and the aluminium or
Bond strength between aluminium alloy layer is 20~100MPa.
A kind of 9. dyeing side of zirconium-base amorphous alloy-aluminum or aluminum alloy composite in claim 6-8 described in any one
Method, including：
(I) zirconium-base amorphous alloy-aluminum or aluminum alloy composite is subjected to anodic oxidation；Anodic oxidation solution is concentration
160~200g/L sulfuric acid solution, anodic oxidation voltage are 14~16V, and anodizing temperature is 19~20 DEG C, during anodic oxidation
Between be 30~45min；
(II) product that step (I) obtains is put into coloring agent, 5~15min of dyeing is carried out at 35~50 DEG C of dyeing temperature,
Then fully cleaned using clear water；
(III) product that step (III) obtains is put into pore-sealing liquid, carried out at 90~100 DEG C of sealing of hole temperature sealing of hole 3~
8min；
(IV) product that step (IV) obtains is subjected to 5~15min of drying at 90~120 DEG C.
10. zirconium-base amorphous alloy-aluminum or aluminum alloy composite wood is dyed made from a kind of colouring method as described in claim 9
Material.
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| CN113369663A (en) * | 2019-01-08 | 2021-09-10 | 浙江大学台州研究院 | Thermoplastic connection method of amorphous alloy |
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