CN102304640A - Silver-base rare-earth alloy material and preparation method and application thereof - Google Patents
Silver-base rare-earth alloy material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a silver-base rare-earth alloy material, which is characterized by comprising the following components in percentage by mass: 0.1 to 8 percent of Cu, 0.01 to 0.5 percent of Ni, 0.01 and 0.3 percent of Sm and the balance of Ag. By the silver-base rare-earth alloy material, the defect that the service life of the conventional silver-base composite material is reduced greatly due to unsuitability for high-temperature environment of a micro motor, the defect that materials are difficult to process due to substantial reduction of elongation of the materials caused by the addition of rare-earth elements in the silver-base composite material which is suitable for the micro motor and the like are overcome, so the invention provides a new silver-base rare-earth alloy material and a preparation method and application thereof. The silver-base rare-earth alloy material has the characteristics of high elongation, high recrystallization temperature, high hardness at high temperature, high abrasive resistance and the like, is suitable to be used as a sliding electric contact material, can be particularly used for manufacturing parts of a commutator of the micro motor and the like, and has the advantages of high quality and long service life at the high temperature of 70 DEG C.
Description
Technical field
The present invention relates to a kind of silver base rare earth alloy material and its production and application.
Background technology
For a long time, in contact material, formed and be main solution strengthening type series alloy with Ag-Cu and be main dispersion strengthening type series alloy with Ag-Ni.Wherein use the most extensive with the Ag-Cu alloy.But the Ag-Cu alloy is under industrial atmosphere, and especially in high temperature, high humidity and sulfide hydrogen atmosphere, the surface generates nonconducting sulfide film and oxide film easily, causes contact resistance unstable, and contact reliability reduces.Simultaneously, because copper content is lower, the recrystallization temperature of alloy low (about 260 ℃), the high temperature under the machine operation environment is prone to make commutator segment local softening even fusing, greatly accelerated wear test process.And the electric arc that motor produced in when work can cause near the quick loss of the pole piece skirt materials reverser groove on the one hand; Make the abrasive dust particle surface fusing that accumulates in the groove on the other hand and be welded to each other; Form metallurgical the connection with the pole piece edge, cause the early stage short circuit of pole piece.
Ni is the grain-refining agent of Ag alloy, can the stable prod size, and significantly improve the wear resistance and the erosion resistance of body material, and further improve the anti electric arc corrosion performance of material; Because the Ag-Cu alloy has the segregation tendency, add an amount of Ni and can significantly reduce the alloy segregation in addition.Even but because under high temperature (about 1000 ℃), Ni and Ag matrix also dissolve each other hardly, Ni gathers in the silver alloys matrix very easily partially, and the homogeneity of structure of founding silver matrix is had very big influence.Therefore also there is certain difficulty in the Ag-Cu alloy of high Ni content (0.5%) aspect melting.At present, the AgCu of Japanese Tanaka company
4Ni
0.5The level of alloy material is in rank first.
Rare earth element has obtained good application in the precious metal contact material.Rare earth is added in the alloy, mainly play the internal oxidation effect.Rare earth oxide is disperse and distributes on crystal boundary, near the particle of these disperses, form dislocation loop, can further strengthen matrix.Therefore, rare earth element is a kind of intensive reductor, can effectively capture the oxygen in the alloy, under the prerequisite that keeps body material good electric conductivity and thermal conductivity, alloy substrate is had tangible strengthening effect.Simultaneously can the refinement matrix grain, alleviate the instability problem of alloy structure and structure to a certain extent, one of problem of the required solution of this current just Ag-Cu-Ni alloy material.
Zn is owing to have higher vapour pressure, and the formation zinc fume can volatilize under lower temperature.In the Working environment of reverser, the volatilization of zinc fume heat absorption can consume a large amount of arc energies, and produced simultaneously zinc fume can play effective arc extinguishing and clean surfaces effect.
In recent years along with the miniaturization of household electrical appliance etc., often micromotor is installed in Heating element near.Hot environment causes the wear resistance of micromotor and has a strong impact on, and makes the life-span of reverser reduce greatly.For the wear resisting property that further improves commutator material and electric erosion resistance can, some scholars have proposed in the Ag-Cu alloy, to add the method for trace rare-earth element etc., some of them have also played effect preferably.CN 101029362A (open day 2007.09.05) discloses a kind of novel silver-copper-rare earth material, and the mass percentage content of its each composition is Sn 0.3-0.8%, Ce 0.3-0.8%, and surplus is AgCu
6Alloy.This material has improved AgCu
6The wear resistance of alloy contact material, arc ablation resistance performance and resistance fusion welding ability.CN 101029361 (open day 2007.09.05) discloses a kind of novel silver rare-earth alloy contact material, and the mass percentage content of its each composition is Cu 4-8%, Ni 0.5-1.5%, and surplus is AgCe
0.5Alloy, this material improved Ag-Ce alloy contact material wear-resistant ability and refinement crystal grain, thereby improve the mechanical property of Ag-Ce alloy.CN 101246758 (open day 2008.08.20) discloses a kind of sliding contact material that is applicable to weak current.Wherein said body material is Ag-Cu-Ni or Ag-Cu-Zn-Ni, and rare earth element is La and/or Ce.
Summary of the invention
Technical problem to be solved by this invention has been to overcome the hot environment that existing silver-based composite material is not suitable for micromotor causes the life-span to be reduced greatly; Or the silver-based composite material that is applicable to micromotor causes the material unit elongation to decline to a great extent owing to adding rare earth element; Be unfavorable for defectives such as materials processing, a kind of new silver base rare earth alloy material and its production and application is provided.Silver base rare earth alloy material of the present invention has good unit elongation, is beneficial to cold deformation, and recrystallization temperature is high; Characteristics such as weave construction is stable, and hardness is high under the high temperature, and wear resistance is good; Be applicable to as sliding contact material especially light, moderate duty micromotor sliding contact material.Process parts such as micromotor reverser after it is can be with copper or copper alloy compound; The small-sized DC motor that is used for household electrical appliance etc.; Especially the reverser high temperature contact resistance of Zhi Zuoing is little and stable; Anti-electroerosion and anti-mechanical wear performance are high, under about 70 ℃ hot environment, still have the advantage that quality is good, the life-span is long.
The invention provides a kind of silver base rare earth alloy material, it comprises following compositions: Cu 0.1～8%, and preferable is 4～6.5%; Ni 0.01%～0.5%, and preferable is 0.2～0.4%; Sm 0.01%～0.3%, and preferable is 0.1～0.25%; And Ag, Ag complements to 100%, and said per-cent is all the mass percent with respect to the silver base rare earth alloy material.Wherein, Cu, Ni and Sm disperse are in Ag.
In the present invention's one preferred implementation, also comprise Zn0.01～0.6% in the described silver base rare earth alloy material, better is 0.15～0.45%; Per-cent is the mass percent with respect to the silver base rare earth alloy material.Wherein, in Zn solid solution other metal ingredients in the silver base rare earth alloy material.
Wherein, the preferable method by comprising the steps of silver base rare earth alloy material of the present invention makes:
1. with raw metal under argon shield melting and cast ingot casting;
2. this ingot casting is carried out homogenizing thermal treatment in 760～800 ℃;
3. surface treatment;
4. the cold rolling ingot casting generation predeformation that makes, the predeformation amount of this ingot casting on thickness direction is 40%～50%;
5. under the atmosphere of vacuum condition or decomposed ammonia, anneal in 650 ℃～700 ℃;
6. roll in;
7. in 680 ℃～700 ℃, under nitrogen and hydrogen atmosphere, protect annealing, get final product;
Wherein, described raw metal comprises the metallic element of following mass percent: Cu 0.1～8%, and preferable is 4～6.5%; Ni 0.01%～0.5%, and preferable is 0.2～0.4%; Sm 0.01%～0.3%, and preferable is 0.1～0.25%; And Ag, Ag complements to 100%.Preferable, also comprise 0.01～0.6% in the described raw metal, better is 0.15～0.45% Zn element, per-cent is the per-cent with respect to the raw metal total mass.The form that described metallic element can pure metal and/or the form of alloy are as raw metal.Said alloy can be selected arbitrarily, and the total amount of each metallic element satisfies above-mentioned mass percent in the raw metal as long as make.
Step 1. in, the purity of said raw metal can be selected according to the conventional purity of this type of material of this area, preferable is Ag >=99.99%, Cu >=99.99%, Zn >=99.99%, Ni >=99.99%, Sm >=99.96%, per-cent is all mass percent.
Step 2. in, described homogenizing heat treatment period can be selected according to this area general knowledge, preferable is 2.5～3 hours.
Step 3. in, described surface treatment refers to mainly adopt wire brush or sand paper etc. to remove defectives such as material surface oxidation point, stain or foreign material.
Step 4. in, described predeformation can give the silver base rare earth alloy material that finally obtains good cold-forming property.
Step 5. in, described annealing time can be selected according to this area general knowledge, preferable is 1.5～2 hours.
Step 7. in, the described protection annealed time can be selected according to this area general knowledge, preferable is 10～15 minutes; Preferable in connecting hot stove, the carrying out of described protection annealing.
Among the present invention, described melting, casting, cold rolling and in roll all and can carry out according to this area ordinary method.
The present invention also provides described silver base rare earth alloy preparation methods, its comprise the steps: 1. with raw metal under argon shield melting and cast ingot casting;
2. this ingot casting is carried out homogenizing thermal treatment in 760～800 ℃;
3. surface treatment;
4. the cold rolling ingot casting generation predeformation that makes, the predeformation amount of this ingot casting on thickness direction is 40%～50%;
5. under the atmosphere of vacuum condition or decomposed ammonia, anneal in 650 ℃～700 ℃;
6. roll in;
7. in 680 ℃～700 ℃, under nitrogen and hydrogen atmosphere, protect annealing, get final product; Wherein, step is 1.～7. all with aforementioned.
In the present invention's one preferred implementation, said silver base rare earth alloy material is processed into various section bars in preparation.For this reason, as long as increase a finish rolling step again after 7. in step.Described finish rolling gets final product according to this area ordinary method.
The present invention also provides the application of said silver base rare earth alloy material as sliding contact material.The micromotor sliding contact material that described sliding contact material is preferable for light or moderate duty.
Except that specified otherwise, raw material of the present invention, reagent and equipment are all commercially available to be got.
Among the present invention, but above-mentioned optimum condition arbitrary combination on the basis that meets this area general knowledge promptly gets each preferred embodiments of the present invention.
Positive progressive effect of the present invention is:
1) it is unstable to adopt silver base rare earth alloy material of the present invention can solve Ag-Cu alloy contact resistance at high temperature; Problems such as contact reliability reduction; The micromotor reverser of making has better high temperature abrasion resistance and anti-electric-arc ability; Be applicable under high temperature (about 70 ℃) condition, be used in the micromotor of light or moderate duty work.
2) silver base rare earth alloy material of the present invention is the high strength yellow gold of low Ni content, can adopt the manufacturing of conventional vacuum melting technology, and equipment and Technology do not need special transformation, and be easy to implement aborning.
3) silver base rare earth alloy prescription provided by the invention is combined with the preparation method not only significantly improve the original microstructure of alloy, crystal grain thinning improves hardness, intensity, the recrystallization temperature of alloy substrate; And guaranteed that alloy material still has good unit elongation, be beneficial to the cold deformation of material;
Description of drawings
Fig. 1 is the SEM figure of silver base rare earth alloy material, wherein the SEM figure of (a) material profile of obtaining after 2. handling for embodiment 7 steps; (b) the SEM figure of the material profile that obtains after 5. handling for embodiment 7 steps.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
The purity (mass percent) of the raw metal that uses among the embodiment 1～7 is: Ag >=99.99%, Cu >=99.99%, Zn >=99.99%, Ni >=99.99%, Sm >=99.96%.
The foreign matter content that allows in the silver base rare earth alloy material that makes among the embodiment 1～7 is (mass percent): Fe≤0.002%, Pd≤0.002%, Sb≤0.002%, Bi≤0.002%.
The proportioning raw materials (50kg altogether) that table 1 is used to slide and electrically contacts the silver base rare earth alloy material
Table 2 is of the present invention to be used to slide and to electrically contact the performance data of silver base rare earth alloy material
Embodiment 1～7 silver base rare earth alloy preparation methods
(%) by mass percentage: with pure Ag, oxygen free copper (Cu), pure Zn, CuNi
35And AgSm
10Alloy is a raw material, carries out following operation (is with the ingot casting 50Kg calculate) according to the prescription among each embodiment in the table 1: 1. raw metal is carried out melting under oxygen free condition and argon shield and cast ingot casting; 2. with this ingot casting in 760 ℃ of homogenizing thermal treatments 3 hours; 3. realize surface treatment with sharpening machine polishing ingot casting surface; 4. the cold rolling predeformation amount of this ingot casting on thickness direction that make is 45%; 5. in 650 ℃, annealing is 2 hours under the ammonia dissolving atmosphere protection; 6. roll in; 7. under nitrogen and hydrogen atmosphere, in connecting hot stove, annealed 15 minutes in 700 ℃ of protections; Finish rolling gets the silver base rare earth alloy material, and wherein the content of each composition is seen table 2.Visible by Fig. 1, among the embodiment 7, the alloy after 5. handling through step with handle before compare, grain-size obviously diminishes.The SEM of embodiment 1～6 schemes same Fig. 1.
Effect embodiment 1
With comparing among the unit elongation of Pd-Ag substrate alloy material in the patent (CN 101029362A) and the present invention.Disclose a kind of silver-copper-rare earth material in this patent, wherein the mass percentage content of each composition is Sn 0.3-0.8%, Ce 0.3-0.8%, and surplus is AgCu
6Alloy.Do not mix the yellow gold AgCu of other elements
6Unit elongation be 29%, mix Sn and Ce after unit elongation obviously drop to 20-23%.Also have 26.5% yet the unit elongation of the silver base rare earth alloy in the embodiment of the invention 1～7 is minimum, reach as high as 36.3%, even than yellow gold AgCu
6Unit elongation higher.Prove the unit elongation that can significantly improve the silver base rare earth alloy material by preparation method of the present invention thus, guaranteed the cold-forming property of alloy material, can obviously reduce the tooling cost of material, have high economic benefit.
Three utmost point reverser experiments endurance life of effect embodiment 2 micromotors
One, the preparation of band
Get the silver base rare earth alloy material and the existing AgCu that make among the embodiment 1～7
4Ni
0.3Alloy material is combined into the stratified composite that thickness is 0.8mm with fine copper respectively, and is rolled into band 1～7 and contrast band.Wherein, alloy material is about 1: 10 with the composite thickness ratio of copper.
Two, test is with the preparation of reverser
Above-mentioned band is made into micromotor three utmost point reversers respectively, this reverser is assemblied in the micromotor, its corresponding brush plate material is AgPd30/C7701.Wherein the commutator face of half is through the abrasive belt milled processed.
Three, testing method and condition
Test condition:
Probe temperature: 70 ℃, test load: 15gcm, test voltage: 4V, test duration: 810h, rotation direction: interrupted way traffic
Testing method: after the test duration motor is torn open machine through regulation and observe, observe electric machine operation state, surface abrasion situation and groove cleanliness factor, thereby analyze.Test result is seen table 3.
Table 3
Visible by table 3, to compare with the micromotor that obtains by the AgCuNi material with the micromotor that silver base rare earth alloy material of the present invention is processed, be improved significantly its endurance life.
Claims (10)
1. silver base rare earth alloy material, it is characterized in that: it comprises following compositions: Cu 0.1～8%; Ni 0.01%～0.5%; Sm 0.01%～0.3%; And Ag, Ag complements to 100%, and said per-cent is all the mass percent with respect to the silver base rare earth alloy material.
2. silver base rare earth alloy material as claimed in claim 1 is characterized in that: Cu is 4～6.5% in the described silver base rare earth alloy material; Ni is 0.2～0.4%; Sm is 0.1～0.25%; Said per-cent is all the mass percent with respect to the silver base rare earth alloy material.
3. silver base rare earth alloy material as claimed in claim 1 or 2 is characterized in that: also comprise Zn in the described silver base rare earth alloy material, its content is 0.01～0.6%, and preferable is 0.15～0.45%; Per-cent is the mass percent with respect to the silver base rare earth alloy material.
4. silver base rare earth alloy material as claimed in claim 1 or 2 is characterized in that: described silver base rare earth alloy material is made by the method that comprises the steps:
1. with raw metal under argon shield melting and cast ingot casting;
2. this ingot casting is carried out homogenizing thermal treatment in 760～800 ℃;
3. surface treatment;
4. cold rolling this ingot casting predeformation that makes, the predeformation amount of this ingot casting on thickness direction is 40%～50%;
5. under vacuum condition or decomposed ammonia atmosphere, anneal in 650 ℃～680 ℃;
6. roll in;
7. in 700 ℃～720 ℃, under nitrogen and hydrogen atmosphere, protect annealing, get final product;
Wherein, the raw metal of step described in 1. comprises the metallic element of following mass percent: Cu0.1～8%; Ni 0.01%～0.5%; Sm 0.01%～0.3%; And Ag, Ag complements to 100%; Preferable, described Cu is 4～6.5%; Ni is 0.2～0.4%; Sm is 0.1～0.25%.
5. silver base rare earth alloy material as claimed in claim 4 is characterized in that: step 1. in, also comprise 0.01～0.6% in the described raw metal, preferable is 0.15～0.45% Zn element, per-cent is the per-cent with respect to the raw metal total mass.
6. like claim 4 or 5 described silver base rare earth alloy materials, it is characterized in that: the homogenizing heat treatment period of step described in 2. is 2.5～3 hours; The annealing time of step described in 5. is 1.5～2 hours; The protection annealed time of step described in 7. is 10～15 minutes; Described protection annealing is carried out in connecting hot stove.
7. silver base rare earth alloy preparation methods as claimed in claim 1 or 2, it is characterized in that: it comprises the steps:
1. with raw metal under argon shield melting and cast ingot casting;
2. this ingot casting is carried out homogenizing thermal treatment in 760～800 ℃;
3. surface treatment;
4. the cold rolling ingot casting generation predeformation that makes, the predeformation amount of this ingot casting on thickness direction is 40%～50%;
5. under the atmosphere of vacuum condition or decomposed ammonia, anneal in 650 ℃～680 ℃;
6. roll in;
7. in 700 ℃～720 ℃, under nitrogen and hydrogen atmosphere, protect annealing, get final product;
Wherein, the raw metal of step described in 1. comprises the metallic element of following mass percent: Cu0.1～8%; Ni 0.01%～0.5%; Sm 0.01%～0.3%; And Ag, Ag complements to 100%; Preferable, described Cu is 4～6.5%; Ni is 0.2～0.4%; Sm is 0.1～0.25%.
8. silver base rare earth alloy preparation methods as claimed in claim 7 is characterized in that: also comprise 0.01～0.6% in the described raw metal, and preferable is 0.15～0.45% Zn element, per-cent is the per-cent with respect to the raw metal total mass.
9. like claim 7 or 8 described silver base rare earth alloy preparation methods, it is characterized in that: the homogenizing heat treatment period of step described in 2. is 2.5～3 hours; The annealing time of step described in 5. is 1.5～2 hours; The protection annealed time of step described in 7. is 10～15 minutes; Described protection annealing is carried out in connecting hot stove.
Like each described silver base rare earth alloy material in the claim 1～6 as the application of sliding contact material, the micromotor sliding contact material that described sliding contact material is preferable for light or moderate duty.
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Cited By (5)
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| JP5913556B1 (en) * | 2014-12-26 | 2016-04-27 | 田中貴金属工業株式会社 | Sliding contact material and manufacturing method thereof |
| CN105648261A (en) * | 2016-02-01 | 2016-06-08 | 重庆川仪自动化股份有限公司 | Material for high-voltage and high-current silver base commutator and preparation method and purpose |
| CN108179304A (en) * | 2018-03-23 | 2018-06-19 | 依波精品（深圳）有限公司 | Silver alloy and its manufacturing process and application |
| CN111411252A (en) * | 2016-01-25 | 2020-07-14 | 田中贵金属工业株式会社 | Sliding contact material and method for producing same |
| US20230187866A1 (en) * | 2020-01-28 | 2023-06-15 | Materion Corporation | Silver alloy clad structure for charging terminals and manufacturing method thereof |
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| JP5913556B1 (en) * | 2014-12-26 | 2016-04-27 | 田中貴金属工業株式会社 | Sliding contact material and manufacturing method thereof |
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| CN111411252A (en) * | 2016-01-25 | 2020-07-14 | 田中贵金属工业株式会社 | Sliding contact material and method for producing same |
| CN105648261A (en) * | 2016-02-01 | 2016-06-08 | 重庆川仪自动化股份有限公司 | Material for high-voltage and high-current silver base commutator and preparation method and purpose |
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| CN108179304A (en) * | 2018-03-23 | 2018-06-19 | 依波精品（深圳）有限公司 | Silver alloy and its manufacturing process and application |
| CN108179304B (en) * | 2018-03-23 | 2019-03-29 | 依波精品（深圳）有限公司 | Silver alloy and its manufacturing process and application |
| US20230187866A1 (en) * | 2020-01-28 | 2023-06-15 | Materion Corporation | Silver alloy clad structure for charging terminals and manufacturing method thereof |
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Effective date of registration: 20180830 Address after: 518122 2 Jinxiu West Road, Pingshan Industrial Zone, Pingshan New District, Shenzhen, Guangdong Patentee after: Shenzhen Nonfemet Technology Co., Ltd. Address before: 201614 Songjiang eighty-sixth, Shanghai, Songjiang. Patentee before: Shanghai Jiqiang Metal Industry Co., Ltd. |
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| TR01 | Transfer of patent right |
Effective date of registration: 20210401 Address after: 518200 Zhongjin Lingnan New Materials and intelligent manufacturing complex building, east of Xinfeng Road, EBU Town, Shenzhen Shantou Special Cooperation Zone, Guangdong Province Patentee after: Shenzhen Shenzhen Shantou Special Cooperation Zone Zhongjin Lingnan New Material Co.,Ltd. Address before: 518122 2 Jinxiu West Road, Pingshan Industrial Zone, Pingshan New District, Shenzhen, Guangdong Patentee before: SHENZHEN NONFEMET TECHNOLOGY Co.,Ltd. |