CN105714148B - A kind of high-strength adonic of spinodal decomposition type - Google Patents
A kind of high-strength adonic of spinodal decomposition type Download PDFInfo
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- CN105714148B CN105714148B CN201610280996.5A CN201610280996A CN105714148B CN 105714148 B CN105714148 B CN 105714148B CN 201610280996 A CN201610280996 A CN 201610280996A CN 105714148 B CN105714148 B CN 105714148B
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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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- 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
- C22C1/02—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 present invention discloses high-strength adonic of a kind of spinodal decomposition type and preparation method thereof, Cu and following addition element is contained in alloy, each addition element and its mass percent are specific as follows：14.0~16.0%Ni, 7.0~9.0%Sn, 0.1~0.3%Si, 0.02~0.10%Ti.Its preparation method is：First dispensing, then carries out melting using antivacuum electric furnace, then carries out hot extrusion, finally carries out heat-treating profiled.The high-strength adonic of this spinodal decomposition type has excellent mechanical property, and its preparation method is simple and easy to apply, compared with ternary Cu 15Ni 8Sn alloys, the alloy material of the present invention has more excellent obdurability, the part that manufacture works under harsh operating mode is can be applied to, the bearing at a high speed with heavy duty is such as born under perishable environment.
Description
Technical field
The present invention relates to metal new material technology field, more particularly to a kind of high-strength adonic of spinodal decomposition type.
Background technology
Cu-Ni-Sn alloys are because with good obdurability, excellent corrosion resistance, good wearability, excellent elastic conducting
Electrical stability and thermal stress relaxation property etc., it is considered to be tool high property copper alloy of new generation with broad prospects for development.
As a kind of spinodal decomposition (Spinodal decomposition) enhanced type alloy, the obdurability of Cu-Ni-Sn alloys is main by closing
Golden composition, preparation technology and Technology for Heating Processing are determined.Wherein, it is to improve one of this kind of alloy property to carry out optimizing components design
Important channel.There are some researches show the intensity of Cu-Ni-Sn alloys is improved with the increase of Ni and Sn constituent contents, and in Ni
Content reaches peak value when being 15wt% and Sn content 8wt%.Therefore, add micro on the basis of principal component Cu-15Ni-8Sn
Alloying element lifts the important directions that alloy property is such alloy research.For example, U.S.Patent No.426043
The 4th constituent element is added in Cu-Ni-Sn alloys with U.S.Patent No.405220,15%Fe, 10%Zn or 15% is such as added
Mn, replacement portion Cu and reduce cost；Adding 0.05-0.2%Zr prevents 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；0.195%Nb is added, after appropriate heat treatment technique, alloy resists
Tensile strength and elongation percentage are effectively improved；Add after the elements such as Mo, Ta, V, alloy does not need pre-cold working with regard to that can reach high intensity
With high ductility and isotropic formability；The alternative part Sn of 0.5-1.0%Mg or 0.5-1.5%Al, save cost.
Mentioned in U.S.Patent No.4130421, a small amount of Se, Te, Pb or MnS are added in Cu-Ni-Sn alloys can improve alloy and cut
Cut performance.Addition B, Zr, Fe, Nb in Cu-15Ni-8Sn alloys are disclosed in WO 2014/176357A1 patents to be promoted
Axialite is formed, and reduces Sn segregation, so as to lift material property.Chinese patent CN03151047 thinks, is closed in Cu-15Ni-8Sn
A small amount of Ti is added in gold, uniform tiny equiax crystal is obtained, improves alloy strength, and keep good ductility.
CN200410053071 adds a small amount of Y in Cu-15Ni-8Sn alloys, reduces Sn segregation, improves alloy conductive and intensity.
At present, the advanced technology of preparing on Cu-15Ni-8Sn alloys and the micro- research to its performance impact
Also non-full maturity, lifts this material property by microalloying and also has very big space, such as normal in copper alloy
Silicon addition and Ti, play an important role to improving copper alloy performance.Therefore, while adding Si and Ti Cu-15Ni-
8Sn alloys are worth further investigation.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of high-strength adonic of spinodal decomposition type,
The alloy material has more excellent obdurability, can be applied to manufacture (such as perishable, at a high speed or heavily loaded) work under harsh operating mode
The part of work.
Another object of the present invention is to provide a kind of preparation method of the high-strength adonic of above-mentioned spinodal decomposition type.
The technical scheme is that：A kind of high-strength adonic of spinodal decomposition type, it is characterised in that in alloy material
Containing Cu and following addition element, each addition element and its mass percent 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 micro impurity element.Plus
The purpose for entering Si and Ti is that, in order to form the indissoluble Second Phase Particle of Dispersed precipitate in the alloy, growing up for obstruction crystal grain suppresses
The generation of discontinuous precipitation phase in ag(e)ing process；The fine particle of transgranular precipitation simultaneously can hinder dislocation motion, play disperse
Invigoration effect, improves the intensity of alloy.But Si and Ti content need to be controlled strictly.When Si, Ti content are too low, alloy strength is carried
High unobvious, when Si, Ti too high levels, second mutually easily occurs aggregation, roughening, drastically reduces alloy plasticity.
As a kind of preferred scheme, the mass percent of each raw material used is as follows in the alloy material：Ni is
15.00%, Sn are that 8.0%, Si is that 0.10%, Ti is 0.02%, and surplus is Cu.
As a kind of preferred scheme, the mass percent of each raw material used is as follows in the alloy material：Ni is
15.00%, Sn are that 8.0%, Si is that 0.20%, Ti is 0.10%, and surplus is Cu.
As a kind of preferred scheme, the mass percent of each raw material used is as follows in the alloy material：Ni is
15.00%, Sn are that 8.0%, Si is that 0.30%, Ti is 0.10%, and surplus is Cu.
The high-strength adonic of above-mentioned spinodal decomposition type is possessed excellent mechanical property, its material preparation method nor
Chang Guanjian.The preparation method of the above-mentioned high-strength adonic of spinodal decomposition type specifically includes following steps：
(1) dispensing：Corresponding raw material is weighed by the mass percent of each raw material；
(2) melting：Melting is carried out using antivacuum electric furnace, Cu and Ni is first added；After after Cu fusings, coverture is added；Treat
Cu and Ni all after fusing, adds Sn and Si, and be passed through argon gas refining degasification；Ti is added after skimming and is stirred, 1250
~1265 DEG C of tapping castings；
(3) hot extrusion：Hot extrusion molding is carried out after 820~840 DEG C of homo genizing annelaings, now extrusion ingot temperature be 870~
920 DEG C, the temperature of recipient is 400~450 DEG C；
(4) it is heat-treated：Squeeze wood carries out water quenching, then at 380~420 DEG C after 800~820 DEG C of solution treatment 1 hour
Timeliness 4 hours.
Wherein, in the step (2), each composition and its mass percent in coverture are：50% glass, 25%
Na2CO3With 25% CaF2。
In the step (3), extrusion ratio during hot extrusion is 17.
The present invention has the advantages that relative to prior art：
The high-strength adonic of this spinodal decomposition type has excellent mechanical property, and its preparation method is simple and easy to apply, with
Ternary Cu-15Ni-8Sn alloys are compared, and alloy material of the invention has more excellent obdurability, can be applied to manufacture in harshness
The part worked under operating mode, such as bears the bearing at a high speed with heavy duty under perishable environment.
The high-strength adonic of this spinodal decomposition type after hot extrusion, its microstructure be improved significantly, obtain uniform
Tiny crystal grain, it is ensured that alloy has excellent plasticity；Appropriate Si and Ti is added, indissoluble Second Phase Particle is formed, hindered again
Growing up for crystallization process crystal grain, suppresses the generation of discontinuous precipitation phase in ag(e)ing process, plays dispersion-strengthened action, further carry
The intensity of high alloy.
With existing ternary alloy three-partalloy Cu-15Ni-8Sn alloy ratios compared with, alloy material aging state tensile strength of the invention and
12% and more than 139% has been respectively increased than existing alloy in elongation percentage, and hardness improves more than 18%.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
A kind of high-strength adonic of spinodal decomposition type of the present embodiment, is made by the following method：
The first step, dispensing：The raw material and its proportioning used is 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, melting sources are warming up to, addition is covered
Lid agent, and tin slab and industrial silicon are added, after stirring.Skimmed after abundant degasification, add titanium sponge, treat that temperature is down to 1250
~1265 DEG C, pour into swage, obtain alloy cast ingot.
3rd step, hot extrusion：After carrying out the homogenizing annealing of 8 hours under conditions of 840 DEG C, alloy is processed into Φ
50mm × 50mm extrusion ingot, carries out hot extrusion molding；Extrusion ingot is incubated 1 hour at a temperature of 900 DEG C, and recipient is 450
2 hours are incubated at a temperature of DEG C, extrusion nozzle is incubated 1 hour at a temperature of 350 DEG C, sets extrusion ratio as 17.
4th step, heat treatment：Squeeze wood is through water quenching after 820 DEG C of solution treatment 1 hour, and then 400 DEG C of timeliness 4 hours will
Obtained bar is processed into test sample, carries out alloy aging state Mechanics Performance Testing, as a result as shown in table 4.
Embodiment 2
A kind of high-strength adonic of spinodal decomposition type of the present embodiment, is made by the following method：
The first step, dispensing：The raw material and its proportioning used is 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, melting sources are warming up to, addition is covered
Lid agent, and tin slab and industrial silicon are added, after stirring.Skimmed after abundant degasification, add titanium sponge, treat that temperature is down to 1250
~1265 DEG C, pour into swage, obtain alloy cast ingot.
3rd step, hot extrusion：After carrying out the homogenizing annealing of 8 hours under conditions of 840 DEG C, alloy is processed into Φ
50mm × 50mm extrusion ingot, carries out hot extrusion molding；Extrusion ingot is incubated 1 hour at a temperature of 900 DEG C, and recipient is 450
2 hours are incubated at a temperature of DEG C, extrusion nozzle is incubated 1 hour at a temperature of 350 DEG C, sets extrusion ratio as 17.
4th step, heat treatment：Squeeze wood is through water quenching after 820 DEG C of solution treatment 1 hour, and then 400 DEG C of timeliness 4 hours will
Obtained bar is processed into test sample, carries out alloy aging state Mechanics Performance Testing, as a result as shown in table 4.
Embodiment 3
A kind of high-strength adonic of spinodal decomposition type of the present embodiment, is made by the following method：
The first step, dispensing：The raw material and its proportioning used is as shown in table 3,
Table 3
Second step, melting：Cathode copper, electrolytic nickel are added in intermediate frequency furnace as raw material, melting sources are warming up to, plus
Enter coverture, and add tin slab and industrial silicon, after stirring；Skimmed after abundant degasification, add titanium sponge, treat that temperature is down to
1250~1265 DEG C, pour into swage, obtain alloy cast ingot.
3rd step, hot extrusion：After carrying out the homogenizing annealing of 8 hours under conditions of 840 DEG C, alloy is processed into Φ
50mm × 50mm extrusion ingot, carries out hot extrusion molding.Extrusion ingot is incubated 1 hour at a temperature of 900 DEG C, and recipient is 450
2 hours are incubated at a temperature of DEG C, extrusion nozzle is incubated 1 hour at a temperature of 350 DEG C, sets extrusion ratio as 17.
4th step, heat treatment：Squeeze wood is through water quenching after 820 DEG C of solution treatment 1 hour, and then 400 DEG C of timeliness 4 hours will
Obtained bar is processed into test sample, carries out alloy aging state Mechanics Performance Testing, as a result as shown in table 4.
Comparative example
The alloy material that comparative example is used is former ternary alloy three-partalloy Cu-15Ni-8Sn alloys, its preparation method and the phase of embodiment 1
Together, it is made after test sample, Mechanics Performance Testing is carried out to the aging state of the sample, its test result difference is as shown in table 4.
Table 4
From table 4, compared, this spinodal decomposition type with existing ternary alloy three-partalloy Cu-15Ni-8Sn alloys (i.e. comparative example 1)
More than 12% and 139% has been respectively increased in the aging state tensile strength and the existing alloy of elongation percentage ratio of high-strength adonic material
More than, hardness improves more than 18%.
As described above, the present invention can be better realized, above-described embodiment is only presently preferred embodiments of the present invention, is not used
To limit the practical range of the present invention；I.e. all equivalent changes and modifications made according to present invention, all will for right of the present invention
Scope claimed is asked to be covered.
Claims (6)
1. a kind of high-strength adonic of spinodal decomposition type, it is characterised in that contain Cu and following addition element in alloy material,
Each addition element and its mass percent are specific as follows：
Ni：14.0~16.0%,
Sn：7.0~9.0%,
Si：0.1~0.3%,
Ti：0.02~0.10%；
The high-strength adonic of spinodal decomposition type is made by following steps：
(1) dispensing：Corresponding raw material is weighed by the mass percent of each raw material；
(2) melting：Melting is carried out using antivacuum electric furnace, Cu and Ni is first added；After after Cu fusings, coverture is added；Treat Cu and
Ni all after fusing, adds Sn and Si, and be passed through argon gas refining degasification；Add and Ti and stir after skimming, 1250~
1265 DEG C of tapping castings；
(3) hot extrusion：Hot extrusion molding is carried out after 820~840 DEG C of homo genizing annelaings, now extrusion ingot temperature is 870~920
DEG C, the temperature of recipient is 400~450 DEG C；
(4) it is heat-treated：Squeeze wood carries out water quenching, then in 380~420 DEG C of timeliness after 800~820 DEG C of solution treatment 1 hour
4 hours.
2. the high-strength adonic of a kind of spinodal decomposition type according to claim 1, it is characterised in that in the alloy material
The mass percent of each raw material used is as follows：Ni is that 15.00%, Sn is that 8.0%, Si is that 0.10%, Ti is 0.02%, and surplus is
Cu。
3. the high-strength adonic of a kind of spinodal decomposition type according to claim 1, it is characterised in that in the alloy material
The mass percent of each raw material used is as follows：Ni is that 15.00%, Sn is that 8.0%, Si is that 0.20%, Ti is 0.10%, and surplus is
Cu。
4. the high-strength adonic of a kind of spinodal decomposition type according to claim 1, it is characterised in that in the alloy material
The mass percent of each raw material used is as follows：Ni is that 15.00%, Sn is that 8.0%, Si is that 0.30%, Ti is 0.10%, and surplus is
Cu。
5. the high-strength adonic of a kind of spinodal decomposition type according to claim 1, it is characterised in that in the step (2),
Each composition and its mass percent in coverture are：50% glass, 25% Na2CO3With 25% CaF2。
6. the high-strength adonic of a kind of spinodal decomposition type according to claim 1, it is characterised in that in the step (3),
Extrusion ratio during hot extrusion is 17.
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| CN106756717B (en) * | 2017-01-22 | 2019-12-31 | 扬州大学 | Preparation method of high-strength wear-resistant copper-nickel-tin alloy 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 |
| 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 |
| 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 |
| 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 |
| CN113278846B (en) * | 2021-04-06 | 2022-08-12 | 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 |
| CN115786766B (en) * | 2022-11-23 | 2024-07-05 | 河南科技大学 | Multi-element Cu-Ni-Sn-based alloy for oil and gas exploitation and preparation method thereof |
| CN115747563B (en) * | 2022-11-23 | 2023-12-19 | 河南科技大学 | Cu-15Ni-8 Sn-based alloy for ocean engineering and preparation method thereof |
| 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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| CN1240863C (en) * | 2003-09-18 | 2006-02-08 | 上海交通大学 | Titaniferous cuprum-nickel-stannum spinodal decomposition type anti-friction bearing alloy and preparation method thereof |
| CN101717878A (en) * | 2009-12-10 | 2010-06-02 | 北京有色金属研究总院 | Seawater scouring corrosion resistant nickel-copper alloy and tubular product and preparation method thereof |
| JP6380855B2 (en) * | 2013-06-04 | 2018-08-29 | 日本碍子株式会社 | Copper alloy manufacturing method and copper alloy |
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