CN1448531A - Caro bronze strip having excellent bending processability - Google Patents
Caro bronze strip having excellent bending processability Download PDFInfo
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- CN1448531A CN1448531A CN03108415A CN03108415A CN1448531A CN 1448531 A CN1448531 A CN 1448531A CN 03108415 A CN03108415 A CN 03108415A CN 03108415 A CN03108415 A CN 03108415A CN 1448531 A CN1448531 A CN 1448531A
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- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 36
- 239000010974 bronze Substances 0.000 title claims abstract description 36
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000005452 bending Methods 0.000 title abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000137 annealing Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000005097 cold rolling Methods 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 238000001953 recrystallisation Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005204 segregation Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 11
- 238000003754 machining Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 238000004453 electron probe microanalysis Methods 0.000 description 7
- 208000037656 Respiratory Sounds Diseases 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000005482 strain hardening Methods 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 230000002950 deficient Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000000306 recurrent effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
-
- 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
- C22C9/02—Alloys based on copper with tin as the next major constituent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
A phosphor bronze strip having excellent bending workability and high mechanical strength for use in electronic parts such as terminal connectors wherein; the phosphor bronze strip has a stripe in a cross sectional microstructure revealed by etching; the difference of the maximum and the minimum of tin concentration in the region containing the stripe is between 5 and 40 mass %, preferably 5 to 25 mass % of that of a base material; and the strip is manufactured by the steps of cold rolling to a reduction ratio of at least 45%, final recrystalization annealing to the extent that the mean grain size (mGS) is from 0.5 to 2 mum and the standard deviation of the grain size (sigmaGS) is not more than 1.5 mum, and final cold rolling to a reduction ratio of 20 to 70%.
Description
Technical field
The present invention relates to be used for electronic units such as terminal connector the phosphor bronze bar and the bendability improved phosphor bronze of punching press when being shaped to terminal.
Background technology
C5210, C5191 phosphor bronze bars such as (JIS alloy numberings) is widely used in purposes such as terminal connector because of having outstanding bendability and high mechanical strength as the electronic unit land used.On the other hand, in recent years, thin lightization of parts and the development of short and smallization are obviously accelerated.From this viewpoint, people require further to improve the intensity and the bendability of the phosphor bronze with high mechanical strength and outstanding bending machining performance.When the phosphor bronze that is conceived to have identical component was considered, physical strength was opposite characteristic with bendability.In other words, the ductility deficiency of the material that physical strength is high, thereby bendability is poor.On the contrary, the material that physical strength is low has good ductility, thereby bendability is outstanding.Correspondingly, in electronic unit processing, such trend is more and more stronger, promptly in the value of the physical strength of used phosphor bronze the same with the past or than in the past higher situation under, processing component is than in the past littler.Under the occasion of processing component miniaturization, the bending radius of the bending machining portion of parts reduces.As a result, and compare in the past, Ministry of worker's fold, orange peel, crackle occur adding easilier at the bending machining place.
In the value of the physical strength of used phosphor bronze the same with the past or than higher and bending radius in the past be set than in the past littler overbending processing in, produced the defective that the past do not take place, promptly not recurrent Ministry of worker's fold, orange peel and the crackle of adding.The Ministry of worker is bad to be meaned a collection of in or occurred the defective that disqualification rate fluctuates in batches adding of often not occurring.In the past, the bad of bending machining portion can change used phosphor bronze kind and avoid by changing the punch process conditioned disjunction.Thus one, can stablize in the stamping procedure of manufacturing in appearance at the component manufacturer place, the defective that disqualification rate increases has suddenly appearred.Along with the same with the past or higher than the past and the development in recent years trend that bending radius is set forr a short time than the past of physical strength of used phosphor bronze, it is obvious all the more that above-mentioned defective becomes.
Summary of the invention
The purpose of this invention is to provide a kind of like this phosphor bronze bar, it is the same with the past or be set than more hour becoming all the more significantly bad in the past than higher and bending radius in the past that it is not easy to occur physical strength when used phosphor bronze.
At above-mentioned bad, the present invention relates to realize simultaneously the high strength of phosphor bronze and invention scheme that bendability improves and as follows.
(1) the outstanding high strength phosphor bronze bar of bendability, it has such metal structure, promptly in the grain structure in the cross section that the corrosion that contains the aqueous solution of hydrogen peroxide and ammonia by use shows, the inhomogeneous banded structure that has white or black, having the maximum value of Sn concentration in zone of this banded structure and the difference of minimum value is 5%-40% (the Δ C of base material Sn concentration
Sn=5%-25% 5%-40%) and preferably, it is characterized in that, so implement this manufacturing processed, be that working modulus is that cold rolling web more than 45% is accepted final recrystallization annealing, crystallization crystal grain diameter (mGS) is that the standard deviation (σ GS) of 0.5 micron-2 microns and crystallization crystal grain diameter is below 1.5 microns, and then carrying out working modulus is the finally cold rolling of 20%-70%.
(2) the phosphor bronze bar outstanding as (1) described bendability is characterized in that, final cold rolling after, make tensile strength reduce the elimination strain annealing of 3%-10%.
Compare with traditional phosphor bronze bar, the bendability of phosphor bronze bar of the present invention is outstanding.Under the occasion of overbending processing, the effect that it is expected to play very well.
Description of drawings
Fig. 1 is the observation example of the banded structure seen in the cross section.
Nomenclature: 1-white stripes; Near the 2-1 the portion that perfects; The 3-blackstreak; Near the 4-3 the portion that perfects; The striped that occurs in the whole cross-sectional area of 5-; Near the 6-5 the portion that perfects.
Concrete form of implementation
As the phosphor bronze of object of the present invention is to be added with the copper alloy of Sn and P and it is the Sn that JIS regulation material ground contains 3.5%-9% in copper.In the alloy beyond the JIS regulation, the copper alloy that contains the low Sn phosphor bronze of 3.5% following Sn and contain 10% Sn above 9% ground also within the scope of the present invention.In addition, the element that also contains in phosphor bronze except that Sn or P is that the matrix of copper and tin can obtain the effect the same with the present invention as the alloy of trace additives (as amounting in 2%) such as Fe, Ni, Zn because of crystallization.
The cross section of the phosphor bronze bar that can buy on market is finish-machined to minute surface, when usefulness contains the aqueous corrosion of hydrogen peroxide and ammonia, manifests metal structure.Grain structure is according to the promptly final cold rolling working modulus of phosphor bronze bar quality but equiax crystal, or the grain structure that extends on rolling direction, or on the thickness of slab direction compressed grain structure.In addition, when working modulus reaches 15% when above,, form uniform formation in a word at once though be difficult to determine crystal boundary.When increasing viewing area, in grain structure uniformly, can see often as shown in Figure 1 white or the inhomogeneous striped of black.The crystal grain of this part is discerned very difficult sometimes, is coarse grain sometimes.The inventor studies in great detail emergent off-grade metal tissue in bending machining.Found that the bad inhomogeneous striped with white or black of bending machining is relevant.In addition, the inventor emphatically research and the inhomogeneous striped that will understand this white or black have which type of influence and which type of material harmful or harmless to bending machining to bendability.Thus, obtained phosphor bronze bar of the present invention.The reason of corroding minute surface precision work cross section with the aqueous solution that contains hydrogen peroxide and ammonia is that this corrosive fluid is easier to manifest the homogeneously crystallized contained uneven white or the striped of black organized than other corrosive fluid.Minute surface precision work cross section can be the cross section parallel, vertical with the plate face and parallel cross section with rolling direction with the plate face or vertical with the plate face and with the vertical cross section of rolling direction.
Often the white of seeing in uniform grain structure or the inhomogeneous striped of black reveal thus, the Sn that promptly produces in melting and casting is segregated in subsequently rolling and the annealing and does not left behind with disappearing, because the recrystallize behavior is different because of Sn concentration, so cause the inhomogeneous of metal structure.Can be only by the product that predetermined thickness of slab is arranged rolling and that annealing processing obtains after the phosphor bronze of having bought on the market is that ingot casting is made in the lead alloy fusion, its manufacturing processed does not comprise forge hot and hot rolling usually.In the phosphor bronze bar of making, although there is the inhomogeneous striped of white or black certainly in the difference of the frequency of occurrences and degree with not carrying out forge hot and hot rolling.Therefore, the inhomogeneous striped of white or black is considered to be in the abnormal structure that produces inevitably in the phosphor bronze manufacturing.In the bending machining in past, the heterogeneous structure of this white or black is not brought baneful influence.But, the physical strength value of used phosphor bronze with in the past the same or be set than higher and final dimension in the past than in the past littler overbending processing in, with not specific frequency such bad of fold, orange peel, crackle appearred resembling.
According to the present invention, measure the inhomogeneous striped comprise white or black the zone Sn concentration and obtain the maximum value and the minimum value of this regional Sn concentration, and in the overall part of grain structure uniformly, also measure Sn concentration and be base material Sn concentration.
Measure Sn concentration with EPMA.Adopt EPMA to be because, EPMA can analyze the composition of small part more accurately, it is the Gneral analysis instrument of extensively popularizing simultaneously.In EPMA analyzed, the intensity of the characteristic X-ray that is sent by this part was calculated in partial irradiation electron rays and measurement.Therefore the intensity of characteristic X-ray and the Sn concentration relation of being in line, can know Sn concentration thus.In EPMA analyzes, can adopt means such as point analysis method, line analysis, surface analysis method, drawing analytical method.The present invention adopts line analysis basically.But, also can adopt means and multimedia array mode except that line analysis in the measuring accuracy occasion higher with line analysis same measuring accuracy being arranged or guarantee than line analysis.
In the on-line analysis, with the zone of inhomogeneous striped that comprises black or white be object make the electron rays scanning probe.Perhaps, electron rays probe maintains static and method that measurement target is moved also is feasible.Like this, measure the Sn concentration curve.The Sn concentration curve is to be that starting point and rising is thus crossed the striate region and measured on the straight line of end in even grained tissue district subsequently in even grained tissue district.And, vast scope and striped that the inhomogeneous striped of black of confirming in the cross section or white feeds through to the 1/5-4/5 of thickness of slab extend under the situation on plate surface always, measure the concentration curve on the straight line that passes whole thickness of slab on the direction perpendicular to phosphor bronze batten face.The minimum value that the probe diameter of the electron rays of irradiation measure portion is got surveying instrument.Usually, represent for 0 micron with nominal mostly.And the measurement spacing is relevant with the striped size and get 0.01 micron-1 micron.In addition, about the conditions such as kind of sample current, acceleration voltage, spectrum crystalline type, characteristic X-ray, the product that adopts surveying instrument manufacturer in Sn analyzes, to recommend.Measure about above EPMA, do not need to take special technique, use known technology commonly used just enough.
In the present invention, the difference with the maximum value of Sn concentration in zone of inhomogeneous striped of white or black and minimum value is defined as 5%-40% (the Δ C of base material Sn concentration
Sn=5%-40%).This difference is a segregation degree and with regard to bendability, it is low more good more.But,, must carry out homogeneous annealing fully, especially further approach zero, must replenish big calorimetric for the segregation degree has been reduced in order to eliminate segregation.Because cost is high and the time spent is many, had better not do like this.Therefore, in the present invention, even if also there is certain segregation, but by combining, found to compare the method for having improved bendability with traditional material with the described processing conditions of back segment that invention constitutes.In this scope, the upper limit is set to 40% reason and is, if surpass 40%, even if then make rolling and combination optimizing recrystallization annealing, can not cause bendability better than traditional material.Be limited to below 25% by preferably making, can access better bendability.
Lower limit gets 5%.If less than 5%, although then the bendability that is caused by segregation reduces fewer and realizes high strength easily, as described above, it is huge to be used to eliminate the homogeneous annealing of segregation required time and cost, considers from the economy angle, does not wish less than 5%.40% the striped that the maximum value of Sn concentration and the difference of minimum value surpass base material Sn concentration has reduced the consistence with base material.And the metamorphosis of striped part is different with deformational behavior and base material.Therefore, in the viscous deformation by bending machining, striped portion can not follow the distortion of base material.Perhaps, striped is partly taked the deformational behavior different with base material part.As a result, discontinuous distortion occurs, caused fold, orange peel, crackle thus at the boundary of striped part and base material part.This and the be full of cracks that occurs in material, when perhaps having the chain material of nonmetal inclusion, the mechanism that occurs orange peel, crackle when carrying out bending machining is similar.
In addition, to get more than 45% be because if working modulus is worth smaller or equal to this, the recrystal grain in the then final recrystallization annealing is difficult to dwindle to the cold working rate before the final recrystallization annealing.In other words, target of the present invention is, reduce final cold rolling cold working rate as much as possible by the particle diameter that to dwindle final crystallization crystal grain diameter before cold rolling be final recrystallized structure, by the intensity that obtains to bring by desirable work hardening, suppress the deterioration of ductility, and guarantee bendability and intensity balance thus.Constitute the tissue that bendability worsens the segregation tissue of key element as described above even if having, also obtained bendability and intensity.And although do not stipulate the upper limit of cold rolling working modulus, if working modulus is too high, then rolling load increases, and therefore, working modulus is generally 90% and is rolled followingly.
Here, crystallization crystal grain diameter (mGS) after the recrystallization annealing is got 0.5 micron-2.0 microns reason, if the crystallization crystal grain diameter is less than 0.5 micron, then the bendability after the cold working with the relation of segregation tissue in can reduce, and, if more than 2.0 microns, then the effect of final cold worked work hardening is insufficient, be difficult to obtain desirable strength by littler working modulus.In addition, recrystallize particulate diameter wishes it is uniformly, if its standard deviation surpasses 1.5 microns, even then average crystallite crystal grain diameter (mGS) is below 2.0 microns, also can't obtain the work hardening by final cold rolling process.In manufacturing procedure subsequently, carry out cold rolling according to the working modulus of 20%-70%.If working modulus is worth smaller or equal to this, even if segregation tissue more or less then, bendability reduces also and is out of question.If surpass 70%, then ductility reduces, and forfeiture finishes the effect of Jingjing grain refinement, so working modulus is 20%-70%.
And, in order to reply ductility and to improve bendability, adopt the method for phosphor bronze being eliminated strain annealing in final cold rolling back mostly.In the present invention, under the occasion with such segregation tissue and processing conditions, the elimination strain annealing that tensile strength is reduced about 3%-10% also is favourable.Here, conditions such as the temperature of elimination strain annealing, atmosphere, tension force are random, and the present invention is not limited in this respect.In addition, in eliminating strain annealing, do not cause proliferation recrystallization and eliminate segregation.
Embodiment
In air, heap covers the phosphor bronze of charcoal ground melting JIS specification as shown in table 1 and casting subsequently, obtains the ingot casting of 100 mm wides * 40 mm thick * 150 millimeters long thus.In the atmosphere of 75% nitrogen+25% hydrogen, the homogeneous that under 600 ℃-800 ℃ ingot casting was carried out 0.5 hour-3 hours is annealed, and grinds away the tin segregation layer on surface and analyzes composition by shredder.Subsequently, as required, carry out cold rolling and recrystallization annealing repeatedly, produce the plate of 0.2 mm thick thus.Then, observe the metal structure of product and confirm white or the inhomogeneous striped of black, measure the Sn concentration in the zone that comprises striped.And, carry out crooked experiment as bendability evaluation ground.
The observation of metal structure is carried out on perpendicular to rolling cross section.Also show metal structure thus with the aqueous corrosion minute surface precision work cross section that contains hydrogen peroxide and ammonia.Adopt such aqueous solution, be about to 20 milliliters 34.5% hydrogen peroxide that can on market, buy with 10 times of dilutions at 28% the ammoniacal liquor of having bought on the market, according to volume ratio and the 10 ml water solution and 20 ml waters that form mix.
Line analysis measurement by EPMA comprises the Sn concentration curve in zone of the striped of white or black.According to line analysis, make the electron rays probe on perpendicular to the direction of plate face, scan and obtain the Sn concentration curve.The Sn concentration curve is to be starting point in uniform crystallization grain structure district and to cross the striate region subsequently and then end at and record on the straight line in the uniform crystallization grain structure district.In addition, involve at striped under the situation of the vast scope of 1/4-3/4 of thickness of slab, measure the concentration curve that runs through whole thickness of slab.Here, the diameter of the electron rays probe minimum value (0 micron of nominal) of getting surveying instrument.And, measure spacing and get 1 micron.
The crystallization crystal grain diameter is got like this, promptly according to the process of chopping (JIS H0501), the number of die that the line segment of calculating by predetermined length cuts off fully, the mean value of this cutting length is exactly the crystallization crystal grain diameter, and the standard deviation of crystallization crystal grain diameter (σ GS) is the standard deviation of this crystallization crystal grain diameter.In other words, to amplify 4000 times perpendicular to the section structure on the direction of rolling direction by scanning electron microscope image (SEM image), under the situation of 50 microns long line segments, remove this line segment with from line and crystal boundary number of hits, deducting the number that obtains after 1, resulting value is exactly the crystallization crystal grain diameter, with 10 mean values of measuring each crystallization crystal grain diameter that line segments measure is exactly the application's average crystallite crystal grain diameter (mGS), and the standard deviation of each crystallization crystal grain diameter is exactly the application's a standard deviation (σ GS).
Bendability (r/t) so obtains, promptly perpendicular to rolling direction take off the print of 10 mm wides * 100 millimeters long, carry out W crooked experiment (JISH3110) with various bending radius, obtain and the rimose minimum bending radius does not take place than (r (bending radius)/t (print thickness)).And the bending axis of W crooked experiment is the direction (bad way) parallel with rolling direction.100 prints are carried out this experiment and obtain disqualification rate, and when length was 100 millimeters, the position that can carry out the W crooked experiment was at random.As for good and bad judgement, what crackle appearred in bend is considered to bad, and what fold did not take place is considered to good.
Table 1
Δ C
Sn(%): the maximum value of the Sn concentration in striped zone and the difference of minimum value are divided by base material Sn concentration (%)
| Numbering | Composition (quality %) | Cold rolling working modulus (%) before the recrystallization annealing | After the recrystallization annealing | Final cold rolling working modulus (%) | ?Δ ?C Sn(％) | Tensile strength (MPa) | ???r/t | Disqualification rate | |||
| ???mGS(μm) | ??∑GS(μm) | After cold rolling | Eliminate under the strain annealing occasion | ||||||||
| Embodiment | ??1 | ????Cu-4.2Sn-0.13P | ????48 | ??????2.0 | ?????1.0 | ???30 | ????30 | ??623 | ????- | ???1.5 | ??0 |
| ??1′ | ????Cu-4.2Sn-0.13P | ????48 | ??????2.0 | ?????1.0 | ???30 | ????20 | ??621 | ????- | ???1.0 | ??0 | |
| ??2 | ????Cu-6.2Sn-0.13P | ????50 | ??????1.8 | ?????1.2 | ???25 | ????28 | ??652 | ????- | ???1.0 | ??0 | |
| ??3 | ????Cu-8.0Sn-0.13P | ????50 | ??????1.6 | ?????1.0 | ???25 | ????18 | ??746 | ????- | ???1.5 | ??0 | |
| ??4 | ????Cu-8.0Sn-0.13P | ????50 | ??????1.6 | ?????1.0 | ???25 | ????18 | ??746 | ???702 | ???0.5 | ??0 | |
| ??4′ | ????Cu-8.0Sn-0.13P | ????50 | ??????1.6 | ?????1.0 | ???25 | ????30 | ??745 | ???705 | ???1.0 | ??0 | |
| ??5 | ????Cu-10Sn-0.13P | ????60 | ??????1.1 | ?????0.7 | ???35 | ????22 | ??901 | ????- | ???4.0 | ??0 | |
| ??6 | ????Cu-10Sn-0.13P | ????60 | ??????1.1 | ?????0.7 | ???35 | ????22 | ??901 | ???819 | ???2.0 | ??0 | |
| Comparative example | ??7 | ????Cu-4.2Sn-0.13P | ????40 | ??????6.0 | ?????2.1 | ???35 | ????45 | ??602 | ????- | ???2.0 | ??4 |
| ??8 | ????Cu-6.2Sn-0.13P | ????40 | ??????8.2 | ?????2.3 | ???30 | ????48 | ??625 | ????- | ???1.0 | ??2 | |
| ??9 | ????Cu-8.0Sn-0.13P | ????44 | ??????5.0 | ?????2.2 | ???25 | ????52 | ??702 | ????- | ???2.0 | ??3 | |
| ??10 | ????Cu-10Sn-0.13P | ????40 | ??????4.2 | ?????2.1 | ???35 | ????44 | ??844 | ????- | ???3.5 | ??5 | |
| ??11 | ????Cu-8.0Sn-0.13P | ????50 | ??????1.6 | ?????1.0 | ???25 | ????48 | ??746 | ????- | ???2.0 | ??3 | |
| ??12 | ????Cu-8.0Sn-0.13P | ????44 | ??????4.5 | ?????1.2 | ???25 | ????18 | ??705 | ????- | ???1.5 | ??0 | |
| ??13 | ????Cu-8.0Sn-0.13P | ????50 | ??????4.3 | ?????1.3 | ???25 | ????17 | ??704 | ????- | ???2.0 | ??0 | |
| ??14 | ????Cu-8.0Sn-0.13P | ????50 | ??????1.5 | ?????2.0 | ???25 | ????17 | ??716 | ????- | ???2.0 | ??0 | |
| ??15 | ????Cu-8.0Sn-0.13P | ????50 | ??????1.5 | ?????1.3 | ???15 | ????17 | ??686 | ????- | ???2.0 | ??2 | |
In table 1, be example with identical Sn concentration based on the JIS specification, can comparing embodiment 1 and comparative example 7, embodiment 2 and comparative example 8, embodiment 3 and comparative example 9, embodiment 5 and comparative example 10.Under the identical situation of Sn concentration, compare with comparative example, embodiment demonstrates the intensity of high 20 MPas-50 MPa.Since the lower and grain size of working modulus before the recrystallization annealing surpass less than the comparative example below 2 microns 12, by recrystallization annealing in 2 microns the comparative example 13 and the discrete bigger comparative example 14 of crystal grain, compare with the example 3 with same Sn concentration, tensile strength is low.In addition, in embodiment and comparative example based on the identical Sn concentration of JIS specification, the r/t of expression bendability is the same, or the value of embodiment is littler, and the disqualification rate of crooked experiment is 0%.Therefore, take all factors into consideration with intensity, example not only has high strength, and has outstanding bendability.And, although all within the scope of the present invention, because homogeneous annealing conditions difference, so be Δ C No. 1 and 1 ' number and No. 4 and 4 ' numbers
SnDifferent examples.Although the mGS after cold rolling working modulus, the recrystallization annealing, σ GS and tensile strength are identical, r/t is different value.By making Δ C
SnValue be below 25%, can access better bendability.On the other hand, at the difference of the maximum value of the Sn concentration in the zone of the inhomogeneous banded structure that has white or black and minimum value value (Δ C divided by base material Sn concentration
Sn) surpass among the comparative example 7-11 of the present invention's regulation, crooked disqualification rate is percentum.And, in the little comparative example 15 of final cold rolling working modulus, although the difference of the maximum value of the Sn concentration in the zone of the inhomogeneous banded structure of band white or black and minimum value is divided by value (the Δ C of base material Sn concentration
Sn) be in claimed scope, but can't obtain to be equivalent to intensity of the present invention.
Claims (3)
1, the outstanding high strength phosphor bronze bar of bendability, it has such metal structure, promptly in the grain structure in the cross section that the corrosion that contains the aqueous solution of hydrogen peroxide and ammonia by use shows, the inhomogeneous banded structure that has white or black comprises that the maximum value of Sn concentration in zone of this banded structure and the difference of minimum value are 5%-40% (the Δ C of base material Sn concentration
SnBe 5%-40%), it is characterized in that, so implement this manufacturing processed, be that working modulus is that cold rolling web more than 45% is accepted final recrystallization annealing, crystallization crystal grain diameter (mGS) is that the standard deviation (σ GS) of 0.5 micron-2 microns and crystallization crystal grain diameter is below 1.5 microns, and then carrying out working modulus is the finally cold rolling of 20%-70%.
2, the outstanding phosphor bronze bar of bendability as claimed in claim 1 is characterized in that Δ C
Sn=5%-25%.
3, the outstanding phosphor bronze bar of bendability as claimed in claim 1 or 2 is characterized in that, final cold rolling after, make tensile strength reduce the elimination strain annealing of 3%-10%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP94216/02 | 2002-03-29 | ||
| JP94216/2002 | 2002-03-29 | ||
| JP2002094216 | 2002-03-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1448531A true CN1448531A (en) | 2003-10-15 |
| CN1287000C CN1287000C (en) | 2006-11-29 |
Family
ID=28786174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03108415XA Expired - Fee Related CN1287000C (en) | 2002-03-29 | 2003-03-31 | Caro bronze strip having excellent bending processability |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20040007294A1 (en) |
| JP (1) | JP3893358B2 (en) |
| KR (1) | KR100508468B1 (en) |
| CN (1) | CN1287000C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203631B (en) * | 2005-06-30 | 2011-08-03 | Jx日矿日石金属株式会社 | Sn-plated copper alloy bar having excellent fatigue characteristics |
| CN111394610A (en) * | 2020-04-29 | 2020-07-10 | 福建紫金铜业有限公司 | Production process of copper plate and strip materials of VC (polyvinyl chloride) uniform-temperature plates for 5G |
| CN116287851A (en) * | 2022-09-09 | 2023-06-23 | 昆明冶金研究院有限公司北京分公司 | Tin phosphor bronze strip, preparation method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4904455B2 (en) * | 2004-09-21 | 2012-03-28 | Ｄｏｗａメタルテック株式会社 | Copper alloy and manufacturing method thereof |
| WO2006093233A1 (en) * | 2005-03-02 | 2006-09-08 | The Furukawa Electric Co., Ltd. | Copper alloy and method for production thereof |
| DE102009034769B3 (en) * | 2009-07-25 | 2010-12-16 | Wieland-Werke Ag | Composite sliding element e.g. plain nearing bush, has sliding bearing layer formed from tin bronze and exhibiting specific thickness, where tin bronze comprises specific weight percentage of tin, copper and impurities |
| CN113215424A (en) * | 2021-04-29 | 2021-08-06 | 中铜华中铜业有限公司 | Preparation process of high-uniformity tin-phosphor bronze strip |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923558A (en) * | 1974-02-25 | 1975-12-02 | Olin Corp | Copper base alloy |
| US5820701A (en) * | 1996-11-07 | 1998-10-13 | Waterbury Rolling Mills, Inc. | Copper alloy and process for obtaining same |
-
2003
- 2003-03-25 KR KR10-2003-0018363A patent/KR100508468B1/en active IP Right Grant
- 2003-03-28 US US10/401,473 patent/US20040007294A1/en not_active Abandoned
- 2003-03-28 JP JP2003091074A patent/JP3893358B2/en not_active Expired - Fee Related
- 2003-03-31 CN CNB03108415XA patent/CN1287000C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101203631B (en) * | 2005-06-30 | 2011-08-03 | Jx日矿日石金属株式会社 | Sn-plated copper alloy bar having excellent fatigue characteristics |
| CN111394610A (en) * | 2020-04-29 | 2020-07-10 | 福建紫金铜业有限公司 | Production process of copper plate and strip materials of VC (polyvinyl chloride) uniform-temperature plates for 5G |
| CN111394610B (en) * | 2020-04-29 | 2021-03-23 | 福建紫金铜业有限公司 | Production process of copper plate and strip materials of VC (polyvinyl chloride) uniform-temperature plates for 5G |
| CN116287851A (en) * | 2022-09-09 | 2023-06-23 | 昆明冶金研究院有限公司北京分公司 | Tin phosphor bronze strip, preparation method and application thereof |
| CN116287851B (en) * | 2022-09-09 | 2024-05-14 | 中铝科学技术研究院有限公司 | Tin phosphor bronze strip, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100508468B1 (en) | 2005-08-17 |
| CN1287000C (en) | 2006-11-29 |
| JP2004002988A (en) | 2004-01-08 |
| US20040007294A1 (en) | 2004-01-15 |
| KR20030078672A (en) | 2003-10-08 |
| JP3893358B2 (en) | 2007-03-14 |
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