CN108220828A - A kind of amorphous alloy composite material and its preparation method and application - Google Patents
A kind of amorphous alloy composite material and its preparation method and application Download PDFInfo
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- CN108220828A CN108220828A CN201810089861.XA CN201810089861A CN108220828A CN 108220828 A CN108220828 A CN 108220828A CN 201810089861 A CN201810089861 A CN 201810089861A CN 108220828 A CN108220828 A CN 108220828A
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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
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
Abstract
The invention discloses a kind of amorphous alloy composite material, including being prepared with the following raw material of weight：Amorphous alloy material 97 99.9%, nitration mixture modified carbon nano-tube 0.1 3%；Wherein, the nitration mixture modified carbon nano-tube is 1 by weight ratio:10 20 carbon nanotube and nitration mixture is prepared.The invention also discloses a kind of preparation method and application of amorphous alloy composite material.The method of the present invention carries out chemical modification using nitration mixture oxidizing process to carbon nanotube, can improve dispersibility of the carbon nanotube in amorphous alloy material, improve binding force between carbon nanotube and amorphous alloy material；There is good toughness and plastic deformation ability, while have the characteristics that microstructure is uniform, interface cohesion is good using the amorphous alloy composite material that this method is prepared.
Description
Technical field
The present invention relates to a kind of amorphous alloy material more particularly to a kind of amorphous alloy composite material and preparation method thereof and
Using.
Background technology
Amorphous alloy material has high specific strength, specific modulus, higher hardness, wear-resisting and corrosion resistance, is navigating
It is applied and causes more and more concerns in the fields such as empty space flight, motor racing product.But since non-crystaline amorphous metal does not have
It is plastically deformed, after arrival elastic limit and the characteristic of failure fracture also limits its application range.Have greatly for this situation
Quantifier elimination work improves the moulding index of non-crystaline amorphous metal, such as by constituent adjustment generate in give birth to hardening constituent, at surface stress
The modes such as reason, face coat, but effect is all undesirable.
Carbon nanotube has unique structure and excellent physics, chemical property, and (its Young's modulus resists up to 1-1.8TPa
Tensile strength is up to 150GPa, and density is up to 1.2-1.8g/cm3, coefficient of thermal expansion is almost nil, while also has good toughness
And plastic deformation ability), comprehensive performance be much better than presently, there are particle or fiber, be composite material a kind of preferable enhancing
Body.However, carbon pipe large specific surface area, surface can be high, being often attached together between them with Van der Waals force, (carbon to contact with each other is received
Van der Waals combination between mitron can about 500eV/ μm) form aggregate；In addition, carbon pipe surface inertia is big, lack work
Property group, the solubility in various solvents is all very low, this is just to its dispersion in the base and they and intermetallic boundary
Face junction belt carrys out very big difficulty.
Invention content
For overcome the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of amorphous alloy composite material,
It has good toughness and plastic deformation ability, while has the characteristics that microstructure is uniform, interface cohesion is good.
The second object of the present invention is to provide a kind of preparation method of amorphous alloy composite material, and this method can improve
Dispersibility of the carbon nanotube in amorphous alloy material improves binding force between carbon nanotube and amorphous alloy material；Using
The amorphous alloy composite material that this method is prepared has good toughness and plastic deformation ability, while has microstructure
Uniformly, the characteristics of interface cohesion is good.
The third object of the present invention is to provide a kind of application of amorphous alloy composite material.
An object of the present invention adopts the following technical scheme that realization：
A kind of amorphous alloy composite material, which is characterized in that including the following raw material preparation with weight
Into：Amorphous alloy material 97-99.9%, nitration mixture modified carbon nano-tube 0.1-3%；Wherein, the nitration mixture modified carbon nano-tube by
Weight ratio is 1:The carbon nanotube and nitration mixture of 10-20 is prepared.
Further, the nitration mixture includes the concentrated sulfuric acid and concentrated nitric acid, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 4:1-1.5.
Further, a diameter of 10-100nm of the carbon nanotube, length are 2-80 μm.
Further, the amorphous alloy material is zirconium-base amorphous alloy, in titanium-based amorphous alloy, al based amorphous alloy
It is a kind of.
The second object of the present invention adopts the following technical scheme that realization：
A kind of preparation method of amorphous alloy composite material, which is characterized in that including：
The preparation process of nitration mixture modified carbon nano-tube：The carbon nanotube of formula ratio is added in the nitration mixture of formula ratio, ultrasound
1-2h is handled, plasma water is then added in and cleans to neutrality, be put into drying box and be dried, after drying completely, obtain nitration mixture
Modified carbon nano-tube, it is spare；
Ball milling, pressing step：The nitration mixture modified carbon nano-tube of the amorphous alloy material of formula ratio and formula ratio is packed into ball
In the ball grinder of grinding machine, it is passed through liquid nitrogen and carries out low temperature ball milling；After ball milling, ball grinder is opened and is stood, after liquid nitrogen volatilization,
Obtain dry mixed-powder；Then by dry mixed-powder briquet, blocky mixture is obtained；
Hot briquetting step：Blocky mixed material heating to non-crystaline amorphous metal is melted, the amorphous comprising carbon nanotube is formed and closes
Gold melting master alloy；Then it is molded by way of die casting, casting or spraying, after cooling, obtains amorphous alloy composite material.
Further, in the preparation process of nitration mixture modified carbon nano-tube, the drying temperature of drying box is 80-98 DEG C.
Further, in ball milling, pressing step, the rotating speed of ball mill is 80-500r/min, Ball-milling Time 0.5-10h,
Temperature is room temperature, and ball material mass ratio is 1:5-50, Material quality of grinding balls be steel or ceramics, a diameter of 3-15mm.
Further, in ball milling, pressing step, time of repose 2-4h, pressing pressure 10-150MPa, the pressing time
For 15s-5min.
Further, in hot briquetting step, mode of heating is resistance heating or sensing heating.
The third object of the present invention adopts the following technical scheme that realization：
Application of a kind of amorphous alloy composite material in consumer electronics product shell, outside the consumer electronics product
Shell is selected from cellular phone, tablet computer, PDA, portable computer, digital camera, navigator, unmanned plane, remote-controlled robot, VR
A kind of shell of equipment in glasses.
The beneficial effects of the present invention are：
The amorphous alloy composite material of the present invention is prepared by amorphous alloy material and nitration mixture modified carbon nano-tube,
In, nitration mixture modified carbon nano-tube carries out chemical modification using nitration mixture oxidizing process to carbon nanotube, in the surface grafting of carbon nanotube
Carboxyl, hydroxyl oxygen-containing group improve dispersibility of the carbon nanotube in amorphous alloy material, improve carbon nanotube and amorphous
Binding force between alloy material, with reference to effect it is more obvious.Low temperature ball milling is carried out under liquid nitrogen environment later, makes carbon nanometer
Pipe further dispersion, and realize depth integration with non-crystaline amorphous metal matrix.The non-crystaline amorphous metal being prepared using this method is compound
Material has good toughness and plastic deformation ability, while has the characteristics that microstructure is uniform, interface cohesion is good.
Description of the drawings
Fig. 1 is that the fracture position SEM when amorphous alloy composite material of embodiment 1 passes through failure detection detects picture.
Fig. 2 is that the fracture position SEM when amorphous alloy composite material of embodiment 2 passes through failure detection detects picture.
Fig. 3 is that the fracture position SEM when amorphous alloy composite material of embodiment 3 passes through failure detection detects picture.
Fig. 4 is that the fracture position SEM when amorphous alloy composite material of embodiment 4 passes through failure detection detects picture.
Specific embodiment mode
In the following, with reference to specific embodiment, the present invention is described further, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
A kind of amorphous alloy composite material, including being prepared with the following raw material of weight：Non-crystaline amorphous metal
Material 97-99.9%, nitration mixture modified carbon nano-tube 0.1-3%；Wherein, the nitration mixture modified carbon nano-tube is 1 by weight ratio:
The carbon nanotube and nitration mixture of 10-20 is prepared.
As the mode that further carries out, the nitration mixture includes the volume of the concentrated sulfuric acid and concentrated nitric acid, the concentrated sulfuric acid and concentrated nitric acid
Than being 4:1-1.5.
As the mode that further carries out, a diameter of 10-100nm of the carbon nanotube, length is 2-80 μm.
As the mode that further carries out, the amorphous alloy material is zirconium-base amorphous alloy, titanium-based amorphous alloy, aluminium base
One kind in non-crystaline amorphous metal.
A kind of preparation method of amorphous alloy composite material, including：
The preparation process of nitration mixture modified carbon nano-tube：The carbon nanotube of formula ratio is added in the nitration mixture of formula ratio, ultrasound
1-2h is handled, plasma water is then added in and cleans to neutrality, be put into drying box and be dried, after drying completely, obtain nitration mixture
Modified carbon nano-tube, it is spare；
Ball milling, pressing step：The nitration mixture modified carbon nano-tube of the amorphous alloy material of formula ratio and formula ratio is packed into ball
In the ball grinder of grinding machine, it is passed through liquid nitrogen and carries out low temperature ball milling；After ball milling, ball grinder is opened and is stood, after liquid nitrogen volatilization,
Obtain dry mixed-powder；Then by dry mixed-powder briquet, blocky mixture is obtained；
Hot briquetting step：Blocky mixed material heating to non-crystaline amorphous metal is melted, the amorphous comprising carbon nanotube is formed and closes
Gold melting master alloy；Then it is molded by way of die casting, casting or spraying, after cooling, obtains amorphous alloy composite material.
As the mode that further carries out, in the preparation process of nitration mixture modified carbon nano-tube, the drying temperature of drying box is
80-98℃。
As the mode that further carries out, in ball milling, pressing step, the rotating speed of ball mill is 80-500r/min, during ball milling
Between for 0.5-10h, temperature is room temperature, and ball material mass ratio is 1:5-50, Material quality of grinding balls be steel or ceramics, a diameter of 3-15mm.
As the mode that further carries out, in ball milling, pressing step, time of repose 2-4h, pressing pressure 10-
150MPa, pressing time 15s-5min.
As the mode that further carries out, in hot briquetting step, mode of heating is resistance heating or sensing heating.
Application of a kind of amorphous alloy composite material in consumer electronics product shell, outside the consumer electronics product
Shell is selected from cellular phone, tablet computer, PDA, portable computer, digital camera, navigator, unmanned plane, remote-controlled robot, VR
A kind of shell of equipment in glasses.
Specific embodiment of the present invention when following, used raw material, equipment etc. remove special limit in the following embodiments
It can be obtained outside fixed by buying pattern.
Embodiment 1：
A kind of amorphous alloy composite material, including being prepared with the following raw material of weight：Non-crystaline amorphous metal
Material 98%, nitration mixture modified carbon nano-tube 2%；Wherein, the nitration mixture modified carbon nano-tube is 1 by weight ratio:15 carbon nanometer
Pipe and nitration mixture are prepared.
Amorphous alloy material is Zr59.67Hf0.97Cu12.98Al18.5Ti7.86Y0.02.
A kind of preparation method of amorphous alloy composite material, including：
The preparation process of nitration mixture modified carbon nano-tube：The carbon nanotube of formula ratio is added in the nitration mixture of formula ratio, ultrasound
1.5h is handled, plasma water is then added in and cleans to neutrality, be put into drying box and be dried, the drying temperature of drying box is 90
DEG C, after drying completely, nitration mixture modified carbon nano-tube is obtained, it is spare；
Ball milling, pressing step：The nitration mixture modified carbon nano-tube of the amorphous alloy material of formula ratio and formula ratio is packed into ball
In the ball grinder of grinding machine, it is passed through liquid nitrogen and carries out low temperature ball milling；After ball milling, ball grinder is opened and is stood, after liquid nitrogen volatilization,
Obtain dry mixed-powder；Then by dry mixed-powder briquet, blocky mixture is obtained；The rotating speed of ball mill is
250r/min, Ball-milling Time 0.8h, temperature are room temperature, and ball material mass ratio is 1:25, Material quality of grinding balls be steel or ceramics, it is a diameter of
10mm；Time of repose is 3h, pressing pressure 100MPa, pressing time 3min；
Hot briquetting step：Blocky mixed material heating to non-crystaline amorphous metal is melted, the amorphous comprising carbon nanotube is formed and closes
Gold melting master alloy；Then it is molded by way of die casting, casting or spraying, after cooling, obtains amorphous alloy composite material.
With reference to Fig. 1, amorphous alloy composite material die casting is made to the exemplar of 100 × 10 × 3mm, it is applied shearing force into
After row destroys, sem analysis is carried out in incision position, darker regions are non-crystaline amorphous metal matrix in figure, and light strip region is carbon
The cluster of nanotube enrichment, it can be seen that carbon nanotube is uniformly dispersed in non-crystaline amorphous metal matrix.
Plastic deformation detection：Three-point bending test, plastic strain 2.3%.
Embodiment 2：
A kind of amorphous alloy composite material, including being prepared with the following raw material of weight：Non-crystaline amorphous metal
Material 97%, nitration mixture modified carbon nano-tube 3%；Wherein, the nitration mixture modified carbon nano-tube is 1 by weight ratio:10 carbon nanometer
Pipe and nitration mixture are prepared.
A kind of preparation method of amorphous alloy composite material, including：
The preparation process of nitration mixture modified carbon nano-tube：The carbon nanotube of formula ratio is added in the nitration mixture of formula ratio, ultrasound
1h is handled, plasma water is then added in and cleans to neutrality, be put into drying box and be dried, the drying temperature of drying box is 80
DEG C, after drying completely, nitration mixture modified carbon nano-tube is obtained, it is spare；
Ball milling, pressing step：The nitration mixture modified carbon nano-tube of the amorphous alloy material of formula ratio and formula ratio is packed into ball
In the ball grinder of grinding machine, it is passed through liquid nitrogen and carries out low temperature ball milling；After ball milling, ball grinder is opened and is stood, after liquid nitrogen volatilization,
Obtain dry mixed-powder；Then by dry mixed-powder briquet, blocky mixture is obtained；The rotating speed of ball mill is
80r/min, Ball-milling Time 10h, temperature are room temperature, and ball material mass ratio is 1:5, Material quality of grinding balls be steel or ceramics, it is a diameter of
3mm；Time of repose is 2h, pressing pressure 50MPa, pressing time 60s；
Hot briquetting step：Blocky mixed material heating to non-crystaline amorphous metal is melted, the amorphous comprising carbon nanotube is formed and closes
Gold melting master alloy；Then it is molded by way of die casting, casting or spraying, after cooling, obtains amorphous alloy composite material.
With reference to Fig. 2, amorphous alloy composite material die casting is made to the exemplar of 100 × 10 × 3mm, it is applied shearing force into
After row destroys, sem analysis is carried out in incision position, darker regions are non-crystaline amorphous metal matrix in figure, and light strip region is carbon
The cluster of nanotube enrichment, it can be seen that carbon nanotube is uniformly dispersed in non-crystaline amorphous metal matrix.
Embodiment 3：
A kind of amorphous alloy composite material, including being prepared with the following raw material of weight：Non-crystaline amorphous metal
Material 99%, nitration mixture modified carbon nano-tube 1%；Wherein, the nitration mixture modified carbon nano-tube is 1 by weight ratio:20 carbon nanometer
Pipe and nitration mixture are prepared.
A kind of preparation method of amorphous alloy composite material, including：
The preparation process of nitration mixture modified carbon nano-tube：The carbon nanotube of formula ratio is added in the nitration mixture of formula ratio, ultrasound
2h is handled, plasma water is then added in and cleans to neutrality, be put into drying box and be dried, the drying temperature of drying box is 98
DEG C, after drying completely, nitration mixture modified carbon nano-tube is obtained, it is spare；
Ball milling, pressing step：The nitration mixture modified carbon nano-tube of the amorphous alloy material of formula ratio and formula ratio is packed into ball
In the ball grinder of grinding machine, it is passed through liquid nitrogen and carries out low temperature ball milling；After ball milling, ball grinder is opened and is stood, after liquid nitrogen volatilization,
Obtain dry mixed-powder；Then by dry mixed-powder briquet, blocky mixture is obtained；The rotating speed of ball mill is
500r/min, Ball-milling Time 0.5h, temperature are room temperature, and ball material mass ratio is 1:50, Material quality of grinding balls be steel or ceramics, it is a diameter of
15mm；Time of repose is 4h, pressing pressure 150MPa, pressing time 15s；
Hot briquetting step：Blocky mixed material heating to non-crystaline amorphous metal is melted, the amorphous comprising carbon nanotube is formed and closes
Gold melting master alloy；Then it is molded by way of die casting, casting or spraying, after cooling, obtains amorphous alloy composite material.
With reference to Fig. 3, amorphous alloy composite material hot pressing is made to the exemplar of 20 × φ 8mm, applies shearing force progress to it
After destruction, sem analysis is carried out in incision position, darker regions are non-crystaline amorphous metal matrix in figure, and light strip region is received for carbon
The cluster of mitron enrichment, it can be seen that carbon nanotube is uniformly dispersed in non-crystaline amorphous metal matrix.
Embodiment 4：
A kind of amorphous alloy composite material, including being prepared with the following raw material of weight：Non-crystaline amorphous metal
Material 99.9%, nitration mixture modified carbon nano-tube 0.1%；Wherein, the nitration mixture modified carbon nano-tube is 1 by weight ratio:15 carbon
Nanotube and nitration mixture are prepared.
A kind of preparation method of amorphous alloy composite material, including：
The preparation process of nitration mixture modified carbon nano-tube：The carbon nanotube of formula ratio is added in the nitration mixture of formula ratio, ultrasound
2h is handled, plasma water is then added in and cleans to neutrality, be put into drying box and be dried, the drying temperature of drying box is 95
DEG C, after drying completely, nitration mixture modified carbon nano-tube is obtained, it is spare；
Ball milling, pressing step：The nitration mixture modified carbon nano-tube of the amorphous alloy material of formula ratio and formula ratio is packed into ball
In the ball grinder of grinding machine, it is passed through liquid nitrogen and carries out low temperature ball milling；After ball milling, ball grinder is opened and is stood, after liquid nitrogen volatilization,
Obtain dry mixed-powder；Then by dry mixed-powder briquet, blocky mixture is obtained；The rotating speed of ball mill is
200r/min, Ball-milling Time 4h, temperature are room temperature, and ball material mass ratio is 1:10, Material quality of grinding balls be steel or ceramics, it is a diameter of
10mm；Time of repose is 3h, pressing pressure 80MPa, pressing time 4min；
Hot briquetting step：Blocky mixed material heating to non-crystaline amorphous metal is melted, the amorphous comprising carbon nanotube is formed and closes
Gold melting master alloy；Then it is molded by way of die casting, casting or spraying, after cooling, obtains amorphous alloy composite material.
With reference to Fig. 4, amorphous alloy composite material hot pressing is made to the exemplar of 20 × φ 8mm, applies shearing force progress to it
After destruction, sem analysis is carried out in incision position, darker regions are non-crystaline amorphous metal matrix in figure, and light strip region is received for carbon
The cluster of mitron enrichment, it can be seen that carbon nanotube is uniformly dispersed in non-crystaline amorphous metal matrix.
The above embodiment is only the preferred embodiment of the present invention, it is impossible to the scope of protection of the invention is limited with this,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of amorphous alloy composite material, which is characterized in that including being prepared with the following raw material of weight：
Amorphous alloy material 97-99.9%, nitration mixture modified carbon nano-tube 0.1-3%；Wherein, the nitration mixture modified carbon nano-tube is by weight
Than being 1:The carbon nanotube and nitration mixture of 10-20 is prepared.
2. amorphous alloy composite material as described in claim 1, which is characterized in that the nitration mixture includes the concentrated sulfuric acid and dense nitre
The volume ratio of acid, the concentrated sulfuric acid and concentrated nitric acid is 4:1-1.5.
3. amorphous alloy composite material as described in claim 1, which is characterized in that a diameter of 10- of the carbon nanotube
100nm, length are 2-80 μm.
4. amorphous alloy composite material as described in claim 1, which is characterized in that the amorphous alloy material is zirconium-base amorphous
One kind in alloy, titanium-based amorphous alloy, al based amorphous alloy.
A kind of 5. preparation method of amorphous alloy composite material as described in claim 1-4 any one, which is characterized in that packet
It includes：
The preparation process of nitration mixture modified carbon nano-tube：The carbon nanotube of formula ratio is added in the nitration mixture of formula ratio, be ultrasonically treated
Then 1-2h adds in plasma water and cleans to neutrality, is put into drying box and is dried, after drying completely, obtain nitration mixture modification
Carbon nanotube, it is spare；
Ball milling, pressing step：The nitration mixture modified carbon nano-tube of the amorphous alloy material of formula ratio and formula ratio is packed into ball mill
Ball grinder in, be passed through liquid nitrogen carry out low temperature ball milling；After ball milling, ball grinder is opened and is stood, after liquid nitrogen volatilization, obtained
Dry mixed-powder；Then by dry mixed-powder briquet, blocky mixture is obtained；
Hot briquetting step：Blocky mixed material heating to non-crystaline amorphous metal is melted, the non-crystaline amorphous metal comprising carbon nanotube is formed and melts
Melt master alloy；Then it is molded by way of die casting, casting or spraying, after cooling, obtains amorphous alloy composite material.
6. the preparation method of amorphous alloy composite material as claimed in claim 5, which is characterized in that nitration mixture modified carbon nano-tube
Preparation process in, the drying temperature of drying box is 80-98 DEG C.
7. the preparation method of amorphous alloy composite material as claimed in claim 5, which is characterized in that in ball milling, pressing step,
The rotating speed of ball mill is 80-500r/min, and Ball-milling Time 0.5-10h, temperature is room temperature, and ball material mass ratio is 1:5-50, mill
Ball material be steel or ceramics, a diameter of 3-15mm.
8. the preparation method of amorphous alloy composite material as claimed in claim 5, which is characterized in that in ball milling, pressing step,
Time of repose is 2-4h, pressing pressure 10-150MPa, pressing time 15s-5min.
9. the preparation method of amorphous alloy composite material as claimed in claim 5, which is characterized in that in hot briquetting step,
Mode of heating is resistance heating or sensing heating.
10. a kind of amorphous alloy composite material as described in claim 1-4 any one is in consumer electronics product shell
Application, which is characterized in that the consumer electronics product shell be selected from cellular phone, tablet computer, PDA, portable computing
Machine, digital camera, navigator, unmanned plane, remote-controlled robot, a kind of shell of equipment in VR glasses.
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| CN109434121A (en) * | 2018-11-22 | 2019-03-08 | 天津大学 | A method of Nb-Al amorphous thin layer is prepared using mechanical alloying method |
| CN110172650A (en) * | 2019-06-18 | 2019-08-27 | 河海大学 | A kind of high anti-corrosion transformer core Fe-based amorphous/carbon nano tube compound material and its preparation method and application of low-loss |
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Application publication date: 20180629 |