CN103667779B - A kind of preparation method of lead-free reflow - Google Patents
A kind of preparation method of lead-free reflow Download PDFInfo
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- CN103667779B CN103667779B CN201310615813.7A CN201310615813A CN103667779B CN 103667779 B CN103667779 B CN 103667779B CN 201310615813 A CN201310615813 A CN 201310615813A CN 103667779 B CN103667779 B CN 103667779B
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- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000005096 rolling process Methods 0.000 claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 22
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 20
- 239000010951 brass Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005275 alloying Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 description 6
- 238000003754 machining Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 229910001340 Leaded brass Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000002180 anti-stress Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
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- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 201000009240 nasopharyngitis Diseases 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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Abstract
The present invention have developed a kind of novel leadless environment-friendly brass; and have developed the rolling and forming technique matched with it; thus obtain the rolling and forming brass alloys section bar of excellent performance; leadless environment-friendly brass section bar in the present invention; be no matter processability or shaping after corrosion resistance nature, all reach the requirement of use.
Description
Technical field
The present invention relates to the technical field of copper alloy, particularly a kind of preparation method of LEAD-FREE BRASS ALLOY.
Background technology
The major ingredient of existing non-environmental protection Winn bronze alloy is copper and zinc, and the ratio of copper and zinc is generally about 7:3(and carobrozne) or 6:4(i.e. six or four brass), the alloying element in addition usually containing larger content.Essential machining property is used in order to reach, more lead alloy element is often added in existing brass alloys, the leaded brass obtained has excellent cold and hot working performance, and the features such as fabulous cutting ability and self-lubricating, can meet the machining of different shape component.But well-known, lead element is a kind of element be very harmful to environment and human body, and its can particularly the kidney of children and cranial nerve etc. cause irreversible damage to blood of human body and neural system.Along with the enhancing gradually of people's environmental consciousness, the plumbous impact for HUMAN HEALTH and the pollution to environment obtain weight-normality day by day, and the use of restriction lead-containing alloy also becomes trend of the times.The developed countries such as the current U.S., Japan, European Union formulate or revise relevant laws and regulations in succession, do one's utmost to promote to reduce the leaded rate in environment, the AB1953 bill that such as California, USA was implemented since in January, 2010, the lead tolerance of household supplying pipe to be reduced to less than 0.25%, European Union even specifies to begin from August, 2011, and the lead tolerance upper limit of metal parts is 0.009%.
Under this background, the researchist of countries in the world have developed various lead-free brass alloys, in copper alloy, such as add the bismuth of more content with alternative lead, but relative to leaded brass, Bi brass is cost intensive not only, and the effect of bismuth is still difficult to be equal to lead completely, the plasticity of copper alloy can be caused sharply to decline; In addition a large amount of research is also had to show to adopt silicon to replace lead to obtain the brass of processing characteristics excellence, but too much silicon addition has the tendency reducing alpha phase zone, the fragility γ phase that easy generation is more, in addition too much silicon addition also can worsen the mobility of melt, thus produces detrimentally affect to performances such as the castings of brass.
Except developing lead-free environmental protection brass, the moulding process for brass is also the Main way of research.Rolling and forming section bar is as a kind of economic section section bar, the each component of such as body frame, chassis, pedal, extraneous adornment, radiator tube, vapor pipe etc. be widely used in each departments, particularly automotive industry such as the manufacture of national economy middle peasant machine, communications and transportation, automobile making all can form with rolling section combination.Rolling and forming technology is compared to machining means such as common cold rolling, cuttings, there is process period short, machining tool long service life, scrap generation and save the many merits such as blank usage quantity, working accuracy be high less, can be described as a kind of material-saving, energy-conservation, efficient metal forming process technology, be specially adapted to large batch of process for processing.Therefore, rolling and forming also obtain and uses widely in the good copper alloy machining of plasticity.
Summary of the invention
Namely object of the present invention is to provide a kind of lead-free reflow with excellent mechanical performance, corrosion resistance nature and machinability, and develops the rolling and forming technique matched with it.
Technical scheme of the present invention realizes particular by following content:
One, prepare burden: be 28-32Zn, 0.8-1.2Ge, 0.1-0.3Al, 0.2-0.5Sn, 0.2-0.5Si by alloy target weight percent, surplus is that Cu and inevitable impurity take raw material, wherein the total content of Al+Sn+Si is less than 1, described raw material to be purity be 99.99% oxygen free copper and purity be the powder of each alloying element of 99.9%;
Two, melting: by the raw material capable melting of Zhong in high frequency furnace under Ar gas atmosphere prepared, guarantee that melt liquid level is covered completely by charcoal in heat fused process, germanium powder and silica flour is added after temperature being risen to 1200-1250 DEG C, be incubated after 2-3 minute, add aluminium powder and glass putty after being cooled to 1050-1100 DEG C, after fully stirring, leave standstill insulation 10-20 minute, through check and finely tune bath composition qualified after complete melting, casting ingot-forming;
Three, hot-extrudable: ingot casting is carried out hot-extrudablely obtaining alloy bar material with the extrusion ratio of 8-10 under the condition of 750-780 DEG C;
Four, annealing before rolling and forming: implement anneal at 320-350 DEG C, annealing time is 2.5-3h;
Five, rolling and forming: adopt the capable rolling and forming of Roll die Zhong, shaping speed is 15-20m/min, and total deformation rate is 30-40%;
Six, finished products: the section bar obtained by rolling and forming implements anneal at 250-300 DEG C, annealing time 1h-1.5.
As preferably, before described rolling and forming, the temperature of anneal is 340 DEG C, annealing time 2.8h.
As preferably, shaping speed is 17m/min.
As preferably, total deformation rate is 33%.
As preferably, hot-extrudable temperature is 770 DEG C, and extrusion ratio is 8.
As preferably, alloy target weight percent is 30Zn, 1.0Ge, 0.1Al, 0.3Sn, 0.4Si, and surplus is Cu.
The invention has the advantages that: have developed a kind of novel leadless environment-friendly brass, and have developed the rolling and forming technique matched with it, thus obtain the rolling and forming brass alloys section bar of excellent performance.
Embodiment
Embodiment 1-9:
One, prepare burden: take raw material with the alloy target weight percent shown in table 1, described raw material to be purity be 99.99% oxygen free copper and purity be the powder of each alloying element of 99.9%;
Two, melting: the raw material prepared is carried out melting under Ar gas atmosphere in high frequency furnace, guarantee that melt liquid level is covered completely by charcoal in heat fused process, germanium powder and silica flour is added after temperature being risen to 1250 DEG C, be incubated after 3 minutes, add aluminium powder and glass putty after being cooled to 1050 DEG C, after fully stirring, leave standstill insulation 20 minutes, through check and finely tune bath composition qualified after complete melting, casting ingot-forming;
Three, hot-extrudable: ingot casting is carried out hot-extrudablely obtaining alloy bar material with the extrusion ratio of 8 under the condition of 750 DEG C;
Four, annealing before rolling and forming: implement anneal at 320 DEG C, annealing time is 2.5h;
Five, rolling and forming: adopt Roll die to carry out rolling and forming, shaping speed is 15/min, and total deformation rate is 30%;
Six, finished products: the section bar obtained by rolling and forming implements anneal at 280 DEG C, annealing time 1h.
The workhardness (HV) of shaping rear measurement Surface of profile; Observe the outward appearance of Surface of profile after rolling and forming and have flawless, if substantially do not have crack signature to be zero, have fine crack to be labeled as △, have obvious crack signature for ×; Adopt the anti-stress corrosion performance of ammonia cure experiment test section bar, specifically 14% ammoniacal liquor ammonia cure 24h after, remove observe with 20 power microscopes after corrosion product surperficial, if substantially do not have crack signature to be zero, have fine crack to be labeled as △, have obvious crack signature for ×.Above-mentioned test result is all listed in table 1.
Can know by inference to draw a conclusion by the result of table 1:
The content of Ge has material impact for the section bar performance of rolling and forming, the too high levels of Ge or too low cause rolling and forming after Surface of profile there is crackle, this may be determine impact because the content of Ge has for the stable existence of α phase in brass alloys.Simultaneously Ge to improve effect for dezincify resistance to after rolling and forming and stress corrosion.
Al is the strengthening element in wanting in brass alloys, the erosion resistance effect and tool increases significantly, its addition is less than 0.1 and will be difficult to play above-mentioned effect, but the content of Al is also not easily too high, too high Al content can cause the plasticity of brass to reduce, thus the cold/hot shaped of severe exacerbation alloy.
Sn and Al is similar, also be strengthening element important in brass alloys, the erosion resistance effect and tool increases significantly, particularly improve resistance to dezincify performance, it also can expand and stable alpha phase region as Ge after low-temperature annealing to a certain extent simultaneously, thus contribute to improving cold/hot shaped, but excessive Sn can cause producing too much β phase thus corrosion resistance nature after reducing rolling and forming performance and rolling and forming.
Si is important strengthening element, and very few interpolation will cause the section bar insufficient strength of rolling and forming, but the interpolation of too much Si will generate a large amount of hard crisp phases thus makes rolling and forming difficulty, and reduces the corrosion resistance nature of profiles.
Table 1
Embodiment 10-20, the composition of alloy is identical with embodiment 2, and the processing parameter such as speed and total deformation rate of the annealing temperature before hot-extrudable temperature and extrusion ratio, roll-forming and time, rolling and forming is see table 2.
Can be known by inference to draw a conclusion by the result of table 2:
Hot-extrudable temperature needs to control at 750-780 DEG C, is difficult to complete hot-extrudable processing smoothly and may produce the crisp hard phase of low temperature, higher than 780 DEG C, then may produces a large amount of β phases and cause disadvantageous effect to follow-up rolling and forming performance lower than 750 DEG C.And for extrusion ratio, must meet certain extrusion ratio can obtain corresponding mechanical property, but excessive extrusion ratio then can worsen follow-up rolling and forming performance.
Annealing temperature before roll-forming and time directly determine the tissue of alloy and the rolling and forming performance of alloy before roll-forming, implementing annealing at 320-350 DEG C, can to obtain the most favourable be the tissue mainly forming phase with α phase, if annealing temperature is lower than 320 DEG C, then can not the quantity of effective control β phase constitution, and the too high appearance also easily causing β phase constitution of annealing temperature.Annealing time has interval the most suitable, if annealing time is too short, ratio then shared by α phase constitution is difficult to reach required number of peaks, and annealing time is long, α phase constitution generation phase in version can be caused, ratio shared by α phase constitution can reduce on the contrary, and therefore preferably annealing time is 2.5-3h, more preferably 2.8h.
Shaping speed and total deformation rate have decisive action for the quality of rolling and forming, too fast shaping speed easily causes forming defect and requires that equipment occupation space is also large, and excessively slow shaping speed is unfavorable for the raising of production efficiency, consider for the above reasons, the upper limit of rolling and forming speed is set to 20m/min, and lower limit is set to 15m/min.Total deformation rate is crossed conference and is caused forming defect, and the problem that hardening strength is inadequate easily appears in the deficiency of total deformation rate, therefore total deformation rate is set as 30-40%.
Table 2
To sum up, the present invention by the proportioning of adjustment alloying element, and controls the related process parameters of melting technology, particularly rolling and forming, obtains the leadless environment-friendly brass alloys of processability excellence, and is processed as corresponding section bar.
Claims (5)
1. a preparation method for leadless environment-friendly brass, is characterized in that comprising the following steps:
One, prepare burden: be 28-32Zn, 0.8-1.2Ge, 0.1-0.3Al, 0.2-0.5Sn, 0.2-0.5Si by alloy target weight percent, surplus is that Cu and inevitable impurity take raw material, wherein the total content of Al+Sn+Si is less than 1, described raw material to be purity be 99.99% oxygen free copper and purity be the powder of each alloying element of 99.9%;
Two, melting: the raw material prepared is carried out melting under Ar gas atmosphere in high frequency furnace, guarantee that melt liquid level is covered completely by charcoal in heat fused process, germanium powder and silica flour is added after temperature being risen to 1200-1250 DEG C, be incubated after 2-3 minute, add aluminium powder and glass putty after being cooled to 1050-1100 DEG C, after fully stirring, leave standstill insulation 10-20 minute, through check and finely tune bath composition qualified after complete melting, casting ingot-forming;
Three, hot-extrudable: ingot casting is carried out hot-extrudablely obtaining alloy bar material with the extrusion ratio of 8-10 under the condition of 750-780 DEG C;
Four, annealing before rolling and forming: implement anneal at 320-350 DEG C, annealing time is 2.5-3h;
Five, rolling and forming: adopt Roll die to carry out rolling and forming, shaping speed is 15-20m/min, and total deformation rate is 30-40%;
Six, finished products: the section bar obtained by rolling and forming implements anneal at 250-300 DEG C, annealing time 1h-1.5h.
2. preparation method according to claim 1, is characterized in that: before described rolling and forming, the temperature of anneal is 340 DEG C, annealing time 2.8h.
3. preparation method according to claim 1, is characterized in that: shaping speed is 17m/min, total deformation rate is 33%.
4. preparation method according to claim 1, is characterized in that: hot-extrudable temperature is 770 DEG C, and extrusion ratio is 8.
5. preparation method according to claim 1, is characterized in that: alloy target weight percent is 30Zn, 1.0Ge, 0.1Al, 0.3Sn, 0.4Si, and surplus is Cu.
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| CN201310615813.7A CN103667779B (en) | 2013-11-27 | 2013-11-27 | A kind of preparation method of lead-free reflow |
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| CN201310615813.7A CN103667779B (en) | 2013-11-27 | 2013-11-27 | A kind of preparation method of lead-free reflow |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020975A (en) * | 2007-03-14 | 2007-08-22 | 宁波博威集团有限公司 | Free-cutting anticorrosive brass alloy and its prepn process |
| CN101161836A (en) * | 2007-10-16 | 2008-04-16 | 中南大学 | Leadless easy-cutting magnesium brass alloy and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8968492B2 (en) * | 2007-10-10 | 2015-03-03 | Toto Ltd. | Lead-free free-machining brass having improved castability |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020975A (en) * | 2007-03-14 | 2007-08-22 | 宁波博威集团有限公司 | Free-cutting anticorrosive brass alloy and its prepn process |
| CN101161836A (en) * | 2007-10-16 | 2008-04-16 | 中南大学 | Leadless easy-cutting magnesium brass alloy and method for preparing same |
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Effective date of registration: 20170929 Address after: 528300, No. 1, No. two, Heng Yi Road, Jian Jian Town, Shunde District, Guangdong, Foshan Patentee after: Foshan light metal ryco Limited by Share Ltd Address before: Yuyao City, Zhejiang province 315400 Ningbo City Yangming streets Liang Yan Cun Patentee before: YUYAO SHISEN COPPER FACTORY |
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Denomination of invention: A preparation method of lead-free brass Effective date of registration: 20200824 Granted publication date: 20151209 Pledgee: Shunde Guangdong rural commercial bank, Limited by Share Ltd branch Pledgor: FOSHAN LIANGLAIKE METAL Co.,Ltd. Registration number: Y2020980005291 |