CN105063418A - Low-alloying copper belt and preparation method thereof - Google Patents
Low-alloying copper belt and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-alloying copper belt and further relates to a preparation method of the low-alloying copper belt. The low-alloying copper belt is characterized by including the following components of, by weight, 0.3-1.2 parts of Sn, 0.1-1.5 parts of Zn, 0.5-2.0 parts of Ni, 0.03-0.2 part of Po, 0-0.1 part of Fe and 93-99 parts of Cu. In the low-alloying copper belt, the Sn, Ni, Zn and P of low contents are subjected to solid solution treatment and exist in a matrix in a solid solution mode, and meanwhile part of the Ni and P form second-phase phosphide, that is, nickel phosphide, so that strength and the stress relaxation resistant performance of materials are improved, and the materials have high elasticity and conductivity; besides, the proportional relation between contents of the Sn, Ni and Zn is good for improvement of intensity and elasticity of the materials, the strengthening effect is not apparent when the contents of the Sn, Ni and Zn are too low, and the material conductivity is reduced seriously when the contents of the Sn, Ni and Zn are too high; compound hard particles separate out from the Ni and P in the low-alloying copper belt, so that the material elasticity is improved.
Description
Technical field
The present invention relates to the low alloying copper strips technical field for automobile terminal, specifically refer to a kind of low alloying copper strips with snappiness, high conductivity, the invention still further relates to the preparation method of above-mentioned low alloying copper strips.
Background technology
Tin-phosphor bronze is conventional elastic alloy, this alloy can obtain good mechanical property by Sn-P element interaction and cold hardening, there is the features such as anti-corrosion, wear-resisting, nonmagnetic and excellent elastic performance, also there is higher elongation, being easy to process the elastic element that punching becomes various complicated shape, is the resilient material that in Copper-Nickel-Aluminium Alloy material, consumption is maximum, purposes is the widest.
Publication number is the Chinese invention patent application " a kind of high-performance tin-phosphor bronze line and production method thereof " (application number: CN201410448856.5) of CN104152742A, publication number is the preparation method that Chinese invention patent application " a kind of preparation method of high-elasticity Sn-P bronze alloy foil " (application number: CN201110171904.7) of CN102259252A etc. all discloses tin-phosphor bronze material, at present, in the composition proportion of conventional tin-phosphor bronze, Theil indices is generally 4 ~ 9%, phosphorus content is 0.1 ~ 0.2%, such proportioning causes that the cost of tin-phosphor bronze material is higher and electric conductivity is lower, electric conductivity is only 11% ~ 19%IACS, the requirement of automobile terminal and high-end product connector high conductivity used thereof cannot be met.
Application number is that the middle Theil indices of Chinese invention patent application " a kind of snappiness low cost Sn-P-Cu alloy band and preparation method thereof " of CN201510275343.3 is 0.5 ~ 2.5wt%, nickel content is 0 ~ 1.0wt%, phosphorus content is 0.05 ~ 0.5wt%, the electric conductivity of this alloy can reach 20%, but this electric conductivity is still due to too low and cannot be applicable to automobile terminal or high-end product connector used.
Summary of the invention
Technical problem to be solved by this invention is the present situation for prior art, provides a kind of low alloying copper strips with snappiness, high conductivity and stress relaxation-resistant.
Another technical problem to be solved by this invention is the present situation for prior art, a kind of preparation method of above-mentioned low alloying copper strips is provided, the method step is simple, and prepared low alloying copper strips has higher stress relaxation-resistant and electric conductivity and preparation cost is low.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of low alloying copper strips, it is characterized in that comprising following component by weight:
In such scheme, in described low alloying copper strips, a part of P and Ni exists with the form of nickel phosphide, and remaining P and Ni and Sn, Zn exist with the form of sosoloid respectively.
A preparation method for low alloying copper strips, is characterized in that comprising the following steps:
(1) 0.3 ~ 1.2 part of Sn, 0.1 ~ 1.5 part of Zn, 0.5 ~ 2.0 part of Ni, 0.03 ~ 0.2 part of P, 0 ~ 0.1 part of Fe and 93 ~ 99 part Cu are added in induction furnace carry out melting, and adopt charcoal to cover, smelting temperature is 1200 ~ 1250 DEG C, after metal all melts, refining adjusting component;
(2) carry out horizontal continuous-casting to step (1) gained copper alloy strand, pouring temperature is 1150 ~ 1250 DEG C;
(3) carry out cold-rolling treatment after being washed one's face by step (2) gained copper alloy strand and obtain finished product.
As improvement, the cold-rolling treatment process described in step (3) comprises strand, cold rolling, process annealing, middle cold rolling and annealing of keeping on file successively, and wherein, described cold rolling and middle cold rolling working modulus is 80 ~ 90%.The temperature of described process annealing is 580 ~ 650 DEG C, is preferably 650 DEG C.Described temperature of keeping to anneal on file is 480 DEG C.
In above-mentioned preferred version, carry out finished product rolling, finished product low-temperature annealing after described step (3) completes again successively and check out finished product process, the stress relief annealed temperature of described finished product is 280 ~ 320 DEG C, and annealing time is 2.5 ~ 3.5h.
As preferably, described P adds with the form of phosphor copper, and in this phosphor copper, the massfraction of P is 14 ~ 14.5%.
Preferably, described Ni and the Cu of surplus adds with the form of electrolytic nickel and electrolytic copper respectively.
Compared with prior art, the invention has the advantages that:
In low-alloy copper strips of the present invention, Sn, Ni, Zn, P solid solution of low levels, be present in matrix with the form of sosoloid, simultaneously, a part Ni and P forms second-phase phosphide, i.e. nickel phosphide, thus the intensity and the stress relaxation resistance that improve material, make material have snappiness and high conductivity; And in the present invention Sn, Ni, Zn content between proportionlity be also conducive to improving the intensity of material and elasticity, when Sn, Ni, Zn content is too low, its strengthening effect is not obvious, and during Sn, Ni, Zn too high levels, seriously will reduce materials conductive rate; Composition proportion of the present invention makes the electric conductivity of material be greater than 30%, and Young's modulus is at 122 ~ 125GPa;
Ni in low-alloy copper strips of the present invention is except playing solution strengthening effect, and all right crystal grain thinning, improves recrystallization temperature; P mono-can play solution strengthening effect in aspect, another aspect can also play deoxidation and improve the effect of fluidity of molten, simultaneously, Ni and P precipitation compounds hard particles, can in crystal boundary and intracrystalline pinning dislocation, improve the stress relaxation-resistant of material and suppress recrystallize, thus improving the elasticity of material; Can in grain boundaries place segregation when P too high levels, serious reduction material plasticity and electric conductivity.
Preparation method's step of low alloying copper strips of the present invention is simple, adopt large working modulus cold-rolling treatment and suitable intermediate anneal temperature to eliminate as-cast structure, strand is after cold-rolling treatment, bulk crystal grain and dendritic structure are all rolled broken, formed and there is the texture structure substantially consistent with rolling direction, rising texture structure with annealing temperature has significantly eliminates sign, when annealing temperature is increased to 620 ~ 650 DEG C, the orientation of texture becomes by fuzzy to elimination, avoid copper strips performance along rolling direction orientation, thus make alloy strip have good transverse and longitudinal performance; After keeping on file to anneal alloy sheet strip metallographic structure on there is no perfect recrystallization, remain certain cold deformed microstructure, there is proper mechanical property, make finished product have higher resistance to stress relaxation force;
Low-alloy copper strips prepared by the present invention has higher stress relaxation-resistant and electric conductivity, and simultaneously because preparation section is simple, Sn, Ni, Zn content reasonable ratio, reduces the production cost of material to a certain extent, improves the market competitiveness of material.
Accompanying drawing explanation
Fig. 1 is cold rolling rear materials microstructure structure iron under different annealing temperature in the embodiment of the present invention;
Fig. 2 is materials microstructure structure iron after keeping on file in the embodiment of the present invention to anneal.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
In the present invention, the preparation method of low alloying copper strips comprises the following steps:
(1) by weight percentage, the raw material of respective amount is taken according to the formula of low alloying copper strips in table 5, electrolytic copper, electrolytic nickel, phosphor copper, zinc ingot metal, tin slab are added in induction furnace successively and carries out melting, and adopt charcoal to cover, smelting temperature is 1200 ~ 1250 DEG C, after metal all melts, refining adjusting component;
(2) carry out horizontal continuous-casting to step (1) gained copper alloy strand, pouring temperature is 1150 ~ 1250 DEG C;
(3) cold-rolling treatment is carried out after being washed one's face by step (2) gained copper alloy strand, this cold-rolling treatment process is: strand → cold rolling → process annealing → centre is cold rolling → and annealing of keeping on file, wherein, the blank dimension that strand obtains is 70 × 16mm, cold rolling working modulus is 90%, middle cold rolling working modulus is 80%, and the temperature of process annealing is 580 ~ 650 DEG C, and the temperature of keeping on file to anneal is 480 DEG C;
(4) finished product rolling, finished product low-temperature annealing carried out successively to step (3) gained strand and check out finished product process.
As shown in Figure 1, Fig. 1 a, 1b are respectively the cold rolling rear horizontal and longitudinal organization chart of material when intermediate anneal temperature is 580 DEG C, Fig. 1 c, 1d are respectively the cold rolling rear horizontal and longitudinal organization chart of material when intermediate anneal temperature is 620 DEG C, and Fig. 1 e, 1f are respectively the cold rolling rear horizontal and longitudinal organization chart of material when intermediate anneal temperature is 650 DEG C.Table 3 is the mechanical performance data of material when centre is cold-rolled to size 70 × 0.2mm.
Table 3
As can be seen from Fig. 1 associative list 3; rising texture structure with annealing temperature has significantly eliminates sign; but the vestige of modulated structure is still high-visible when temperature is increased to 580 DEG C; mechanical property has very large reply, and matrix still keeps the texture structure with rolling direction, and the orientation of texture is still very clear; along with the vestige of raising 620 DEG C of modulated structures of temperature also has; but unintelligible, when temperature disappears to modulated structure when 650 DEG C, alloy strip has good transverse and longitudinal performance.
As shown in Figure 2, in Fig. 2,2a, 2b are respectively 480 DEG C of annealing of keeping on file, to be cold-rolled to thickness be the hard state of 0.8mm alloy sheet strip and the organization chart of annealed state in centre, and table 4 be that centre is cold-rolled to the data of mechanical that thickness is 0.7mm alloy sheet strip.Can find out, metallographic structure does not have perfect recrystallization, remain certain cold deformed microstructure, have proper mechanical property, finished product has higher resistance to stress relaxation force, i.e. snappiness.
Table 4
Table 5
| Element | Cu | Sn | P | Ni | Fe | Zn |
| Content | 97.56 | 0.9 | 0.06 | 0.9 | 0.08 | 0.5 |
Table 1 is the material prescription of embodiment 1 ~ 3 and comparative example 1, and wherein, the material of comparative example 1 is C5191 phosphor bronze, and in table 1, each data all by weight percentage; The performance test data of table 2 material prepared by the formula according to embodiment 1 ~ 3 and comparative example 1.
Induction furnace in embodiment 1,2,3 adopts 300Kg medium-frequency induction furnace, smelting temperature 1200 ~ 1250 DEG C, and teeming temperature is 1150 ~ 1220 DEG C, and adopt horizontal continuous-casting, blank is 70 × 16mm.Cold-rolling treatment process: strand 70 × 16mm → cold rolling (working modulus 90%) (70 × 2.0mm) → process annealing (temperature 650 DEG C) → centre cold rolling (70 × 0.8mm) → keep on file to anneal (temperature 480 DEG C).
Table 1
| Element | Cu | Sn | P | Ni | Fe | Zn |
| Embodiment 1 | 97.5 | 0.8 | 0.05 | 1.1 | 0.05 | 0.5 |
| Embodiment 2 | 97.3 | 1.1 | 0.05 | 1.1 | 0.05 | 0.4 |
| Embodiment 3 | 95.8 | 1.5 | 0.1 | 1.0 | 0.05 | 1.5 |
| Comparative example 1 | 92-94 | 6.0-7.0 | 0.10-0.25 | ≤0.2 | ≤0.1 | — |
Table 2
Visible, the low alloying copper strips of formula preparation of the present invention has and has higher stress relaxation-resistant and electric conductivity simultaneously, is a kind of comparatively ideal high conductivity, elastomeric copper strips material, may be used for electronic connector, automobile terminal manufactures field.
Claims (9)
1. a low alloying copper strips, is characterized in that comprising following component by weight:
2. low alloying copper strips according to claim 1, is characterized in that: in described low alloying copper strips, a part of P and Ni exists with the form of nickel phosphide, and remaining P and Ni and Sn, Zn exist with the form of sosoloid respectively.
3. a preparation method for low alloying copper strips, is characterized in that comprising the following steps:
(1) 0.3 ~ 1.2 part of Sn, 0.1 ~ 1.5 part of Zn, 0.5 ~ 2.0 part of Ni, 0.03 ~ 0.2 part of P, 0 ~ 0.1 part of Fe and 93 ~ 99 part Cu are added in induction furnace carry out melting, and adopt charcoal to cover, smelting temperature is 1200 ~ 1250 DEG C, after metal all melts, refining adjusting component;
(2) carry out horizontal continuous-casting to step (1) gained copper alloy strand, pouring temperature is 1150 ~ 1250 DEG C;
(3) carry out cold-rolling treatment after being washed one's face by step (2) gained copper alloy strand and obtain finished product.
4. the preparation method of low alloying copper strips according to claim 3, it is characterized in that: the cold-rolling treatment process described in step (3) comprises strand, cold rolling, process annealing, middle cold rolling and annealing of keeping on file successively, wherein, described cold rolling and middle cold rolling working modulus is 80 ~ 90%.
5. the preparation method of low alloying copper strips according to claim 4, is characterized in that: the temperature of described process annealing is 580 ~ 650 DEG C.
6. the preparation method of low alloying copper strips according to claim 4, is characterized in that: described in keep on file anneal temperature be 480 DEG C.
7. the preparation method of low alloying copper strips according to claim 1, it is characterized in that: carry out finished product rolling, finished product low-temperature annealing after described step (3) completes again successively and check out finished product process, the stress relief annealed temperature of described finished product is 280 ~ 320 DEG C, and annealing time is 2.5 ~ 3.5h.
8. the preparation method of low alloying copper strips according to claim 1, is characterized in that: described P adds with the form of phosphor copper, and in this phosphor copper, the massfraction of P is 14 ~ 14.5%.
9. the preparation method of low alloying copper strips according to claim 8, is characterized in that: described Ni and the Cu of surplus adds with the form of electrolytic nickel and electrolytic copper respectively.
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| CN105316520A (en) * | 2015-11-26 | 2016-02-10 | 山西春雷铜材有限责任公司 | Preparation method of Cu-Ni-Sn plate strip |
| CN107951461A (en) * | 2017-12-25 | 2018-04-24 | 张永生 | A kind of obstetrics and gynecology department vaginal speculum expansion shade leaf piece |
| CN108384985A (en) * | 2018-01-19 | 2018-08-10 | 无锡名精密铜带有限公司 | Low alloying copper strips and preparation method thereof |
| CN110643850A (en) * | 2019-10-24 | 2020-01-03 | 宁波博威合金材料股份有限公司 | Copper alloy with excellent bending performance and preparation method and application thereof |
| CN114507794A (en) * | 2022-02-11 | 2022-05-17 | 无锡日月合金材料有限公司 | Copper-nickel-tin alloy material for high-elasticity element and preparation method thereof |
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| CN114507794A (en) * | 2022-02-11 | 2022-05-17 | 无锡日月合金材料有限公司 | Copper-nickel-tin alloy material for high-elasticity element and preparation method thereof |
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