CN105714148A - Spinodal decomposition type high-strength copper nickel tin alloy and preparation method thereof - Google Patents
Spinodal decomposition type high-strength copper nickel tin alloy and preparation method thereof Download PDFInfo
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- CN105714148A CN105714148A CN201610280996.5A CN201610280996A CN105714148A CN 105714148 A CN105714148 A CN 105714148A CN 201610280996 A CN201610280996 A CN 201610280996A CN 105714148 A CN105714148 A CN 105714148A
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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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Abstract
The invention discloses a spinodal decomposition type high-strength copper nickel tin alloy and a preparation method thereof. The alloy comprises Cu and the following addition elements in percentage by mass: 14.0-16.0% of Ni, 7.0-9.0% of Sn, 0.1-0.3% of Si, and 0.02-0.10% of Ti. The preparation method comprises the following steps of firstly preparing materials, then performing melting by using an antivacuum electric furnace, then performing hot extrusion, and finally, performing heat treatment forming. The spinodal decomposition type high-strength copper nickel tin alloy has excellent mechanical properties, and the preparation method is simple and easy to operate. Compared with a ternary Cu-15Ni-8Sn alloy, the alloy material disclosed by the invention has better obdurability, and can be used for manufacturing spare parts under severe working conditions, such as bearings bearing high speed, heavy loads and the like under corrodible environment.
Description
Technical field
The present invention relates to metal new material technology field, close particularly to a kind of high-strength cuprum-nickel-stannum of spinodal decomposition type
Gold and preparation method thereof.
Background technology
Cu-Ni-Sn alloy is because having good obdurability, excellent corrosion resistance, good wearability, excellent
Good elastic conduction stability and thermal stress relaxation property etc. are it is considered to be have with broad prospects for development new one
For high property copper alloy.
As a kind of spinodal decomposition (Spinodal decomposition) enhanced type alloy, the obdurability of Cu-Ni-Sn alloy
Mainly determined by alloying component, preparation technology and Technology for Heating Processing.Wherein, carrying out optimizing components design is to change
One important channel of kind this kind of alloy property.There are some researches show, the intensity of Cu-Ni-Sn alloy along with
The increase of Ni and Sn constituent content and improve, and reach when Ni content is 15wt% and Sn content 8wt%
To peak value.Therefore, on the basis of main constituent Cu-15Ni-8Sn, add trace alloying element and promote alloy
Performance is an important directions of such alloy research.Such as, U.S.Patent No.426043 and U.S.Patent
No.405220 adds the 4th constituent element in Cu-Ni-Sn alloy, as added 15%Fe, 10%Zn or 15%Mn,
Replacement portion Cu and reduce cost；Add 0.05-0.2%Zr and prevent face checking in ingot casting hot-working；
0.1-0.3%Nb or 0.5-1.0%Cr can improve the plasticity after alloy deformation；Add 0.195%Nb, pass through
After appropriate heat treatment technique, strength of alloy and elongation percentage are all effectively improved；Add Mo, Ta, V etc.
After element, alloy need not pre-cold working just can reach high intensity and high ductility and isotropic shaping
Property；Alternative part Sn of 0.5-1.0%Mg or 0.5-1.5%Al, cost-effective.U.S.Patent No.4130421
In mention, Cu-Ni-Sn alloy adds a small amount of Se, Te, Pb or MnS and can improve alloy machinability
Energy.WO 2014/176357A1 patent discloses in Cu-15Ni-8Sn alloy add B, Zr, Fe,
Nb can promote that equiax crystal is formed, and reduces the segregation of Sn, thus promotes material property.Chinese patent
CN03151047 thinks, adds a small amount of Ti in Cu-15Ni-8Sn alloy, it is thus achieved that uniform tiny equiax crystal,
Make alloy strength improve, and keep good ductility.CN200410053071 is at Cu-15Ni-8Sn alloy
Add a small amount of Y, reduce the segregation of Sn, improve alloy conductive and intensity.
Advanced technology of preparing and trace element currently, with respect to Cu-15Ni-8Sn alloy are to its performance impact
The most non-full maturity of research, promote this material property by microalloying and also have the biggest space, such as
As silicon addition conventional in copper alloy and Ti, play an important role to improving copper alloy performance.Cause
This, the Cu-15Ni-8Sn alloy simultaneously adding Si and Ti is worth further investigation.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of high-strength cuprum-nickel-stannum of spinodal decomposition type
Alloy, this alloy material has more excellent obdurability, can be applicable to manufacture under harsh operating mode (as perishable
Erosion, at a high speed or heavy duty) part that works.
Another object of the present invention is to provide the preparation of a kind of high-strength adonic of above-mentioned spinodal decomposition type
Method.
The technical scheme is that a kind of high-strength adonic of spinodal decomposition type, it is characterised in that close
Containing Cu and following addition element in gold copper-base alloy, each addition element and mass percent thereof are specific as follows:
Ni:14.0～16.0%,
Sn:7.0～9.0%,
Si:0.1～0.3%,
Ti:0.02～0.1%.
In above-mentioned alloy material, in addition to each addition element, its surplus is Cu and inevitable trace is miscellaneous
Prime element.The purpose adding Si and Ti is the indissoluble Second Phase Particle in order to form Dispersed precipitate in the alloy,
Hinder growing up of crystal grain, the generation of discontinuous precipitation phase in suppression ag(e)ing process；What intracrystalline separated out simultaneously is tiny
Granule can hinder dislocation motion, plays dispersion-strengthened action, puies forward heavy alloyed intensity.But Si's and Ti
Content need to strictly control.When Si, Ti content is too low, alloy strength improves inconspicuous, when Si, Ti contain
When measuring too high, the second phase is easily assembled, is roughened, and makes alloy plasticity drastically reduce.
As a kind of preferred version, in described alloy material, the mass percent of each raw material used is as follows: Ni
Being 15.00%, Sn is 8.0%, and Si is 0.10%, and Ti is 0.02%, and surplus is Cu.
As a kind of preferred version, in described alloy material, the mass percent of each raw material used is as follows: Ni
Being 15.00%, Sn is 8.0%, and Si is 0.20%, and Ti is 0.10%, and surplus is Cu.
As a kind of preferred version, in described alloy material, the mass percent of each raw material used is as follows: Ni
Being 15.00%, Sn is 8.0%, and Si is 0.30%, and Ti is 0.10%, and surplus is Cu.
The high-strength adonic of above-mentioned spinodal decomposition type is made to possess the mechanical property of excellence, its material preparation side
Method is the most crucial.The preparation method of the high-strength adonic of above-mentioned spinodal decomposition type specifically includes following step
Rapid:
(1) dispensing: weigh corresponding raw material by the mass percent of each raw material；
(2) melting: use antivacuum electric furnace to carry out melting, be initially charged Cu and Ni；After Cu melts,
Add coverture；After Cu and Ni all melts, add Sn and Si, and be passed through argon refine degasification；
Add Ti after skimming and stir, 1250～1265 DEG C of tapping casting；
(3) hot extrusion: carry out hot extrusion molding, now extrusion ingot temperature after 820～840 DEG C of homo genizing annelaings
Degree is 870～920 DEG C, and the temperature of recipient is 400～450 DEG C；
(4) heat treatment: squeeze wood, after 800～820 DEG C of solution treatment 1 hour, carries out shrend, then
380～420 DEG C of timeliness 4 hours.
Wherein, in described step (2), each composition and mass percent thereof in coverture be: 50%
Glass, the Na of 25%2CO3With 25% CaF2。
In described step (3), extrusion ratio during hot extrusion is 17.
The present invention, relative to prior art, has the advantages that
The high-strength adonic of this spinodal decomposition type has the mechanical property of excellence, and its preparation method is the easiest
OK, compared with ternary Cu-15Ni-8Sn alloy, the alloy material of the present invention has more excellent obdurability,
Can be applicable to manufacture the part worked under harsh operating mode, as born under perishable environment at a high speed and heavy duty
Bearing etc..
The high-strength adonic of this spinodal decomposition type after hot extrusion, its microstructure be improved significantly, obtain
Obtain the most tiny crystal grain, it is ensured that alloy has the plasticity of excellence；Add appropriate Si and Ti, form difficulty
Molten Second Phase Particle, hinders growing up of recrystallization process crystal grain, discontinuous precipitation phase in suppression ag(e)ing process
Produce, play dispersion-strengthened action, put forward heavy alloyed intensity further.
With existing ternary alloy three-partalloy Cu-15Ni-8Sn alloy ratio relatively, the alloy material aging state tension of the present invention
Intensity and elongation percentage have been respectively increased 12% and more than 139% than existing alloy, and hardness improves more than 18%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention
It is not limited to this.
Embodiment 1
The high-strength adonic of the present embodiment one spinodal decomposition type, prepares by the following method:
The first step, dispensing: the raw material used and proportioning thereof are as shown in table 1,
Table 1
| Composition | The trade mark | Standard | Mass percent consumption |
| Cathode copper | Cu 99.95 | GB/T 467-1997 | 76.88% |
| Electrolytic nickel | Ni 99.99 | GB/T 467-1997 | 15.00% |
| Tin slab | Sn 99.95 | GB/T 728-1998 | 8.0% |
| Industrial silicon | Si-1 | GB 2881-1991 | 0.10% |
| Titanium sponge | MHT-110 | GB/T 2524-2002 | 0.02% |
Second step, melting: cathode copper, electrolytic nickel are added in induction furnace as raw material, be warming up to raw material and melt
Change, add coverture, and add tin slab and industrial silicon, after stirring.Fully skim after degasification, then add
Enter titanium sponge, treat that temperature is down to 1250～1265 DEG C, pour in swage, obtain alloy cast ingot.
3rd step, hot extrusion: after carrying out the homogenizing annealing of 8 hours under conditions of 840 DEG C, by alloy
It is processed into the extrusion ingot of Φ 50mm × 50mm, carries out hot extrusion molding；Extrusion ingot is at a temperature of 900 DEG C
Being incubated 1 hour, recipient is incubated 2 hours at a temperature of 450 DEG C, and extrusion nozzle is at a temperature of 350 DEG C
It is incubated 1 hour, sets extrusion ratio as 17.
4th step, heat treatment: squeeze wood shrend after 820 DEG C of solution treatment 1 hour, then 400 DEG C time
Imitate 4 hours, the bar obtained is processed into test sample, carry out alloy aging state Mechanics Performance Testing, knot
Fruit is as shown in table 4.
Embodiment 2
The high-strength adonic of the present embodiment one spinodal decomposition type, prepares by the following method:
The first step, dispensing: the raw material used and proportioning thereof are as shown in table 2,
Table 2
| Composition | The trade mark | Standard | Mass percent consumption |
| Cathode copper | Cu 99.95 | GB/T 467-1997 | 76.70% |
| Electrolytic nickel | Ni 99.99 | GB/T 467-1997 | 15.00% |
| Tin slab | Sn 99.95 | GB/T 728-1998 | 8.0% |
| Industrial silicon | Si-1 | GB 2881-1991 | 0.20% |
| Titanium sponge | MHT-110 | GB/T 2524-2002 | 0.10% |
Second step, melting: cathode copper, electrolytic nickel are added in induction furnace as raw material, be warming up to raw material and melt
Change, add coverture, and add tin slab and industrial silicon, after stirring.Fully skim after degasification, then add
Enter titanium sponge, treat that temperature is down to 1250～1265 DEG C, pour in swage, obtain alloy cast ingot.
3rd step, hot extrusion: after carrying out the homogenizing annealing of 8 hours under conditions of 840 DEG C, by alloy
It is processed into the extrusion ingot of Φ 50mm × 50mm, carries out hot extrusion molding；Extrusion ingot is at a temperature of 900 DEG C
Being incubated 1 hour, recipient is incubated 2 hours at a temperature of 450 DEG C, and extrusion nozzle is at a temperature of 350 DEG C
It is incubated 1 hour, sets extrusion ratio as 17.
4th step, heat treatment: squeeze wood shrend after 820 DEG C of solution treatment 1 hour, then 400 DEG C time
Imitate 4 hours, the bar obtained is processed into test sample, carry out alloy aging state Mechanics Performance Testing, knot
Fruit is as shown in table 4.
Embodiment 3
The high-strength adonic of the present embodiment one spinodal decomposition type, prepares by the following method:
The first step, dispensing: the raw material used and proportioning thereof are as shown in table 3,
Table 3
Second step, melting: cathode copper, electrolytic nickel are added in intermediate frequency furnace as raw material, is warming up to former
Material fusing, adds coverture, and adds tin slab and industrial silicon, after stirring；Fully skim after degasification,
Add titanium sponge, treat that temperature is down to 1250～1265 DEG C, pour in swage, obtain alloy cast ingot.
3rd step, hot extrusion: after carrying out the homogenizing annealing of 8 hours under conditions of 840 DEG C, by alloy
It is processed into the extrusion ingot of Φ 50mm × 50mm, carries out hot extrusion molding.Extrusion ingot is at a temperature of 900 DEG C
Being incubated 1 hour, recipient is incubated 2 hours at a temperature of 450 DEG C, and extrusion nozzle is at a temperature of 350 DEG C
It is incubated 1 hour, sets extrusion ratio as 17.
4th step, heat treatment: squeeze wood shrend after 820 DEG C of solution treatment 1 hour, then 400 DEG C time
Imitate 4 hours, the bar obtained is processed into test sample, carry out alloy aging state Mechanics Performance Testing, knot
Fruit is as shown in table 4.
Comparative example
The alloy material that comparative example uses is former ternary alloy three-partalloy Cu-15Ni-8Sn alloy, its preparation method and reality
Execute example 1 identical, after making test sample, the aging state of this sample is carried out Mechanics Performance Testing, its test
Result is the most as shown in table 4.
Table 4
From table 4, compare with existing ternary alloy three-partalloy Cu-15Ni-8Sn alloy (i.e. comparative example 1),
Aging state tensile strength and the elongation percentage of this spinodal decomposition type high-strength adonic material divide than existing alloy
Not improve more than 12% and more than 139%, hardness improves more than 18%.
As it has been described above, just can preferably realize the present invention, above-described embodiment is only presently preferred embodiments of the present invention,
Not it is used for limiting the practical range of the present invention；The most all impartial changes made according to present invention and modification,
All contained by the claims in the present invention scope required for protection.
Claims (7)
1. the high-strength adonic of spinodal decomposition type, it is characterised in that containing Cu in alloy material
With following addition element, each addition element and mass percent thereof are specific as follows:
Ni:14.0～16.0%,
Sn:7.0～9.0%,
Si:0.1～0.3%,
Ti:0.02～0.10%.
A kind of high-strength adonic of spinodal decomposition type, it is characterised in that
In described alloy material, the mass percent of each raw material used is as follows: Ni is 15.00%, and Sn is 8.0%,
Si is 0.10%, and Ti is 0.02%, and surplus is Cu.
A kind of high-strength adonic of spinodal decomposition type, it is characterised in that
In described alloy material, the mass percent of each raw material used is as follows: Ni is 15.00%, and Sn is 8.0%,
Si is 0.20%, and Ti is 0.10%, and surplus is Cu.
A kind of high-strength adonic of spinodal decomposition type, it is characterised in that
In described alloy material, the mass percent of each raw material used is as follows: Ni is 15.00%, and Sn is 8.0%,
Si is 0.30%, and Ti is 0.10%, and surplus is Cu.
5. the preparation method of the high-strength adonic of a kind of spinodal decomposition type described in any one of Claims 1 to 4,
It is characterized in that, comprise the following steps:
(1) dispensing: weigh corresponding raw material by the mass percent of each raw material；
(2) melting: use antivacuum electric furnace to carry out melting, be initially charged Cu and Ni；After Cu melts,
Add coverture；After Cu and Ni all melts, add Sn and Si, and be passed through argon refine degasification；
Add Ti after skimming and stir, 1250～1265 DEG C of tapping casting；
(3) hot extrusion: carry out hot extrusion molding, now extrusion ingot temperature after 820～840 DEG C of homo genizing annelaings
Degree is 870～920 DEG C, and the temperature of recipient is 400～450 DEG C；
(4) heat treatment: squeeze wood, after 800～820 DEG C of solution treatment 1 hour, carries out shrend, then
380～420 DEG C of timeliness 4 hours.
A kind of preparation method of the high-strength adonic of spinodal decomposition type, its
Being characterised by, in described step (2), each composition and mass percent thereof in coverture be: 50%
Glass, the Na of 25%2CO3With 25% CaF2。
A kind of preparation method of the high-strength adonic of spinodal decomposition type, its
Being characterised by, in described step (3), extrusion ratio during hot extrusion is 17.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756227A (en) * | 2017-02-21 | 2017-05-31 | 江阴华瑞电工科技股份有限公司 | A kind of copper alloy of high resiliency, seawater corrosion resistance |
| CN106756717A (en) * | 2017-01-22 | 2017-05-31 | 扬州大学 | A kind of preparation method of high-strength wearable adonic coating |
| CN106834795A (en) * | 2017-02-21 | 2017-06-13 | 江阴华瑞电工科技股份有限公司 | A kind of high resiliency, corrosion-resistant, wear-resisting Cu Ni Sn alloy preparation methods |
| CN108677059A (en) * | 2018-05-28 | 2018-10-19 | 中色奥博特铜铝业有限公司 | Cu-15Ni-8Sn copper alloys, Copper alloy bar and preparation method thereof |
| CN111020284A (en) * | 2019-12-19 | 2020-04-17 | 无锡隆达金属材料有限公司 | Preparation method of high-strength wear-resistant copper alloy pipe |
| CN111719065A (en) * | 2020-06-08 | 2020-09-29 | 广东中发摩丹科技有限公司 | Cu-Ni-Sn-Si-Ag-P multi-element alloy foil and preparation method thereof |
| CN111826547A (en) * | 2020-07-13 | 2020-10-27 | 苏州金江铜业有限公司 | Copper-nickel-tin-silver-boron alloy and preparation method thereof |
| CN113278846A (en) * | 2021-04-06 | 2021-08-20 | 中铝材料应用研究院有限公司 | Wear-resistant copper-nickel-tin alloy and preparation method thereof |
| CN113351879A (en) * | 2021-05-27 | 2021-09-07 | 北京科技大学 | Preparation method for cold deformation and heat treatment reinforced additive manufacturing of Cu-Ni-Sn alloy |
| CN113755716A (en) * | 2021-09-07 | 2021-12-07 | 大连理工大学 | High-performance copper-nickel-tin alloy and preparation method thereof |
| CN115786766A (en) * | 2022-11-23 | 2023-03-14 | 河南科技大学 | Multi-element Cu-Ni-Sn-based alloy for oil and gas exploitation and preparation method thereof |
| WO2023061514A1 (en) * | 2022-11-23 | 2023-04-20 | 河南科技大学 | Cu-15ni-8sn-based alloy for ocean engineering, and preparation method therefor |
| CN116287857A (en) * | 2023-04-04 | 2023-06-23 | 昆明理工大学 | High-elasticity high-strength high-conductivity Cu-Ni-Sn alloy and preparation method thereof |
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| CN106756717A (en) * | 2017-01-22 | 2017-05-31 | 扬州大学 | A kind of preparation method of high-strength wearable adonic coating |
| CN106834795A (en) * | 2017-02-21 | 2017-06-13 | 江阴华瑞电工科技股份有限公司 | A kind of high resiliency, corrosion-resistant, wear-resisting Cu Ni Sn alloy preparation methods |
| CN106756227A (en) * | 2017-02-21 | 2017-05-31 | 江阴华瑞电工科技股份有限公司 | A kind of copper alloy of high resiliency, seawater corrosion resistance |
| CN108677059A (en) * | 2018-05-28 | 2018-10-19 | 中色奥博特铜铝业有限公司 | Cu-15Ni-8Sn copper alloys, Copper alloy bar and preparation method thereof |
| CN108677059B (en) * | 2018-05-28 | 2020-05-19 | 中色奥博特铜铝业有限公司 | Cu-15Ni-8Sn copper alloy, copper alloy bar and preparation method thereof |
| CN111020284B (en) * | 2019-12-19 | 2021-10-29 | 江苏隆达超合金股份有限公司 | Preparation method of high-strength wear-resistant copper alloy pipe |
| CN111020284A (en) * | 2019-12-19 | 2020-04-17 | 无锡隆达金属材料有限公司 | Preparation method of high-strength wear-resistant copper alloy pipe |
| CN111719065B (en) * | 2020-06-08 | 2021-11-16 | 广东中发摩丹科技有限公司 | Cu-Ni-Sn-Si-Ag-P multi-element alloy foil and preparation method thereof |
| CN111719065A (en) * | 2020-06-08 | 2020-09-29 | 广东中发摩丹科技有限公司 | Cu-Ni-Sn-Si-Ag-P multi-element alloy foil and preparation method thereof |
| CN111826547B (en) * | 2020-07-13 | 2021-09-17 | 苏州金江铜业有限公司 | Copper-nickel-tin-silver-boron alloy and preparation method thereof |
| CN111826547A (en) * | 2020-07-13 | 2020-10-27 | 苏州金江铜业有限公司 | Copper-nickel-tin-silver-boron alloy and preparation method thereof |
| CN113278846A (en) * | 2021-04-06 | 2021-08-20 | 中铝材料应用研究院有限公司 | Wear-resistant copper-nickel-tin alloy and preparation method thereof |
| CN113351879A (en) * | 2021-05-27 | 2021-09-07 | 北京科技大学 | Preparation method for cold deformation and heat treatment reinforced additive manufacturing of Cu-Ni-Sn alloy |
| CN113755716A (en) * | 2021-09-07 | 2021-12-07 | 大连理工大学 | High-performance copper-nickel-tin alloy and preparation method thereof |
| CN115786766A (en) * | 2022-11-23 | 2023-03-14 | 河南科技大学 | Multi-element Cu-Ni-Sn-based alloy for oil and gas exploitation and preparation method thereof |
| WO2023061514A1 (en) * | 2022-11-23 | 2023-04-20 | 河南科技大学 | Cu-15ni-8sn-based alloy for ocean engineering, and preparation method therefor |
| CN116287857A (en) * | 2023-04-04 | 2023-06-23 | 昆明理工大学 | High-elasticity high-strength high-conductivity Cu-Ni-Sn alloy and preparation method thereof |
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