A kind of high-performance complicated pluralism phosphor bronze alloy material and preparation method thereof
Technical field
The present invention relates to a kind of high-performance complicated pluralism phosphor bronze alloy material and preparation method thereof, belong to non-ferrous metal and add
Work field.
Background technology
With the development of modernization science and technology, electronics, communication and automobile industry are in the high speed development stage, to patching
The demand of the flexible member Copper-Nickel-Aluminium Alloy such as part, connector increasingly increases.Meanwhile, the performance to Copper-Nickel-Aluminium Alloy is carried
Harsher requirement is gone out, such as alloy requirement has high intensity, high conductivity, high resiliency, high resistance to stress relaxation property, height tired
Labor intensity etc..On domestic market high-strength high elasticity acid bronze alloy it is main with beryllium-bronze and tin-phosphor bronze high (QSn8-0.3,
) etc. QSn10-0.3 based on alloy series, wherein beryllium-bronze as nonferrous materials elasticity king, can not with other materials
Analogy performance advantage, but because beryllium has a serious detrimental effect to the health and environment of people, and beraloy processing work
Skill is complicated and actual production difficulty is big, causes it to be only applied in special dimension.Conventional Sn-P-Cu alloy high, Theil indices are high
Up to 8-10%, strand is also easy to produce tin segregation phenomena, it is necessary to the homogenization of long period is heat-treated after alloy is produced through horizontal casting
Eliminated with multiple heat treatment, production efficiency is relatively low, and Sn price costly, Theil indices corresponding raw material more high
It is relatively costly.In addition, the conductance of Sn-P-Cu alloy high only has 12%IACS, it is difficult to meet high resiliency conductive-type acid bronze alloy
The growth requirement of material, affects further industrialization production and the marketing of Sn-P-Cu alloy high.
The content of the invention
The main object of the present invention is the deficiency for making up existing copper alloy property, in classical tin-phosphor bronze (QSn8-0.3)
On the basis of carry out reduce Sn contents and meanwhile add the alloying elements such as Ni, Zn, Fe and by tri- kinds of elements of Co, B and Zr constitute be combined
Fining agent, improves to alloying component and tissue, the performance of alloy is compared favourably therewith.Due to the Sn contents of alloy of the present invention
Relatively low and fine microstructures, Sn degree of segregation is improved, and can save the prolonged homogenizing annealing process of high temperature, improves conjunction
The production efficiency of gold, greatly reduces the production cost of alloy.
In order to achieve the above object, the present invention is realized in:
A kind of high-performance complicated pluralism phosphor bronze alloy material, its percentage by weight constitutes and is:Sn 3.9~4.4%,
Ni 0.05~0.1%, Zn 0.05~0.2%, Fe 0.05~0.2%, P 0.02~0.08%, remaining is Cu.
Further, also containing selected from the two or more elements in Co, B and Zr, weight content is respectively Co to the alloy
0.002~0.015%, B 0.003~0.015%, Zr 0.005~0.015%, total content be 0.01%≤Co+B+Zr≤
0.03%.
Added alloys producing:
Nickel:Nickel element can play solution strengthening effect, and the addition of nickel element in addition can also increase the heat-resisting temperature of alloy
Degree.
Tin:Because tin atom differs larger with copper atom radius, tin element is added in copper alloy, larger crystalline substance can be caused
Lattice distort, the motion of effective obstruction dislocation, improve the intensity and elastic performance of alloy.In addition, the addition of tin element can be significantly
Improve the decay resistance of alloy.
Phosphorus:Micro P elements can not only play phlogistication, can also form phosphate copper compound with copper, improve alloy
Anti-softening temperature and stress relaxation resistance.
Zinc:Zn-ef ficiency mainly improves alloy to scolding tin stain permeability and heat-resisting adhesive performance in the alloy.
Iron:Ferro element can effectively adjust alloy grain tissue size, improve the uniformity of tissue, and improving the resistance to of alloy should
Power corrosion susceptibility.
Boron, cobalt and zr element:Three kinds of additions of element can primarily serve crystal grain thinning size, reduce tin degree of segregation
Effect.In three kinds of elements are jointly added to alloy, due to there are interation between nutrients between three kinds of elements, can be substantially thin
Change crystal grain and reduce tin segregation, its effect is better than two kinds of alloying elements of addition.
It is a further object of the present invention to provide the preparation processing method of above-mentioned high-performance complicated pluralism tin bronze alloys material.
A kind of preparation processing method of high-performance complicated pluralism tin copper alloy material, including following technological process:A. according to
Mass percent carry out dispensing, feed intake, melting and casting, b. milling faces, c. roughing, d. trimmings, intermediate annealings of e., f. acid
Wash, rolled in g., bis- intermediate annealings of h., i. pickling, j. finish rolling, k. process annealings, l. pickling, m. stretch-bending straightenings, n. sub-cuts enter
Storehouse.
In step a, melting and casting are carried out under non-vacuum environment using power frequency induction furnace, described smelting temperature is
1260~1300 DEG C, described casting temperature is controlled at 1220~1250 DEG C.
Before melting, in power frequency induction furnace add 70w% tin-phosphor bronze QSn6.5-0.1 leftover pieces and 30w% it is new
Material, carries out non-vacuum melting.Wherein virgin material includes being closed in the middle of cathode copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron, copper and iron and copper zirconium
Gold, 1260~1300 DEG C are risen to by temperature, and after copper fusing to be electrolysed, the charcoal for adding calcination is covered, quiet after being sufficiently stirred for
15~25min is put, horizontal casting casting is carried out, casting technological parameter is:The speed that is pulled is 14~16mm/s, stops 2.5~3.5s,
For 10~12mm/s, made-up belt outlet temperature is 350~450 DEG C to the anti-speed that pushes away.
In step b, horizontal continuous casting blank is carried out into the treatment of milling face, upper and lower milling face is measured about 1mm, mainly removes surface defect.
In step c, the ingot blank behind milling face is carried out into cold rolling cogging, the total deformation of roughing cogging is 65~85%.
In step e, intermediate annealing, an intermediate annealing heat are carried out during the cold-reduced sheet after trimming is placed into bell-type annealing furnace
The temperature for the treatment of is 475~525 DEG C, and soaking time is 4~6h.
In step g, rolled during the sheet material after pickling is carried out, it is described in the total deformation rolled be 50~70%.
In step h, the Strip after being rolled by carries out secondary intermediate annealing process, and secondary intermediate annealing process temperature is
450~500 DEG C, soaking time is 4~6h.
In step j, the band after pickling is carried out into finish rolling, finish rolling total deformation is 30~50%.
In step k, process annealing is carried out during the band after finish rolling is placed into bell-jar annealing, low-temperature anneal temperature is 200
~250 DEG C, annealing time is 4~6h.
Advantages of the present invention:The present invention is the reduction Sn contents on the basis of traditional tin-phosphor bronze (QSn8-0.3), and is added
Plus Fe, Ni and Zn element, make the performance of alloy suitable therewith, while by adding one kind by Co, B and Zr tri- in fusion-casting process
The composite modifiers of at least two compositions in element are planted, structure refinement is mainly risen to invention alloy, reduce the segregation of Sn elements
The effect of degree, goes high temperature long-time homogenizing annealing handling process after saving, reduce production cost, improves the life of alloy
Produce efficiency.The chemical composition of the high-performance complicated pluralism phosphor bronze alloy material developed by the present invention is respectively:Theil indices
3.9~4.4%, nickel content 0.05~0.1%, iron content 0.05~0.20%, Zn content 0.05~0.2%, phosphorus content 0.02
~0.08%, remaining is copper.In addition, also at least containing at least two in cobalt, boron and zr element in copper alloy, wherein cobalt contains
It is 0.002~0.015% to measure, and Boron contents are 0.003~0.015%, and zirconium content is 0.005~0.015%, and total content is
0.01%≤cobalt+boron+zirconium≤0.03%.In addition, the present invention further developed a kind of preparation processing suitable for above-mentioned copper alloy
Method, the tensile strength of the high-performance complicated pluralism phosphor bronze alloy material of processed heat treatment is 800~850MPa, conductance
It is 20~25%, elongation 5~7%, elastic modelling quantity is 110~120GPa, stress relaxation resistance is for (125 DEG C, 1000h)
75%~80%, classical tin-phosphor bronze QSn8-0.3 alloys can be substituted completely, using making electronics, automobile connector and company
Connect the components such as device.
Below by specific embodiment, the present invention will be further described, but is not meant to the scope of the present invention
Limitation.
Specific embodiment
High-performance complicated pluralism phosphor bronze alloy material of the invention, it contains the chemical composition of following percetage by weight:
Sn 3.9~4.4%, Ni 0.05~0.1%, Zn 0.05~0.2%, P 0.02~0.08%, Fe 0.05~0.20%, its
Remaining is Cu.In addition, also at least containing at least two in Co, B and Zr element in copper alloy, wherein Co 0.002~
0.015%, B 0.003~0.015%, Zr 0.005~0.015%, total content is 0.01%~0.03%.
The preparation of above-mentioned high-performance complicated pluralism phosphor bronze alloy material and processing method, including following technological process:a.
According to mass percent carry out dispensing, feed intake, melting and casting, b. milling faces, c. roughing, d. trimmings, e. first time intermediate annealings,
F. pickling, rolls in g., second intermediate annealing of h., i. pickling, j. finish rolling, k. process annealings, l. pickling, m. stretch-bending straightenings, n.
Sub-cut is put in storage.Wherein, specific feeding sequence is:The tin-phosphor bronze QSn6.5-0.1 sides of 70w% are added in power frequency induction furnace
The virgin material of corner material and 30w% carries out non-vacuum melting, and wherein virgin material includes cathode copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron, copper
Iron and copper zirconium intermediate alloy, 1260~1300 DEG C are risen to by temperature, and after copper fusing to be electrolysed, the charcoal for adding calcination is covered
Lid, after being sufficiently stirred for, stands 15~25min, carries out horizontal casting casting, and casting technological parameter is:The speed that is pulled be 14~
16mm/s, stops 2.5~3.5s, and for 10~12mm/s, made-up belt outlet temperature is 350~450 DEG C to the anti-speed that pushes away.Milling face is processed, on
About 1mm is measured in lower milling face, mainly removes surface defect.Cold rolling cogging, deflection is 65~85%.First time intermediate annealing, annealing
Temperature is 475~525 DEG C, and annealing time is 4~6h.In roll deflection for 50~70%.Second intermediate annealing process, annealing
Temperature is 450~500 DEG C, and annealing time is 4~6h.Finish rolling deflection is 30~50%.Process annealing, annealing temperature is 200
~250 DEG C, annealing time is 4~6h.
Embodiment 1
Alloy of the invention uses following raw material melting:Tin-phosphor bronze QSn6.5-0.1 leftover pieces, cathode copper, electrolytic nickel,
Electrolytic cobalt, pure zinc, copper boron and copper and iron intermediate alloy.The composition of alloy is shown in Table 1 embodiment 1.
1. melting:70% tin-phosphor bronze QSn6.5-0.1 leftover pieces and 30% virgin material are added in power frequency induction furnace,
Wherein virgin material includes cathode copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron and copper and iron intermediate alloy, and temperature is risen into 1260 DEG C, treats
After cathode copper fusing, the charcoal for adding calcination is covered, and after being sufficiently stirred for, stands 15min, treats that holding temperature is 1220 DEG C
When, horizontal casting casting is carried out, casting technological parameter is:The speed that is pulled is 14mm/s, stops 2.5s, and the anti-speed that pushes away is 12mm/s,
Made-up belt outlet temperature is 450 DEG C.
2. roughing:Cold rolling cogging is carried out to the alloy behind milling face, processing capacity is 65%.
3. first time intermediate annealing heat treatment:Intermediate annealing process are carried out to slab after roughing, annealing temperature is 475 DEG C,
Annealing time is 6h.
4. rolled in:Rolled in being carried out by the Strip after intermediate annealing process, a pickling, processing capacity is 70%.
5. second intermediate annealing heat treatment:Strip after centering is rolled carries out intermediate annealing process, and annealing temperature is 500
DEG C, annealing time is 4h.
6. finish rolling:To carrying out finish rolling by the band after secondary intermediate annealing process, pickling, processing capacity is 30%.
7. process annealing treatment:To carrying out process annealing treatment by band after finish rolling, annealing temperature is 200 DEG C, annealing
Time is 6h.
By above melting and casting, roughing, intermediate annealing process, pickling, in roll, secondary intermediate annealing process,
After the working processes such as pickling, finish rolling, process annealing, its performance is shown in Table the embodiment 1 in 2.
Embodiment 2
Alloy of the invention uses following raw material melting:Tin-phosphor bronze QSn6.5-0.1 leftover pieces, cathode copper, electrolytic nickel,
Electrolytic cobalt, pure zinc, copper and iron and copper zirconium intermediate alloy.The composition of alloy is shown in Table 1 embodiment 2.
1. melting:70% tin-phosphor bronze QSn6.5-0.1 leftover pieces and 30% virgin material are added in power frequency induction furnace,
Wherein virgin material includes cathode copper, electrolytic cobalt, electrolytic nickel, pure zinc, copper and iron and copper zirconium intermediate alloy, and temperature is risen into 1280 DEG C, treats
After cathode copper fusing, the charcoal for adding calcination is covered, and after being sufficiently stirred for, stands 25min, treats that holding temperature is 1250 DEG C
When, horizontal casting casting is carried out, casting technological parameter is:The speed that is pulled is 16mm/s, stops 3.5s, and the anti-speed that pushes away is 10mm/s,
Made-up belt outlet temperature is 350 DEG C.
2. roughing:Cold rolling cogging is carried out to the alloy behind milling face, processing capacity is 85%.
3. first time intermediate annealing heat treatment:Intermediate annealing process are carried out to slab after roughing, annealing temperature is 500 DEG C,
Annealing time is 4h.
4. rolled in:Rolled in being carried out by the Strip after intermediate annealing process, a pickling, processing capacity is 50%.
5. second intermediate annealing heat treatment:Strip after centering is rolled carries out intermediate annealing process, and annealing temperature is 450
DEG C, annealing time is 6h.
6. finish rolling:To carrying out finish rolling by the band after secondary intermediate annealing process, pickling, processing capacity is 50%.
7. process annealing treatment:To carrying out process annealing treatment by band after finish rolling, annealing temperature is 250 DEG C, annealing
Time is 4h.
By above melting and casting, roughing, intermediate annealing process, pickling, in roll, secondary intermediate annealing process,
After the working processes such as pickling, finish rolling, process annealing, its performance is shown in Table the embodiment 2 in 2.
Embodiment 3
Alloy of the invention uses following raw material melting:Tin-phosphor bronze QSn6.5-0.1 leftover pieces, cathode copper, electrolytic nickel,
Pure zinc, copper boron, copper and iron and copper zirconium intermediate alloy.The composition of alloy is shown in Table 1 embodiment 3.
1. melting:70% tin-phosphor bronze QSn6.5-0.1 leftover pieces and 30% virgin material are added in power frequency induction furnace,
Wherein virgin material includes cathode copper, electrolytic nickel, pure zinc, copper boron, copper and iron and copper zirconium intermediate alloy, and temperature is risen into 1300 DEG C, treats electricity
After solution copper fusing, the charcoal for adding calcination is covered, and after being sufficiently stirred for, stands 20min, when holding temperature is 1230 DEG C,
Horizontal casting casting is carried out, casting technological parameter is:The speed that is pulled is 15mm/s, stops 3s, and for 11mm/s, made-up belt goes out the anti-speed that pushes away
Mouth temperature is 400 DEG C.
2. roughing:Cold rolling cogging is carried out to the alloy behind milling face, processing capacity is 75%.
3. first time intermediate annealing heat treatment:Intermediate annealing process are carried out to slab after roughing, annealing temperature is 480 DEG C,
Annealing time is 5h.
4. rolled in:Rolled in being carried out by the Strip after intermediate annealing process, a pickling, processing capacity is 60%.
5. second intermediate annealing heat treatment:Strip after centering is rolled carries out intermediate annealing process, and annealing temperature is 475
DEG C, annealing time is 5h.
6. finish rolling:To carrying out finish rolling by the band after secondary intermediate annealing process, pickling, processing capacity is 40%.
7. process annealing treatment:To carrying out process annealing treatment by band after finish rolling, annealing temperature is 225 DEG C, annealing
Time is 5h.
By above melting and casting, roughing, intermediate annealing process, pickling, in roll, secondary intermediate annealing process,
After the working processes such as pickling, finish rolling, process annealing, its performance is shown in Table the embodiment 3 in 2.
Embodiment 4
Alloy of the invention uses following raw material melting:Tin-phosphor bronze QSn6.5-0.1 leftover pieces, cathode copper, electrolytic nickel,
Electrolytic cobalt, pure zinc, copper boron, copper and iron and copper zirconium intermediate alloy.The composition of alloy is shown in Table 1 embodiment 4.
1. melting:70% tin-phosphor bronze QSn6.5-0.1 leftover pieces and 30% virgin material are added in power frequency induction furnace,
Wherein virgin material includes cathode copper, electrolytic nickel, electrolytic cobalt, pure zinc, copper boron, copper and iron and copper zirconium intermediate alloy, and temperature is risen into 1270
DEG C, after copper fusing to be electrolysed, the charcoal for adding calcination is covered, and after being sufficiently stirred for, stands 22min, treats that holding temperature is
At 1240 DEG C, horizontal casting casting is carried out, casting technological parameter is:The speed that is pulled is 14mm/s, stops 3s, and the anti-speed that pushes away is
10mm/s, made-up belt outlet temperature is 425 DEG C.
2. roughing:Cold rolling cogging is carried out to the alloy behind milling face, processing capacity is 70%.
3. first time intermediate annealing heat treatment:Intermediate annealing process are carried out to slab after roughing, annealing temperature is 500 DEG C,
Annealing time is 5h.
4. rolled in:Rolled in being carried out by the Strip after intermediate annealing process, a pickling, processing capacity is 50%.
5. second intermediate annealing heat treatment:Strip after centering is rolled carries out intermediate annealing process, and annealing temperature is 475
DEG C, annealing time is 4h.
6. finish rolling:To carrying out finish rolling by the band after secondary intermediate annealing process, pickling, processing capacity is 50%.
7. process annealing treatment:To carrying out process annealing treatment by band after finish rolling, annealing temperature is 200 DEG C, annealing
Time is 5h.
By above melting and casting, roughing, intermediate annealing process, pickling, in roll, secondary intermediate annealing process,
After the working processes such as pickling, finish rolling, process annealing, its performance is shown in Table the embodiment 4 in 2.
The alloying component table (wt%) of the embodiment 1-4 of table 1
The alloy property table of the embodiment 1-4 of table 2
The present invention by melting and casting, roughing, an intermediate annealing, pickling, in roll, secondary intermediate annealing, pickling, essence
Roll, a kind of high-performance complicated pluralism phosphor bronze alloy material is obtained after the working process such as process annealing treatment.Because the present invention is closed
Gold Sn contents are relatively low and fine microstructures, Sn degree of segregation is improved, and can save the prolonged homogenizing annealing work of high temperature
Skill, improves the production efficiency of alloy, greatly reduces the production cost of alloy.
The tensile strength of blaster fuse frame material of the invention is 800~850MPa, and electrical conductivity is 20~25%IACS, is extended
Rate is 5~7%, and elastic modelling quantity is 110~120GPa, and stress relaxation resistance (in 125 DEG C, 1000h) is 75%~80%, can
To substitute classical tin-phosphor bronze QSn8-0.3 alloys, it is applied to make the portions of unit such as electronic apparatus, automobile contact and connector
Part.