CN109593987A - A kind of enhanced copper alloy of copper-based aeroge and preparation method thereof - Google Patents
A kind of enhanced copper alloy of copper-based aeroge and preparation method thereof Download PDFInfo
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- CN109593987A CN109593987A CN201811596485.XA CN201811596485A CN109593987A CN 109593987 A CN109593987 A CN 109593987A CN 201811596485 A CN201811596485 A CN 201811596485A CN 109593987 A CN109593987 A CN 109593987A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next 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
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
Abstract
The invention discloses a kind of copper-based enhanced copper alloys of aeroge and preparation method thereof, belong to metal material and its preparation technical field.The mass percentage composition of the copper-based enhanced copper alloy of aeroge are as follows: zinc: 0.5%~10%, silica: 2%~8%, surplus is copper.Preparation step are as follows: ingredient, ball milling, mixing, cold moudling, pressure sintering and finished product.Cu-base composites tensile strength prepared by the present invention is higher than 300MPa, and yield strength is suitable with common copper-based Al 2 O 3 composition, and wear rate is lower than 1 × 10‑9cm3·J‑1, for heat-resistance coefficient higher than 35000, heat resistance and wear-resisting property are more preferable than copper-based Al 2 O 3 composition, therefore the wear part of material production can meet the needs of product or equipment work normally for a long time under higher temperature conditions.
Description
Technical field
The present invention relates to metal material and its preparation technical fields, are specifically related to a kind of enhanced copper conjunction of copper-based aeroge
Gold and preparation method thereof.
Background technique
Copper alloy is used as integrated circuit, traffic, boat due to its good conduction, thermal conductivity, corrosion-resistant and wear-resisting property
It, aviation, in the various fields such as ship engineering machinery conductive and heat-conductive components, brake and brake apparatus.Both at home and abroad to high temperature
The research of the Cu-base composites of lower application is long-standing, and has formd copper-base composite oxidate, carbide, boride and nitrogen
Compound etc. industrializes series of products.
As equipment is to high speed, overload direction development, wearability and heat resistance to copper base friction material propose higher
It is required that.The result of study of Cu-base composites shows: using nanometer Al2O3, nanometer ZrO2Equal nano-scale oxides increase as disperse
The copper-based nano composite material mutually prepared by force forms the hard of Dispersed precipitate using particle enhancing technology in soft tough Cu matrix
Particle improves intensity, the wearability of material, while being able to maintain copper itself high thermal conductivity, improves softening properties resistant to high temperatures,
Achieve the effect that conductive and intensity, wear-resisting property are comprehensive to improve, has the advantages that other intensifying methods are incomparable.Therefore, will
Nanometer oxide material is applied to copper-based wear-resistant material, provides new way to improve the tribological property of wear-resistant material.
According to data at home and abroad, studying at present more is Cu/Al2O3Composite material.Nano-meter SiO_22(n-SiO2) due to it
Special structure and there is the characteristics such as light weight, wear-resisting, high temperature resistant, corrosion-resistant and thermal expansion coefficient be small, thermally conductive, electric conductivity
Although being declined, higher level is remained at, and its price is only nanometer Al2O3Half.However, due to n-
SiO2Easily reunite, be not easy in Copper substrate evenly dispersed, leads to the SiO prepared2Enhance Cu-base composites performance and Cu/
Al2O3Composite material is compared to having no advantage, therefore by n-SiO2It is not much and sees for the research of Copper substrate as reinforced phase.
In recent years, Cu-base composites are increasingly used in every field as wear part.Therefore, it develops
A kind of copper-based silicon dioxide composite material with higher-strength, high-wearing feature, low cost used under high temperature environment, is allowed to
Applied to the manufacture of the fields such as aerospace, automobile hot environment brake parts, raising product quality and equipment are used
There is great meaning in service life etc..
Summary of the invention
First problem to be solved by this invention is to provide a kind of with excellent mechanical performance, antiwear heat resisting performance, height
Conductive copper-based aeroge enhances base Cu alloy material, is allowed to for industry fields such as aerospace, vehicular traffic, microelectronics.
Second Problem to be solved by this invention is to provide a kind of with excellent mechanical performance, antiwear heat resisting performance, height
The preparation method of conductive copper-based aeroge enhancing base copper alloy.
To achieve the above object, the invention provides the following technical scheme:
A kind of enhanced copper alloy of copper-based aeroge, i.e., a kind of nanoporous aerogel (SiO2) enhancing Cu-base composites,
Mass percentage composition are as follows: zinc: 0.5%~30%, aeroge (SiO2): 2%~8%, surplus is copper.
As further scheme of the invention, the mass percentage composition of the enhanced copper alloy of copper-based aeroge
Are as follows: zinc: 1%~5%, aeroge (SiO2): 3%~6%, surplus is copper.
Wherein, mass percent≤0.1% of inevitable impurity.
Role is as follows in the composite for the above components element:
Zinc: the mechanical property of Cu alloy material can be improved in solution strengthening type copper alloying element, and solid solution β phase has
The characteristics of hardness is high, good toughness, can significantly improve the wear-resisting property of copper alloy.
Aeroge (SiO2): have the function of improving wearability, hardness and anti stick to Cu-base composites.While by
Dislocation motion and Grain Boundary Sliding can be effectively hindered in its nano effect, has the function of significantly improving matrix strength；On the other hand,
The second phase of aeroge of Dispersed precipitate is due to reducing to the obstruction of electron scattering to have rush to the electric conductivity of Cu alloy material
Into effect.
The preparation method of the copper-based enhanced copper alloy of aeroge of the present invention mainly includes raw material mixing, cold-press moulding, finally
The technique of pressure sintering, specific steps include: the preparation method of copper-based silicon dioxide composite material, include the following steps: to match
Powder is weighed, all raw materials are placed in by copper powder and the nano silica ball milling in planetary high-energy ball mill in advance later
It is uniformly mixed in small-sized V-type batch mixer, it is 4~5g/cm that powder, which is then pressed into density, in punching block3Briquet；Finally will
Green compact is sintered in bell-type furnace.
In the present invention, using cathode copper, atomized zinc dust, micron silica and nano silica as raw material.It is used
The quality of raw material is as follows: electrolytic copper powder average particle size≤74 μm, purity >=99.9wt%；The average particle size of atomized zinc dust is 40
~50 μm, purity >=98wt%；Micron order SiO2Average particle size is 40~50 μm, moisture content≤1wt%；Nano-meter SiO_22It is average
Partial size is 20~40nm.
Firstly, by copper powder and nano silica in planetary high-energy ball mill 2~4h of ball milling, then with other raw materials
3~5h is remixed in V-type batch mixer together；When green compact is sintered in bell-type furnace, sintering pressure is 1.0~4.0MPa, is burnt
Junction temperature is 800~1000 DEG C, and average heating rate is 4~7 DEG C/min, protects gas using hydrogen reduction during the sintering process
Atmosphere, sintering time are 20~40min, and furnace is cooled to room temperature under last protective atmosphere, and finished product is made.
300~500MPa of tensile strength of the copper-based enhanced copper alloy of aeroge of the present invention, yield strength is 200~
300MPa, elongation are 5~15%, and dynamic friction coefficient is 0.054~0.080, confficient of static friction 0.12~0.15, wear rate
0.3~1.0 × 10-9cm3·J-1, heat-resistance coefficient 35000~50000, opposite heat resistance 1.0~1.5,5.5~8g of density
cm3, resistivity 1.8~2.8 × 10-8Ω m, 50~85Hv of hardness.Compared with copper-based Al 2 O 3 composition, the present invention
The tensile mechanical properties of the prepared enhanced copper alloy of copper-based aeroge are suitable, and heating conduction, wear-resisting property are preferable, simultaneously
Cost is lower.
It is a kind of based on the enhanced copper alloy of copper-based aeroge in the purposes prepared in brake parts product.
In conclusion compared with the prior art, the invention has the following beneficial effects:
(1) present invention improves the mechanical property, wear-resisting of alloy by addition micron silica, nanomorphic silica
Performance and heat resistance；Wear-resisting property can be improved in the addition of zinc, accelerates matrix densification process；The hard nanometer of free state
Grain is being can be distributed in friction process between friction pair, is played " ball effect ", is reduced friction factor and wear rate.Work as SiO2?
Grain is distributed evenly in the matrix of copper base friction material, can effectively be hindered dislocation motion and Grain Boundary Sliding, be improved matrix
Intensity and heat resistance.The copper-based enhanced copper alloy of aeroge designed by the present invention has good processing performance, with copper-based three
Al 2 O composite material is compared, and heat-resisting and wearability is more preferable.
(2) present invention keeps nano silica evenly dispersed in Copper substrate by preparatory high-energy ball milling, and it is multiple to reach raising
The purpose of condensation material comprehensive performance.
(3) the enhanced copper alloy of copper-based aeroge prepared by the present invention, cost are lower.
In order to explain the structural features and functions of the invention more clearly, come to carry out the present invention combined with specific embodiments below
It is described in detail.
Specific embodiment
The following further describes the technical solution of the present invention combined with specific embodiments below.
The preparation method of the copper-based enhanced copper alloy of aeroge of the present invention, preparation step are as follows: ingredient, high-energy ball milling, mixing,
Cold moudling, pressure sintering and finished product.Its specific process step includes:
(1) high-energy ball milling: by load weighted electrolytic copper powder (average particle size≤74 μm, purity >=99.9wt%), nanoscale
SiO2(average grain diameter is 20~40nm) is placed in planetary high-energy ball mill 2~4h of preparatory ball milling.
(2) raw material mixes: by copper-Nano-meter SiO_2 after ball milling2Mixed powder, atomized zinc dust (average particle size be 40~50 μm,
Purity >=98wt%), micron order SiO2(average particle size is 40~50 μm, moisture content≤1wt%) is placed in small-sized V-type batch mixer
3~5h of middle mixing；The quality of raw material employed in embodiment is same as above.
(2) cold-press moulding: it is 4~5g/cm that powder, which is pressed into density, in the punching block of Ф 26mm × 6.5mm3Briquet；
(3) pressure sintering: green compact is sintered under 1.0~4.0MPa pressure in bell-type furnace, sintering temperature be 800~
1000 DEG C, average heating rate is 4~7 DEG C/min, uses hydrogen reduction protective atmosphere during the sintering process, and sintering time is
20~40min, furnace is cooled to room temperature under last protective atmosphere, and finished product is made.
Embodiment 1
Its technological process of production method is as follows: ingredient, ball milling, mixing, cold moudling, pressure sintering and finished product.
Detailed process are as follows: by ingredient composition shown in table 1: zinc: 5%, aeroge (SiO2): 5%, surplus is copper.By copper and
Nano-meter SiO_22Mixed powder ball milling 3h in high energy ball mill is placed in small-sized V-type batch mixer with other raw materials mixes 3h later；?Punching block in by powder be pressed into density be 4g/cm3Briquet；By green compact in 1.0MPa in bell-type furnace
It is sintered under pressure, sintering temperature is 980 DEG C, and average heating rate is 6 DEG C/min, uses restitutive protection's gas during the sintering process
Atmosphere, sintering time 40min, finally furnace is cooled to room temperature under protective atmosphere, and finished product is made.Prepared end properties is such as
Shown in table 2.
Embodiment 2
The technological process of production method of the copper-based enhanced copper alloy of aeroge is as follows: ingredient, ball milling, mixing, cold moudling,
Pressure sintering and finished product.
Detailed process are as follows: by ingredient composition shown in table 1: zinc: 2%, aeroge (SiO2): 3%, surplus is copper.By copper and
Nano-meter SiO_22Mixed powder ball milling 2h in high energy ball mill is placed in small-sized V-type batch mixer with other raw materials mixes 5h later；?Punching block in by powder be pressed into density be 4.2g/cm3Briquet；By green compact in bell-type furnace in
It is sintered under 2.5MPa pressure, sintering temperature is 900 DEG C, and average heating rate is 5 DEG C/min, during the sintering process also using hydrogen
Originality protective atmosphere, sintering time 35min, finally furnace is cooled to room temperature under protective atmosphere, and finished product is made.It is prepared at
The performance of product is as shown in table 2.
Embodiment 3
Its technological process of production method is as follows: ingredient, ball milling, mixing, cold moudling, pressure sintering and finished product.
Detailed process are as follows: by ingredient composition shown in table 1: zinc: 4%, aeroge (SiO2): 6%, surplus is copper.By copper and
Nano-meter SiO_22Mixed powder ball milling 4h in high energy ball mill is placed in small-sized V-type batch mixer with other raw materials mixes 5h later；?Punching block in by powder be pressed into density be 4.4g/cm3Briquet；By green compact in bell-type furnace in
It is sintered under 3.5MPa pressure, sintering temperature is 800 DEG C, and average heating rate is 5 DEG C/min, uses reproducibility during the sintering process
Protective atmosphere, sintering time 40min, finally furnace is cooled to room temperature under protective atmosphere, and finished product is made.Prepared finished product
Performance is as shown in table 2.
Embodiment 4
Its technological process of production method is as follows: ingredient, ball milling, mixing, cold moudling, pressure sintering and finished product.
Detailed process are as follows: by ingredient composition shown in table 1: zinc: 1%, aeroge (SiO2): 6%, surplus is copper.By copper and
Nano-meter SiO_22Mixed powder ball milling 3h in high energy ball mill is placed in small-sized V-type batch mixer with other raw materials mixes 3h later；?Punching block in by powder be pressed into density be 4.6g/cm3Briquet；By green compact in bell-type furnace in
It is sintered under 2.0MPa pressure, sintering temperature is 850 DEG C, and average heating rate is 6 DEG C/min, uses reproducibility during the sintering process
Protective atmosphere, sintering time 30min, finally furnace is cooled to room temperature under protective atmosphere, and finished product is made.Prepared finished product
Performance is as shown in table 2.
Embodiment 5
Its technological process of production method is as follows: ingredient, ball milling, mixing, cold moudling, pressure sintering and finished product.
Detailed process are as follows: by ingredient composition shown in table 1: zinc: 5%, aeroge (SiO2): 4%, surplus is copper.By copper and
Nano-meter SiO_22Mixed powder ball milling 3h in high energy ball mill is placed in small-sized V-type batch mixer with other raw materials mixes 4h later；?Punching block in by powder be pressed into density be 4.8g/cm3Briquet；By green compact in bell-type furnace in
It is sintered under 3.0MPa pressure, sintering temperature is 950 DEG C, and average heating rate is 6 DEG C/min, uses reproducibility during the sintering process
Protective atmosphere, sintering time 35min, finally furnace is cooled to room temperature under protective atmosphere, and finished product is made.Prepared finished product
Performance is as shown in table 2.
Embodiment 6
Its technological process of production method is as follows: ingredient, ball milling, mixing, cold moudling, pressure sintering and finished product.
Detailed process are as follows: by ingredient composition shown in table 1: zinc: 0.5%, aeroge (SiO2): 2%, surplus is copper.By copper
And Nano-meter SiO_22Mixed powder ball milling 3h in high energy ball mill is placed in small-sized V-type batch mixer with other raw materials mixes 3h later；
?Punching block in by powder be pressed into density be 5g/cm3Briquet；By green compact in bell-type furnace in
It is sintered under 1.0MPa pressure, sintering temperature is 1000 DEG C, and average heating rate is 4 DEG C/min, during the sintering process using reduction
Property protective atmosphere, sintering time 25min, finally furnace is cooled to room temperature under protective atmosphere, and finished product is made.Prepared finished product
Performance it is as shown in table 2.
Embodiment 7
Its technological process of production method is as follows: ingredient, ball milling, mixing, cold moudling, pressure sintering and finished product.
Detailed process are as follows: by ingredient composition shown in table 1: zinc: 10%, aeroge (SiO2): 8%, surplus is copper.By copper and
Nano-meter SiO_22Mixed powder ball milling 3h in high energy ball mill is placed in small-sized V-type batch mixer with other raw materials mixes 3h later；?Punching block in by powder be pressed into density be 4.5g/cm3Briquet；By green compact in bell-type furnace in
It is sintered under 4.0MPa pressure, sintering temperature is 800 DEG C, and average heating rate is 7 DEG C/min, uses reproducibility during the sintering process
Protective atmosphere, sintering time 40min, finally furnace is cooled to room temperature under protective atmosphere, and finished product is made.Prepared finished product
Performance is as shown in table 2.
The present invention finally improves the synthesis of alloy by addition zinc, micron silica and nanometer grade silica
Mechanical property, wear-resisting and heat resistance, while guaranteeing that alloy has good processing performance；By the method for powder metallurgy, most
It can get the enhanced copper alloy of copper-based aeroge eventually.
As shown in table 2, the Cu-base composites tensile strength prepared by the present invention is higher than 300MPa, yield strength and common
Copper-based compound aluminum oxide material it is suitable, wear rate be lower than 1.6 × 10-9cm3·J-1, heat-resistance coefficient is higher than 27900, resistance
Rate is lower than 3.2 × 10-8cm3·J-1, density is lower than 8gcm3, heat resistance and wear-resisting property are than copper-based aluminum oxide composite wood
Material is more preferable, therefore the wear part of material production can meet what product or equipment worked normally for a long time under higher temperature conditions
Demand.
A kind of copper-based silicon dioxide composite material of table 1 at being grouped as (wt.%)
| Embodiment | Zn | SiO2 | Cu |
| Embodiment 1 | 5% | 5% | Surplus |
| Embodiment 2 | 2% | 3% | Surplus |
| Embodiment 3 | 4% | 6% | Surplus |
| Embodiment 4 | 1% | 6% | Surplus |
| Embodiment 5 | 5% | 4% | Surplus |
| Embodiment 6 | 0.5% | 2% | Surplus |
| Embodiment 7 | 10% | 8% | Surplus |
The performance of table 2 embodiment and common Cu-base composites
The technical principle of the invention is described above in combination with a specific embodiment, is only the preferred embodiment of the present invention.This
The protection scope of invention is not limited merely to above-described embodiment, and all technical solutions belonged under thinking of the present invention belong to the present invention
Protection scope.Those skilled in the art, which does not need to pay for creative labor, can associate other specific realities of the invention
Mode is applied, these modes will fall within the scope of protection of the present invention.
Claims (9)
1. a kind of enhanced copper alloy of copper-based aeroge, it is characterised in that: its mass percentage composition are as follows: zinc: 0.5%~
10%, silica: 2%~8%, surplus is copper.
2. the enhanced copper alloy of copper-based aeroge according to claim 1, which is characterized in that the quality percentage of composite material
Than composition are as follows: zinc: 1%~5%, silica: 3%~6%, surplus is copper.
3. the enhanced copper alloy of copper-based aeroge according to claim 2, which is characterized in that the Cu alloy material also wraps
It is impure, mass percent≤0.1% of impurity.
4. a kind of preparation method of such as copper-based enhanced copper alloy of aeroge as claimed in any one of claims 1-3, feature exist
In including the following steps: that proportion weighs powder, by copper and nano silica mixed powder in advance in planetary high-energy ball mill
Then ball milling is placed in V-type batch mixer together with other raw materials and is uniformly mixed, powder, which is then pressed into density, in punching block is
4~5g/cm3Briquet；Finally green compact is sintered in bell-type furnace.
5. the preparation method of the enhanced copper alloy of copper-based aeroge according to claim 4, which is characterized in that with electrolysis
Copper, atomized zinc dust, micron silica and nano silica are raw material.
6. the preparation method of the enhanced copper alloy of copper-based aeroge according to claim 5, which is characterized in that electrolytic copper powder
Average particle size≤74 μm, purity >=99.9wt%；The average particle size of atomized zinc dust is 40~50 μm, purity >=98wt%；Micron
Grade SiO2Average particle size is 40~50 μm, moisture content≤1wt%；Nano-meter SiO_22Average grain diameter is 20~40nm.
7. the preparation method of the enhanced copper alloy of copper-based aeroge according to claim 6, which is characterized in that in high energy ball
Ball-milling Time is 2~4h in grinding machine, and the time mixed in V-type batch mixer is 3~5h.
8. the preparation method of the enhanced copper alloy of copper-based aeroge according to claim 7, which is characterized in that green compact exists
When being sintered in bell-type furnace, sintering pressure is 1.0~4.0MPa, and sintering temperature is 800~1000 DEG C, and average heating rate is 4~7
DEG C/min, hydrogen reduction protective atmosphere is used during the sintering process, and sintering time is 20~40min, last protective atmosphere
Lower furnace is cooled to room temperature, and finished product is made.
9. a kind of preparing brake parts product based on any enhanced copper alloy of copper-based aeroge of claim 1-3
In purposes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811596485.XA CN109593987A (en) | 2018-12-26 | 2018-12-26 | A kind of enhanced copper alloy of copper-based aeroge and preparation method thereof |
| KR1020217020266A KR20210095937A (en) | 2018-12-26 | 2019-12-26 | Airgel-reinforced metal-based composite material and its manufacturing method and application |
| JP2021538142A JP2022515532A (en) | 2018-12-26 | 2019-12-26 | Airgel reinforced metal-based composite materials and their manufacturing methods and applications |
| PCT/CN2019/128689 WO2020135582A1 (en) | 2018-12-26 | 2019-12-26 | Aerogel-reinforced metal matrix composite material, preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110423916A (en) * | 2019-08-23 | 2019-11-08 | 厦门理工学院 | Aerosil loads Cu-base composites and preparation method thereof |
| WO2020135582A1 (en) * | 2018-12-26 | 2020-07-02 | 北京弘微纳金科技有限公司 | Aerogel-reinforced metal matrix composite material, preparation method and application thereof |
| CN113061768A (en) * | 2021-03-22 | 2021-07-02 | 中南大学 | Preparation method of dispersion-strengthened copper-based composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020135582A1 (en) * | 2018-12-26 | 2020-07-02 | 北京弘微纳金科技有限公司 | Aerogel-reinforced metal matrix composite material, preparation method and application thereof |
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| CN113061768A (en) * | 2021-03-22 | 2021-07-02 | 中南大学 | Preparation method of dispersion-strengthened copper-based composite material |
| CN113061768B (en) * | 2021-03-22 | 2023-08-25 | 中南大学 | Preparation method of dispersion strengthening copper-based composite material |
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Application publication date: 20190409 |