CN100365154C - Cu-Ag-RE alloy in-situ nano fiber composite material - Google Patents
Cu-Ag-RE alloy in-situ nano fiber composite material Download PDFInfo
- Publication number
- CN100365154C CN100365154C CNB2005100486398A CN200510048639A CN100365154C CN 100365154 C CN100365154 C CN 100365154C CN B2005100486398 A CNB2005100486398 A CN B2005100486398A CN 200510048639 A CN200510048639 A CN 200510048639A CN 100365154 C CN100365154 C CN 100365154C
- Authority
- CN
- China
- Prior art keywords
- alloy
- adopt
- electric conductivity
- situ
- composite materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to in-situ nanometer fibre-reinforced Cu-based composite materials containing CuAgRE alloys and having high strength and high electric conductivity, and a preparation technique of the composite materials. The composite materials use Cu as basal bodies, and are prepared from at most 15% of Ag and at most 0.1% of RE. The in-situ nanometer fibre-reinforced composite materials using Ag nanometer fibers as reinforcing phases are perpared by utilizing the functions of CuAg alloy eutectic structures and the functions of the refining alloy structures of trace RE additives through large deformation and reasonable thermal mechanical treatment. The composite materials with good tensile strength and high electric conductivity can be obtained by optimizing various technological parameters in a preparing process, the ultimate tensile strength UTS is larger than or equal to 1.5GPa, and the relative electric conductivity is larger than or equal to 60% IACS. The CuAgRE alloy in-situ nanometer Ag fibre-reinforced Cu-based composite materials of the present invention can be used as conductor materials with high strength and electric conductivity.
Description
Technical field
The present invention relates to needs the matrix material and the preparation thereof of high strength and high conductivity over-all properties as high strong pulsed magnetic field conductor material, unicircuit frame material, high-performance contact material and all, particularly relates to the technology of preparing and the performance of the fibre-reinforced Cu based composites of Cu-Ag-RE (rare earth) alloy in-situ nanometer Ag that contains low Ag.
Background technology
Modern industry and development of high-tech, the excellence conductor material that needs to have high strength and high conductivity over-all properties in a lot of fields.As the ruhmkorff coil material of high strong pulsed magnetic field magnet, require to have high intensity and resist Lorentz force that electromagnetic induction produces to avoid the coil explosion, also require to have high electric conductivity simultaneously to reduce joule heating.High high-intensity magnetic field to the general requirement of conductor material is: ultimate tensile strength UTS 〉=1000MPa, electric conductivity 〉=70%IACS (IACS is the international annealed copper conductivity standard) relatively.Development along with microelectronics, the unicircuit frame material has been proposed more and more higher requirement, and most important performance requriements also is high strength and high conductivity, high intensity can make framework keep good rigidity and deformation resistance, and high electric conductivity (thermal conductivity) can reduce the thermal value of high integrated silicon chip.In general, the requirement of large-scale integrated circuit lead frame material over-all properties is: UTS 〉=600MPa, electric conductivity 〉=80%IACS relatively.In addition, the high-strength high-conductivity material all has important application prospects at the aspects such as housing, superconductor technology, electric works and aerospace of the focusing of other field such as high-energy particle accelerator and accelerating coil, controlled thermonuclear reaction device.
Fine copper has high electric conductivity, can not meet the demands but its intensity is low, thereby need to improve by multiple reinforcement means the intensity of copper.The main schedule of reinforcement of copper has: microalloying reinforcement, solution strengthening, working hardening, refined crystalline strengthening, precipitation strength, dispersion-strengthened and complex intensifying etc.Alloying can improve the intensity of copper and copper alloy, but also reduces its electric conductivity simultaneously, therefore can only adopt microalloying usually.Though microalloying copper alloy can keep high electrical conductivity, its intensive property is still lower, only is suitable for requiring high conductivity and the occasion very not high to requirement of strength.Existing work and empirical evidence are difficult to obtain the over-all properties that high strength and high conductivity combine by traditional solution strengthening and ageing strengthening, they be not strength property low be exactly that electric conductivity obviously reduces.Complex intensifying is the effective ways of strengthened copper alloy.Press the generation method of wild phase in the matrix material, the preparation method of Cu-base composites has outer implantation and in-situ compositing.The outer composite algorithm complex process of implanting, and because wild phase is to be implanted by the outside, is difficult to make second to be evenly distributed mutually, and unavoidably brings contaminating impurity into, interface bond strength is weakened, thereby make composite property inhomogeneous and unstable.In-situ compositing is the structure by founding means control cast alloy, and makes in the alloy second to hand down the machine direction distortion and form fiber or laminar structured to reach the purpose that strengthens matrix through mechanical workout.Because these strengthen second is that original position generates and directly processes and forms in alloy mutually, there is not external contamination, there is not the side reaction inclusion, the interface is in conjunction with firm, and strengthening phase is evenly distributed, and can make matrix obtain obviously to strengthen, be a kind of advanced person's compounding technology, be subjected to the attention of countries in the world.Adopting in-situ compositing to prepare the high-strength high-conductivity Cu-base composites mainly concentrates on the two class copper alloys at present.The first is copper alloy such as Cu-Nb, Cu-Fe and the Cu-Cr etc. of mechanical mixture in as cast condition, and they are that body-centered cubic second is embedded in the face-centered cubic copper matrix mutually, forms matrix material through the original position distortion.It two is to utilize Cu-Ag eutectic structure original position distortion and form matrix material.By comparison to this two classes original position deformation complex copper based composites performance, Cu-Ag alloy in-situ matrix material have a comprehensive performance.
The character that the intensity of Cu-Ag alloy in-situ matrix material and specific conductivity are a pair of contradiction, i.e. the measure of all raising intensive properties all can reduce electric conductivity matter.In this class matrix material, along with increasing, Ag content adds, and the intensity of matrix material increases, but specific conductivity descends.The Cu-Ag alloy in-situ matrix material of high Ag content increases cost, and specific conductivity often can not meet the demands; The cost of the Cu-Ag alloy in-situ matrix material of low Ag content reduces, and can keep high specific conductivity, but intensity often can not meet the demands.In order to solve this contradiction, the present invention adopts low Ag content and adds trace rare-earth element (RE), preparation Cu-Ag-RE alloy in-situ nano fiber composite material in conjunction with the overall merit of in-situ compositing and microalloying.In this matrix material, by the solution strengthening of trace rare-earth element (RE) additive and the effect of refinement alloy structure (comprising the Ag fiber), can give the material additional hardening, to remedy the deficiency of the intensity that contains the Cu-Ag alloy in-situ matrix material that hangs down Ag.Therefore, the Cu-Ag-RE alloy in-situ nano fiber composite material that contains low Ag of the present invention had both had high strength and high conductivity over-all properties, also have the effect of saving the Ag resource and reducing material cost, simultaneously, also developed the application of rare earth element in this class material of China's high yield.
Summary of the invention
The purpose of this invention is to provide a kind of fibre-reinforced Cu based composites of Cu-Ag-RE alloy in-situ nanometer Ag that contains low Ag and micro-RE, this material has the over-all properties that good high strength combines with high conductivity.
Another object of the present invention provides the original position recombining process of preparation Cu-Ag-RE alloy in-situ nano fiber composite material, promptly coagulate teeming speed degree, cold deformation amount and middle thermo-mechanical treatment process, obtain to have the fibre-reinforced Cu based composites of Cu-Ag-RE alloy in-situ nanometer Ag that otherwise limit tensile strength and electric conductivity combine by the control cast alloy.
High strength that the present invention is prepared and high conductivity Cu-Ag-RE alloy in-situ fibre composite can be used for that high strong pulsed magnetic field is made conductor material, circuit lead frame material, high-performance contact material and other needs the application of high strength and high conductivity over-all properties.
The intensive property of Cu-Ag alloy in-situ fibre composite increases with Ag content, comes to reduce conductivity of electrolyte materials but increase the Ag content back.The Cu-Ag alloy in-situ fibre composite of the low Ag content of preparation can obtain high specific conductivity and save the Ag consumption, but its intensive property does not often reach requirement.Purpose of the present invention is exactly to add trace rare-earth (RE) element in the Cu-Ag alloy that contains low Ag, strong solution strengthening effect and the particularly effect of Ag fiber size of refinement alloy structure size by rare earth addition, give Cu-Ag-RE alloy in-situ fibre composite additional hardening effect, thereby improve the intensity of matrix material and keep high specific conductivity.In this class matrix material, the Ag fiber size can remain the nano level yardstick, be evenly distributed in the Cu matrix, make the Cu matrix obtain highly enriched and the maintenance high conductivity, and by different hot mechanical treatments, can obtain to have the over-all properties of otherwise limit tensile strength (UTS) and electric conductivity performance optimization combination, its highest intensity value reaches UTS 〉=1.5GPa and keeps electric conductivity 〉=60%IACS simultaneously.
The present invention adopts the preparation of original position deformation compounding technology to contain the Cu-Ag-RE alloy in-situ fibre composite of low Ag and micro-RE, and wherein the size of Ag fiber and distribution thereof have decisive influence to the intensity and the electric conductivity character of matrix material.The present invention proposes in development Cu-Ag-RE alloy in-situ fibre composite, Ag Fibre diameter d and cast alloy original grain dimensional parameters λ
0And there is following relation between the true strain η:
d＝λ
0exp(-0.228η) (1)
Since the rare earth addition refining effect strong to the alloy as-cast structure, in formula (1), the λ of Cu-Ag-RE alloy
0Value is than the λ of the Cu-Ag alloy that does not add the RE element
0Value almost reduces 1 times and 1 order of magnitude.Such as, the λ of Cu-10Ag alloy
0=1500nm, and Cu-10Ag-RE alloy λ
0=830nm.Therefore, when identical true strain, the Ag fiber size of Cu-Ag-RE alloy in-situ fibre composite is tiny more than the Ag fiber size of the Cu-Ag alloy that does not add the RE element.Again according to the intensity (σ of Cu-Ag alloy in-situ fibre composite
Cu/Ag) and true strain between relation:
σ
Cu/Ag＝σ
0(Cu)+[k
Cu/Agλ
0 -1/2]exp(η/3) (2)
(σ in the formula (2)
0 (Cu)Be the intensity of pure Cu, k
Cu/AgBe the Hull-Petch constant), have littler λ
0The Cu-Ag-RE alloy in-situ fibre composite ratio of value has bigger λ
0The Cu-Ag alloy in-situ fibre composite of value has higher reinforcement speed, thereby obtains higher strengthening effect.
According to formula (1), following processing parameter has decisive influence to the size of Ag fiber in the Cu-Ag-RE alloy in-situ fibre composite and the final performance of matrix material, and these factors are:
1) RE additive RE additive directly reduces the original grain dimensional parameters λ of cast alloy
0With increase composite material strength;
2) true strain amount η by formula (1) formula as can be known, true strain η value is big more, the d value is more little, the Ag Fibre diameter is thin more, and when η＞8, the Ag Fibre diameter can be lower than 100nm, promptly reach nanofiber diameter, form the fibre-reinforced Cu-Ag-RE fibre composite of nanometer Ag; On the other hand, the η value is big more, and deformation quantity is big more, can make the Ag fiber form more uniform distribution.By (2) formula, true strain η value is big more again, and composite material strength is high more.
3) intermediate heat mechanical treatment intermediate heat treatment can be controlled the precipitation process and the size of Ag precipitated phase, and in the following process process, the Ag precipitation changes the Ag fiber that size is thinner and be more evenly distributed into, can further increase the intensity of matrix material; Separate out the minimizing Cu solid solubility of middle Ag mutually because Ag is sedimentary again, thereby increase the specific conductivity of matrix material.
Therefore, two of the object of the invention is that it comprises following processing step about the preparation technology of acquisition high-performance Cu-Ag-RE alloy in-situ fibre composite:
1. adopt Ar gas shiled molten alloy and control the content of RE additive;
2. control ingot solidification rate of cooling ε=10
1～10
3The K/s order of magnitude;
3. adopt extruding, forging or rolling procedure of processing to do the ingot casting cogging;
4. adopt cold forging, cold rolling or cold drawing procedure of processing to do preliminary working;
5. adopt fine drawing to process and make product silk material for the alloy finished product;
6. adopt 350 ℃ of following temperature to make intermediate heat treatment, the thermal treatment number of times is controlled at below 1～3 time; Adopt 300 ℃ of following temperature to make stabilization treatment; Intermediate heat treatment and stabilization treatment are carried out in Ar gas shiled atmosphere or vacuum.
Embodiment
Embodiment 1
The alloying constituent of matrix material of the present invention is for containing the Cu-Ag-Sc alloy of 8%Ag, 0.02%Sc (massfraction), adopt and vacuumize earlier (＜0.1Pa) fill Ar gas shiled melting again.Earlier fusing Cu and Ag or Cu-Ag alloy add the 3rd constituent element Sc then, moltenly pour into preheating high purity graphite mold after clear, and the about 60K/s of control ingot casting rate of cooling obtains having the right cylinder ingot casting of certain taper.Ingot casting is after preliminary working such as cold forging, cold rolling and drawing, o'clock 350 ℃/1h of the work intermediate heat treatment in true strain η=3.0, the cold deformation of implementing true strain η=8 again is prepared into in-situ nano fiber composite material, and its performance is: UTS=1180MPa, electric conductivity=80%IACS.
Embodiment 2
The alloying constituent of matrix material of the present invention is for containing the Cu-Ag-Ce alloy of 10%Ag, 0.04%Ce (massfraction), adopt melting and the complete processing similar with embodiment 1, o'clock 350 ℃/1h of the work intermediate heat treatment in true strain η=3.0, the cold deformation of true strain η=9.8 again, prepared performance of composites is: UTS=1360MPa, electric conductivity=68%IACS.
Embodiment 3
The alloying constituent of matrix material of the present invention and melting and complete processing with embodiment 2, but alloy experiences twice intermediate heat treatment in the course of processing: promptly in true strain η=2.3 with made 350 ℃/1h intermediate heat treatment at 2.95 o'clock respectively, impose the gross distortion of true strain η=10.2 again, the performance of prepared Cu-10Ag composite wire material is: UTS=1500MPa, electric conductivity=65%IACS.
Embodiment 4
The alloying constituent of matrix material of the present invention is for containing the Cu-Ag-Y alloy of 12%Ag, 0.06%Y (massfraction), adopt melting and the complete processing similar with embodiment 1, o'clock 350 ℃/1h of the work intermediate heat treatment in true strain η=3.0, the cold deformation of true strain η=9.8 again, prepared performance of composites is: UTS=1300MPa, electric conductivity=65%IACS.
Embodiment 5
The alloying constituent of matrix material of the present invention contains the Cu-Ag-Gd alloy of 15%Ag, 0.08%Gd (massfraction), adopt the melting technology similar with embodiment 1, ingot casting through processing such as cold forging, cold rolling and drawings until true strain η=7.6, in the course of processing without intermediate heat treatment, prepared performance of composites is: UTS=1040MPa, electric conductivity=75%IACS.
Embodiment 6
The alloying constituent of matrix material of the present invention contains the Cu-Ag-Gd alloy of 15%Ag, 0.08%Gd (massfraction), adopt melting and the complete processing similar with embodiment 1, o'clock 350 ℃/1h of the work intermediate heat treatment in true strain η=3.0, the cold deformation of true strain η=9.8 again, prepared performance of composites is: 1280MPa, electric conductivity=65%IACS.
Embodiment 7
The alloying constituent of matrix material of the present invention is for containing the Cu-Ag-Er alloy of 15%Ag, 0.1%Er (massfraction), adopts the melting technology similar with embodiment 1, Ar gas shiled melting, and melt pours into the water-cooled copper mold, control ingot casting rate of cooling ε=6 * 10
3K/s.Ingot casting o'clock is made 350 ℃/1h intermediate heat treatment in true strain η=2.95 after preliminary working such as cold forging, cold rolling and cold drawing, through the cold deformation of true strain η=9., the performance of prepared composite wire material is: UTS=1300MPa, electric conductivity=68% again.
Embodiment 8
The alloying constituent of matrix material of the present invention is the Cu-Ag-Yb alloy of 12%Ag, 0.06%Yb (massfraction), adopt melting and the complete processing similar with embodiment 1, o'clock 350 ℃/1h of the work intermediate heat treatment in true strain η=3.0, the cold deformation of true strain η=9.8 again, prepared performance of composites is: UTS=1290MPa, electric conductivity=70%IACS.
Claims (1)
1. the preparation technology of a Cu-Ag-RE alloy in-situ nano fiber composite material, Cu is a matrix in this matrix material, and rare earth RE is for adding element, and Ag is a wild phase, the Ag wild phase is made and is evenly distributed in the Cu matrix by original position deformation composite algorithm, it is characterized in that comprising successively following process steps:
1. adopt Ar gas shiled molten alloy and control the content of RE additive;
2. control ingot solidification rate of cooling ε=10
1～10
3The K/s order of magnitude;
3. adopt extruding, forging or rolling procedure of processing to do the ingot casting cogging;
4. adopt cold forging, cold rolling or cold drawing procedure of processing to do preliminary working;
5. adopt fine drawing to process and make product silk material for the alloy finished product;
6. adopt 350 ℃ of following temperature to make intermediate heat treatment, the thermal treatment number of times is controlled at 1～3 time; Adopt 300 ℃ of following temperature to make stabilization treatment; Intermediate heat treatment and stabilization treatment are carried out in Ar gas shiled atmosphere or vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100486398A CN100365154C (en) | 2005-11-22 | 2005-11-22 | Cu-Ag-RE alloy in-situ nano fiber composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100486398A CN100365154C (en) | 2005-11-22 | 2005-11-22 | Cu-Ag-RE alloy in-situ nano fiber composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1775989A CN1775989A (en) | 2006-05-24 |
| CN100365154C true CN100365154C (en) | 2008-01-30 |
Family
ID=36765707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100486398A Expired - Fee Related CN100365154C (en) | 2005-11-22 | 2005-11-22 | Cu-Ag-RE alloy in-situ nano fiber composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100365154C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177613A (en) * | 2008-10-08 | 2011-09-07 | 莱尔德技术股份有限公司 | Method for protecting a condutive material structure provided on a carrier |
| CN103774206B (en) * | 2013-12-27 | 2017-08-15 | 威瑞泰科技发展(宁波)有限公司 | A kind of preparation technology of metallic fiber |
| CN110004320B (en) | 2019-05-15 | 2020-07-28 | 东北大学 | High-strength high-conductivity Cu-Ag-Sc alloy and preparation method thereof |
| CN111250560B (en) * | 2020-01-21 | 2022-01-28 | 中国科学院电工研究所 | Preparation method of Cu-Ag alloy wire |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380431A (en) * | 2002-02-04 | 2002-11-20 | 浙江大学 | Silver fibre heterogeneous reinforced rare earth copper base alloy and its production process |
| CN1555065A (en) * | 2003-12-26 | 2004-12-15 | 昆明贵金属研究所 | High strength high conductivity copper base composite material and its preparing method |
-
2005
- 2005-11-22 CN CNB2005100486398A patent/CN100365154C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380431A (en) * | 2002-02-04 | 2002-11-20 | 浙江大学 | Silver fibre heterogeneous reinforced rare earth copper base alloy and its production process |
| CN1555065A (en) * | 2003-12-26 | 2004-12-15 | 昆明贵金属研究所 | High strength high conductivity copper base composite material and its preparing method |
Non-Patent Citations (2)
| Title |
|---|
| 稀土元素对Cu-Ag原位纤维复合材料的结构与性能影响. 张晓辉，闫琳，宁远涛.功能材料，第35卷第增刊期. 2004 * |
| 稳定化处理对Cu-10Ag-0.04Ce原位纳米纤维复合材料的组织及性能的影响. 张晓辉，闫琳，宁远涛.稀有金属，第29卷第4期. 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1775989A (en) | 2006-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103388090B (en) | A kind of high-strength, high connductivity, deep drawing quality rare-earth copper alloy and preparation method thereof | |
| CN104946936B (en) | A kind of aerial condutor high conductivity rare earth duralumin monofilament material | |
| CN101775520B (en) | Method for preparing high-performance Cu-Fe deformation in-situ composite material by magnetic field treatment | |
| CN103952605B (en) | A kind of preparation method of middle strength aluminium alloy monofilament | |
| CN105609155B (en) | A kind of high-conductivity hard aluminum wire monofilament and preparation method thereof | |
| CN104975211B (en) | Strength aluminum alloy conductive monofilament in a kind of high conductivity heat treatment type | |
| CN106381414B (en) | A kind of copper-based in-situ composite alloy and preparation method thereof | |
| CN103382535B (en) | A kind of high-strength, high connductivity, deep drawing quality copper alloy and preparation method thereof | |
| CN108754267A (en) | High-strength deforming magnesium alloy and preparation method thereof containing rare earth samarium | |
| CN102903415B (en) | A kind of special-shaped oxidation-resistant high-conductivity aluminum alloy carbon fiber lead wire and manufacture method | |
| CN105839038B (en) | A kind of preparation method of high-strength high-conductivity Cu Ag Fe alloys | |
| CN101709401B (en) | Cu-Cr in-situ composite with boron, silver and rare earth elements added and preparation method thereof | |
| CN109722560B (en) | ZrC reinforced Cu-Fe-based composite material and preparation method thereof | |
| CN106676334A (en) | High-strength high-conductivity aluminum-scandium alloy as well as preparation method thereof and use thereof | |
| CN105088010A (en) | High-strength and high-conductivity rare earth copper and zirconium alloy and preparation method thereof | |
| CN103266247B (en) | Superplastic high-strength heatproof magnesium alloy and preparation method thereof | |
| CN100365154C (en) | Cu-Ag-RE alloy in-situ nano fiber composite material | |
| CN104911408B (en) | A kind of hard aluminum wire monofilament and preparation method thereof | |
| CN108315581A (en) | A kind of low beryllium content copper alloy and preparation method thereof of high intensity high softening temperature | |
| CN102400007B (en) | Eutectic strengthening reinforced Cu-Ag alloy and preparation method thereof | |
| CN102690971B (en) | High-strength copper alloy strip and preparation method thereof | |
| CN106676318A (en) | Zirconium-containing brass material for asynchronous traction motor rotor conducting bar and preparation method of zirconium-containing brass material | |
| CN110819853A (en) | High-conductivity soft aluminum monofilament and preparation method thereof | |
| CN1286120C (en) | High strength high conductivity copper base composite material and its preparing method | |
| CN102676868B (en) | Ultrahigh strength copper alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080130 Termination date: 20091222 |