CN105648248B - Controllable thermal expansion composite conductive ceramic material α-Cu2V2O7-Al - Google Patents
Controllable thermal expansion composite conductive ceramic material α-Cu2V2O7-Al Download PDFInfo
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- CN105648248B CN105648248B CN201610005531.9A CN201610005531A CN105648248B CN 105648248 B CN105648248 B CN 105648248B CN 201610005531 A CN201610005531 A CN 201610005531A CN 105648248 B CN105648248 B CN 105648248B
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- conductive ceramic
- thermal expansion
- composite conductive
- ceramic material
- controllable thermal
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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
-
- 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
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
-
- 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
- C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The invention belongs to inorganic composite materials technical fields, and in particular to a kind of novel controllable thermal expansion composite conductive ceramic materialα‑Cu2V2O7- Al and preparation method thereof.The material byα‑Cu2V2O7And Al powder is made through solid-phase sintering, wherein the mass percent of Al powder is between 5 ~ 80%.Preparation method include material mixing, tabletting base, sintering and etc..Controllable thermal expansion composite conductive ceramic material provided by the present inventionα‑Cu2V2O7- Al, preparation process is simple, of low cost, environment friendly and pollution-free, it is suitble to industrialized production, it is good with high-temperature electric conduction performance that material has the advantages that the coefficient of expansion is adjusted simultaneously in itself, has broad application prospects in the technical field that thermally matched requirement is high to base material, high-temperature electric conduction requirement is high such as integrated circuit, optic electronics instrument and its in Related product.
Description
Technical field
The invention belongs to inorganic composite materials technical fields, and in particular to a kind of novel controllable thermal expansion composite conductive ceramic
Materialα-Cu2V2O7- Al and preparation method thereof.
Background technology
In recent years, it is led with advances in technology with the needs of production in accurate measurement and the manufacture of optic electronics instrument
Domain, it is higher and higher to the thermal stability requirement of parts.However nature major part material has the property expanded with heat and contract with cold, heat
Swollen shrinkage can generate thermal stress between instrument and meter parts leads to instrument performance decline, the lost of life, serious
Instrument even can be damaged.
The appearance of negative thermal expansion material and develop into solve storeroom heat expansion matching provide opportunity, by negative expansion material
Material and the coefficient of expansion of the compound controlled material of positive thermal expansion material improve the measurement accuracy of device and service life and have become material science
One of research hotspot, it is good with metal composite to prepare controllable thermal expansion, electrical and thermal conductivity performance especially by negative thermal expansion material
Composite material, be expected to make a breakthrough in fields such as integrated circuit, chip packages.
Invention content
Present invention aims at provide a kind of novel controllable thermal expansion composite conductive ceramic materialα-Cu2V2O7- Al, with it
New selection can be provided for the precision equipments demand such as instrument and meter.
The technical solution used in the present invention is as described below.
A kind of controllable thermal expansion composite conductive ceramic materialα-Cu2V2O7- Al, byα-Cu2V2O7With Al powder through solid-phase sintering
Be made, the wherein mass percent of Al powder between 5 ~ 80%, aluminium powder mass percent specifically be, for example, 5 ~ 70%, 5 ~ 60%, 5 ~
50%、5~40%、5~30%、5~20%、5~10%、10~80%、10~70%、10~60%、10~50%、10~40%、10~30%、10~20%、
20~80%、20~70%、20~60%、20~50%、20~40%、20~30%、30~80%、30~70%、30~60%、30~50%、30~40%、
40 ~ 80%, 40 ~ 70%, 40 ~ 60%, 40 ~ 50%, 50 ~ 80%, 50 ~ 70%, 50 ~ 60%, 60 ~ 80%, 60 ~ 70%, 70 ~ 80% etc..
The controllable thermal expansion composite conductive ceramic materialα-Cu2V2O7The preparation method of-Al, includes the following steps：
（1）It willα-Cu2V2O7Uniform with Al powder ground and mixeds, wherein the mass percent of Al powder is between 5 ~ 80%；
（2）By step（1）The mixed material of gained carries out tabletting base；Pressure is in 100 ~ 200MPa during tabletting base；
（3）By step（2）Gained biscuit is sintered, and 610 DEG C ~ 660 DEG C are sintered 5 ~ 10 hours, preferably 650 DEG C sintering 10
Hour, obtain controllable thermal expansion composite conductive ceramic material after Temperature fallα-Cu2V2O7- Al products.
Controllable thermal expansion composite conductive ceramic material provided by the present inventionα-Cu2V2O7- Al, while there is the coefficient of expansion
The adjustable and good advantage of high-temperature electric conduction performance, has a extensive future.Beneficial effects of the present invention are embodied in：α-
Cu2V2O7- Al composite conductive ceramics material is prepared using solid phase method under air atmosphere, and preparation process is simple, of low cost, ring
Protect pollution-free, suitable industrialized production.α-Cu2V2O7- Al composite conductive ceramic materials, hot expansibility is excellent, wherein, Al's
When mass fraction is 0.3, RT（Room temperature）The average linear measured in the range of -600 DEG C using LINSEIS L76 type thermal dilatometers
The coefficient of expansion is 4.93 × 10-6℃-1, the only aluminium coefficient of expansion (23.8 × 10-6℃-1) 1/5, at this time utilize RST5000 types electricity
The impedance that chem workstation measures is about 50 ohm, and electric conductivity is preferable；When the mass fraction of Al is 0.6, RT -600 DEG C range
The average linear coefficient of expansion that thermal expansion instrument measures is 15.9 × 10-6℃-1, the aluminium coefficient of expansion is reduced 1/3, electrochemistry
The admittance that work station measures is 400 milli west, nearly equivalent to aluminium（500 milli west）Conductivity level.It is thus provided by the present invention
Compound electroceramics materialα-Cu2V2O7- Al is led in the requirement height thermally matched to base material such as integrated circuit, optic electronics instrument, high temperature
Electricity requires to have broad application prospects in high technical field and its Related product.
Description of the drawings
Fig. 1 is the XRD spectrum of composite material prepared by embodiment 3,5,7,9；
Fig. 2 is the SEM photograph of composite material prepared by embodiment 1,2,3,4,5,7,9；
Fig. 3 is the DSC curve of composite material prepared by embodiment 3,5,7,9；
Fig. 4 is the CTE curves of composite material prepared by embodiment 1,2,3,4,5,7,9；
Fig. 5 is the ac impedance spectroscopy of composite material prepared by embodiment 1,2,3,4,5,6,7,8,9（Because the pass of engineer's scale
System, the details of the wherein ac impedance spectroscopy of embodiment 4,5,6,7,8,9 are shown in the illustration in Fig. 5 upper right corner）；
Fig. 6 is admittance change curve compound prepared by embodiment 1,2,3,4,5,6,7,8,9（56.26 hertz）；
Fig. 7 is the density of composite material and relative density change curve prepared by embodiment 1,2,3,4,5,6,7,8,9；
Fig. 8 is the Vickers hardness change curve of composite material prepared by embodiment 2,3,4,5,7,9.
Specific embodiment
With reference to embodiment the present invention will be further explained explanation so that those skilled in the art can be better
Understand and put into practice technical scheme of the present invention.
Embodiment 1
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.05 in-Al
（I.e. Al accounts for the 5% of gross mass in composite material）, preparation method is specific as follows：
（1）By Al powder andα-Cu2V2O7Appropriate absolute ethyl alcohol is added in agate mortar, is ground 1 hour, it is ensured that mixing is equal
It is 30 minutes dry in 60 DEG C of baking ovens after even, it is spare；
（2）By step（1）The material that gained is uniformly mixed, using 769YP-15A type powder single shaft tablet press machines in 200 MPa
Pressure depresses to the cylinder morph idiosome of diameter 10mm, high 5mm；
（3）By step（2）Gained element idiosome is placed in tube furnace, is sintered 10 hours at 650 DEG C, Temperature fall.
Embodiment 2
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.10 in-Al
（I.e. Al accounts for the 10% of gross mass in composite material）.
Preparation method is same as Example 1.
Embodiment 3
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.20 in-Al
（I.e. Al accounts for the 20% of gross mass in composite material）.
Preparation method is same as Example 1.
To prepared novel composite conductive ceramic materialα-Cu2V2O7- Al carries out X-ray diffraction（XRD）Compose object phase point
Analysis, the results are shown in Figure 1, knows that main component is through analysisα-Cu2V2O7And Al.
Embodiment 4
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.30 in-Al
（I.e. Al accounts for the 30% of gross mass in composite material）.
Preparation method is same as Example 1.
Embodiment 5
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.40 in-Al
（I.e. Al accounts for the 40% of gross mass in composite material）.
Preparation method is same as Example 1.
To prepared novel composite conductive ceramic materialα-Cu2V2O7- Al carries out X-ray diffraction（XRD）Compose object phase point
Analysis, the results are shown in Figure 1, knows that main component is through analysisα-Cu2V2O7And Al.
Embodiment 6
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.50 in-Al
（I.e. Al accounts for the 50% of gross mass in composite material）.
Preparation method is same as Example 1.
Embodiment 7
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.60 in-Al
（I.e. Al accounts for the 60% of gross mass in composite material）.
Preparation method is same as Example 1.
To prepared novel composite conductive ceramic materialα-Cu2V2O7- Al carries out X-ray diffraction（XRD）Compose object phase point
Analysis, the results are shown in Figure 1, knows that main component is through analysisα-Cu2V2O7And Al.
Embodiment 8
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.70 in-Al
（I.e. Al accounts for the 70% of gross mass in composite material）.
Preparation method is same as Example 1.
Embodiment 9
Novel composite conductive ceramic material prepared by the present embodimentα-Cu2V2O7The mass fraction of Al is 0.80 in-Al
（I.e. Al accounts for the 80% of gross mass in composite material）.
Preparation method is same as Example 1.
To prepared novel composite conductive ceramic materialα-Cu2V2O7- Al carries out X-ray diffraction（XRD）Compose object phase point
Analysis, the results are shown in Figure 1, knows that main component is through analysisα-Cu2V2O7And Al.
Scanning electron microscopy is tested
Fig. 2 is the SEM photograph of composite material prepared by embodiment 1,2,3,4,5,7,9, it can be seen that with aluminium content
Increase, the molecule gap in composite material significantly reduces.
Heat stability testing
Fig. 3 is the DSC curve of composite material prepared by embodiment 3,5,7,9, it can be seen that in RT（Room temperature）—550℃
In the range of material keep stablizing, have faint exothermic peak 550 DEG C of position, be because the aluminium on a small amount of surface aoxidizes, with
Afterwards until 660 DEG C or so have a endothermic peak, this is the reason of aluminium melts.
Hot expansibility is tested
Fig. 4 is the CTE curves of composite material prepared by embodiment 1,2,3,4,5,7,9, it can be seen that with aluminium content
Increase, material thermal expansion coefficient gradually changes from negative to positive, and softening temperature is gradually increased（As shown in arrow in figure）, wherein in fact
3,4 average thermal linear expansion coefficient in the measurement range of RT -600 DEG C of example only has 1.94 × 10 respectively-6℃-1With 4.93 × 10-6℃-1, with aluminium (23.8 × 10-6℃-1) compared to substantially reducing so that solve thermal stress between alumina-base material and other base materials into
It is possible.
Conducting performance test
Fig. 5 is the ac impedance spectroscopy of composite material prepared by embodiment 1,2,3,4,5,6,7,8,9（Because the pass of engineer's scale
System, the details of the wherein ac impedance spectroscopy of embodiment 4,5,6,7,8,9 are shown in the illustration in Fig. 5 upper right corner）, it can be seen that composite wood
For material when aluminium content is less than 20 wt%, sample has certain semiconductor property, and very low frequencies show certain capacitive properties, with
Frequency increase rapidly go to it is resistive；Purely resistive is shown as when aluminium content is more than 20 wt%.
Fig. 6 is admittance change curve compound prepared by embodiment 1,2,3,4,5,6,7,8,9（56.26 hertz）, can be with
Find out, when aluminium content is more than 20 wt%, admittance increases rapidly material, and the admittance of example 8,9 has been even more than fine aluminium.
Density measurement
Fig. 7 be the density of composite material and relative density change curve prepared by embodiment 1,2,3,4,5,6,7,8,9, can
To find out, as the increase of aluminium content, density taper into composite material, relative density becomes larger.Second order polynomial is intended
The empirical equation of the composite density of conjunction, relative density and aluminium content is respectively：ρ=3.09-9.15×10-3 x+4.39×10-5 x 2, d=76.6-1.46 × 10-2 x+2.18×10-3 x 2。
Vickers-hardness hardness tests
Fig. 8 is the Vickers hardness change curve of composite material prepared by embodiment 2,3,4,5,7,9, it can be seen that compound
As the increase of aluminium content, Vickers hardness continuously decrease in material, certain toughness is shown.The composite material dimension of exponential fitting
The empirical equation of family name's hardness and aluminium content is：HV=20e-4.35x +34。
Claims (5)
1. a kind of controllable thermal expansion composite conductive ceramic material α-Cu2V2O7- Al, which is characterized in that the material is by α-Cu2V2O7With
Al powder is made through solid-phase sintering, and wherein the mass percent of Al powder is between 10 ~ 40%；Specific preparation method is as follows：
（1）By α-Cu2V2O7It is uniform with Al powder ground and mixeds；
（2）By step（1）The mixed material of gained carries out tabletting base, obtains biscuit；
（3）By step（2）Gained biscuit is sintered 10 hours in 650 DEG C, and controllable thermal expansion composite conductive ceramic is obtained after cooling
Material α-Cu2V2O7-Al。
2. controllable thermal expansion composite conductive ceramic material α-Cu as described in claim 12V2O7- Al, which is characterized in that Al powder
Mass percent is 20% or 30%.
3. any one of the claim 1 ~ 2 controllable thermal expansion composite conductive ceramic material α-Cu2V2O7The preparation method of-Al,
It is characterized in that, this method includes the following steps：
（1）By α-Cu2V2O7It is uniform with Al powder ground and mixeds；
（2）By step（1）The mixed material of gained carries out tabletting base, obtains biscuit；
（3）By step（2）Gained biscuit is sintered 10 hours in 650 DEG C, and controllable thermal expansion composite conductive ceramic is obtained after cooling
Material α-Cu2V2O7-Al。
4. controllable thermal expansion composite conductive ceramic material α-Cu as claimed in claim 32V2O7The preparation method of-Al, feature exist
In step（2）Pressure is 100 ~ 200MPa during middle tabletting.
5. composite conductive ceramic material α-Cu described in claims 1 or 22V2O7Applications of-the Al as conductive material.
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| Application Number | Priority Date | Filing Date | Title |
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| JP7441522B2 (en) * | 2018-11-09 | 2024-03-01 | 国立大学法人東海国立大学機構 | Method for manufacturing negative thermal expansion material |
| JP7338881B2 (en) * | 2019-01-18 | 2023-09-05 | 国立大学法人東海国立大学機構 | NEGATIVE THERMAL EXPANSION MATERIAL PARTICLE GROUP, COMPOSITE MATERIAL AND METHOD FOR MANUFACTURING SAME |
| JP7383446B2 (en) * | 2019-10-16 | 2023-11-20 | 日本化学工業株式会社 | Manufacturing method of vanadium compound |
| CN112390642B (en) * | 2020-12-01 | 2023-01-31 | 郑州大学 | Negative thermal expansion material Cu 2 V 2-x P x O 7 And method for preparing the same |
| TW202337821A (en) * | 2022-03-23 | 2023-10-01 | 日商日本化學工業股份有限公司 | Negative thermal expansion material, method for manufacturing same, and composite material |
| JP7410249B2 (en) | 2022-03-23 | 2024-01-09 | 日本化学工業株式会社 | Negative thermal expansion material, its manufacturing method and composite material |
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| CN103540806B (en) * | 2013-10-23 | 2016-04-13 | 郑州大学 | A kind of composite A l-Y 2w 3o 12and preparation method thereof |
| CN104120309B (en) * | 2014-07-14 | 2017-01-11 | 郑州大学 | Metal-negative thermal expansion material composite material and preparation method thereof |
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