CN101988164A - Dezincification resistant brass alloy with low lead content - Google Patents
Dezincification resistant brass alloy with low lead content Download PDFInfo
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- CN101988164A CN101988164A CN2009101641168A CN200910164116A CN101988164A CN 101988164 A CN101988164 A CN 101988164A CN 2009101641168 A CN2009101641168 A CN 2009101641168A CN 200910164116 A CN200910164116 A CN 200910164116A CN 101988164 A CN101988164 A CN 101988164A
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Abstract
The invention discloses a dezincification resistant brass alloy with low lead content, comprising less than 0.3 wt% of lead (Pb), 0.02 to 0.15 wt% of stibium (Sb), 0.02 to 0.25 wt% of arsenic (As), 0.4 to 0.8 wt% of aluminum (Al), 1 to 20 ppm of boron (B), and more than 97 wt% of copper (Cu) and zinc (Zn), wherein the copper content in the dezincification resistant brass alloy is 58 to 70 wt%. The dezincification resistant brass alloy with low lead content of the invention has excellent casting performance, good toughness and machinability, and corrosion resistance, and can reduce the dezincification on the surface.
Description
Technical field
The present invention relates to a kind of copper alloy of anti-dezincify, especially, the present invention relates to a kind of anti-dezincify brass alloys of low lead.
Background technology
The major ingredient of brass is copper and zinc, the ratio between two example is generally about 7: 3 or 6: 4, and the corrosion phenomenon of dezincify (dezincification) easily takes place when the zinc content in the brass surpasses 20 weight %, for example when the brass alloys object is applied in the environment, the zinc of optimum solvation alloy surface, and the contained copper of alloy still remains on the mother metal, forms the corrosion phenomenon of the fragility copper of multiple hole.Generally speaking, when zinc content during, be difficult for taking place dezincify, but, then improve the susceptibility of dezincify along with zinc content increases less than 15 weight %; After zinc was greater than 30 weight %, the Dezincification corrosion phenomenon can be more obvious.
Existing reported in literature, alloy composition structure and environmental factors can influence the Dezincification corrosion phenomenon, it seems that by alloy composition zinc content stays porous copper after greater than 20% single-phase alpha brass dezincify, and the Dezincification corrosion of alpha+beta two-phase brass begins mutually from β at first, after β changes loose copper into mutually fully, expand to again the α phase (referring to people such as Wang Jihui, 1999, the investigation of materials journal, the 13rd phase, the 1-8 page or leaf).
Because the structure of dezincification of brass phenomenon meeting havoc brass alloys reduces the surface strength of brass ware, even causes the brazed copper tube perforation, significantly shortens the work-ing life of brass ware, and causes the problem in the application.Therefore, for the anti-dezincify ability of brass ware, international generally acceptance is as standards such as AS2345, ISO 6509, and promptly the degree of depth of brass product surface dezincify layer must not surpass 100 μ m.
At the prescription of anti-dezincify brass alloys, except the neccessary composition of copper and zinc, existing at present US4,417,929 disclosures comprise compositions such as iron, aluminium and silicon; US 5,507,885 and US 6,395,110 disclose and comprise compositions such as phosphorus, tin and nickel; US 5,653, and 827 disclosures comprise compositions such as iron, nickel and bismuth; US6,974,509 disclose the composition that comprises tin, bismuth, iron, nickel and phosphorus; US 6,787, and 101 disclosures comprise phosphorus, tin, nickel, iron, aluminium, silicon and arsenic simultaneously; And US 6,599,378 and US 5,637,160 Patent publish such as grade are added into brass alloys to reach anti-dezincify effect with compositions such as selenium and phosphorus; Or referring to people such as Wang Jihui, 1999, the investigation of materials journal, the 13rd phase, the 1-8 page or leaf discloses and is added into brass alloys to reach anti-dezincify effect with boron and arsenic etc.
Yet, know anti-dezincify brass lead tolerance higher usually (mostly being 1-3wt%), be beneficial to the cold/hot-work of brass material, but along with environmental consciousness comes back, heavy metal comes into one's own gradually for the problem of health effects and environmental pollution, therefore, the use of restriction lead-containing alloy is present trend, Japan, states such as the U.S. revise relevant laws and regulations successively, do one's utmost to promote to reduce the leaded rate in the environment, comprise and be used for household electrical appliances, automobile, the lead-containing alloy material of the peripheral product of water, special requirement can not be from this product stripping lead to tap water, and must avoid Lead contamination in procedure for processing.Therefore, this area still continues the exploitation brass material, seeks alternative leaded anti-dezincify brass, but still takes into account the alloy formula of casting and machining property and anti-Dezincification corrosion.
Summary of the invention
For reaching above-mentioned and other purpose, the invention provides the anti-dezincify of a kind of low lead (dezincificationresistant) brass alloys, comprise: the lead (Pb) that 0.3 weight % (wt%) is following; 0.02 antimony (Sb) to 0.15 weight %; 0.02 arsenic (As) to 0.25 weight %; 0.4 aluminium (Al) to 0.8 weight %; 1 to 20ppm boron (B); And the above copper (Cu) and zinc (Zn) of 97 weight %, wherein, the content of copper in the brass alloys of described anti-dezincify is 58 to 70 weight %.
Anti-dezincify copper alloy of the present invention is brass alloys, and the total content of copper and zinc can reach more than the 97wt%.In an embodiment, the content of this copper is 58-70wt%, and the copper of the content of this scope can provide alloy good toughness, is beneficial to the following process of alloy material.In a preferred embodiment, the content of this copper is 61 to 65 weight %.
In the anti-dezincify brass of low lead of the present invention, the content of antimony is 0.02 to 0.15 weight %.In a preferred embodiment, the content of antimony is 0.04 to 0.12 weight %.According to element formation intermetallic compounds such as the copper of alloy formula of the present invention and antimony, improving the machinability of this alloy material, and be unlikely to produce casting flaw.
In the anti-dezincify brass of low lead of the present invention, the content of aluminium is 0.4 to 0.8wt%.In a preferred embodiment, the content of aluminium is 0.5 to 0.7wt%.Add an amount of aluminium and can increase the flowability of copper water, and improve the castability of this alloy material.
In the brass alloys of anti-dezincify of the present invention, the content of arsenic is 0.02 to 0.25wt%.In a preferred embodiment, the content of arsenic is 0.13 to 0.17wt%.Add an amount of arsenic and can significantly improve the performance of the anti-Dezincification corrosion of brass.
In the brass alloys of anti-dezincify of the present invention, the content of boron is 1 to 20ppm.In a preferred embodiment, the content of boron is 8 to 14ppm.Add an amount of boron and the grain refining of alloy material can be improved the alloy material performance.
The brass alloys of anti-dezincify of the present invention also comprise at least a element in nickel and the tin of being selected from of 0.2 to 1.25 weight %.In an embodiment, the brass alloys of this anti-dezincify can comprise nickel and tin simultaneously.In a preferred embodiment, the content of tin is 0.1 to 1 weight %.In a preferred embodiment, the content of nickel is 0.1 to 0.25 weight %.
The lead content that brass alloys comprised of anti-dezincify of the present invention is extremely low, is below the 0.3 weight %.In an embodiment, this lead content is 0.05 to 0.3 weight %.And also may have impurity in this alloy, unavoidable impurities content is below the 0.1wt%.
Description of drawings
Figure 1A is the metallographic structure distribution plan of the brass alloys test piece of the low plumbous anti-dezincify of the present invention;
Figure 1B is the metallographic structure distribution plan of CW602N brass test piece;
Fig. 1 C is the metallographic structure distribution plan of 59 leaded brass test pieces;
Fig. 2 A is the metallographic structure distribution plan of the anti-Dezincification corrosion test of the brass alloys test piece of the anti-dezincify of the low lead of the present invention;
Fig. 2 B is the metallographic structure distribution plan of the anti-Dezincification corrosion test of CW602N brass test piece; With
Fig. 2 C is the metallographic structure distribution plan of the anti-Dezincification corrosion test of 59 leaded brass test pieces.
Embodiment
Below by particular specific embodiment explanation embodiments of the present invention, those skilled in the art can understand other advantage of the present invention and effect according to the content that this specification sheets disclosed.
In this manual, " brass alloys of the copper alloy of anti-dezincify/anti-dezincify " are this area Essential Terms, mean that this alloy surface has tolerance for the environmental corrosion condition and be difficult for producing dezincify, this sentences Australian AS 2345 standard rules (Dezincification resistance of copper alloys) and is as the criterion, and the dezincify layer depth of the product surface of definition brass alloys can not surpass 100 μ m.
In this manual, except as otherwise noted, otherwise the composition that brass alloys comprised of anti-dezincify is a benchmark with this alloy gross weight all, and represents with weight percent (wt%).
Brass alloys according to the anti-dezincify of low lead of the present invention, only need use the antimony of 0.02-0.15wt% and the arsenic of 0.02-0.25wt% can reach the material behavior of knowing that leaded brass possessed (as machinability etc.), and the brass alloy material of the anti-dezincify of this low lead such as is difficult for cracking or is mingled with at product defects, and meets the anti-dezincify requirement of Australian AS-2345.And brass alloys prescription of the present invention effectively reduces the production cost of the brass alloys that hang down plumbous anti-dezincify, goes up very advantageous for commercial mass production and application.
In addition, the brass alloys prescription of anti-dezincify of the present invention can make lead content be low to moderate below the 0.3wt%, even reach below the 0.2wt%.Therefore, help making water tap and bathroom spare part, tap water pipeline, waterworks etc.
In one embodiment, the brass alloys of the anti-dezincify of low lead of the present invention comprise: the copper of 58-70 weight %; 0.02 antimony to 0.15 weight %; 0.02 arsenic to 0.25 weight %; 0.4 aluminium to 0.8 weight %; 1 to 20ppm boron; 0.05 lead to 0.3 weight %; 0.1 the unavoidable impurities that weight % is following; And all the other content are zinc.
In another embodiment, the brass alloys of the anti-dezincify of low lead of the present invention comprise: the copper of 58-70 weight %; 0.02 antimony to 0.15 weight %; 0.02 arsenic to 0.25 weight %; 0.4 aluminium to 0.8 weight %; 1 to 20ppm boron; 0.2 nickel and/or tin to 1.25 weight %; And the lead of 0.05 to 0.3 weight %; 0.1 the unavoidable impurities that weight % is following; And all the other content are zinc.
In another embodiment, the brass alloys of the anti-dezincify of low lead of the present invention comprise: the copper of 61-65 weight %; 0.04-0.12 the antimony of weight %; 0.13-0.17 the arsenic of weight %; 0.5-0.7 the aluminium of weight %; The boron of 8-14ppm; The tin of 0.1-1wt%; The nickel of 0.1-0.25wt%; 0.05 lead to 0.3 weight %; 0.1 the unavoidable impurities that weight % is following; And all the other content are zinc.
Below, will elaborate the present invention with exemplary embodiments.
The present invention who is used for aftermentioned test example hangs down the composition of the brass alloys of plumbous anti-dezincify, and as described below, wherein, each components in proportions is a benchmark with the alloy gross weight:
Embodiment 1:
Cu：61.95wt％ Al：0.469wt％
Sb：0.0415wt％ B：13ppm
As：0.151wt％ Ni：0.143wt％
Pb：0.141wt％ Sn：0.294wt％
Zn: all the other content.
Embodiment 2:
Cu：62.05wt％ Al：0.557wt％
Sb：0.0763wt％ B：8ppm
As：0.162wt％ Ni：0.231wt％
Pb：0.173wt％ Sn：0.546wt％
Zn: all the other content.
Embodiment 3:
Cu：62.6wt％ Al：0.671wt％
Sb：0.1137wt％ B：11ppm
As：0.147wt％ Ni：0.187wt％
Pb：0.159wt％ Sn：0.741wt％
Zn: all the other content.
Test example 1:
With round sand, Precondensed UreaFormaldehyde Resin, furane resin and solidifying agent is that raw material prepares core with core shooting machine, and measures the resin gas forming amount with the gas-forming property trier.The gained core must be finished using in 5 hours, otherwise needed with oven for drying.
With the anti-dezincify brass alloys of low lead of the present invention and foundry returns preheating 15 minutes, temperature is reached more than 400 ℃, the ratio that with both with weight ratio is 7: 1 is again carried out melting with induction furnace, and the refining slag-cleaning agent of interpolation 0.2wt%, treat that these brass alloys reach certain molten state (calling fusion copper liquid in the following text), cooperate core and restrike mold to cast with the metal mold gravity casting machine, also, pouring temperature is maintained between 1010-1060 ℃ with temperature monitoring system control.Each charging capacity of casting is advisable with 1-2kg, and pouring time is controlled at 3-8 in second.
Treat that mold cools down solidifies back die sinking discharging cleaning dead head, the monitoring die temperature makes die temperature be controlled in 200-220 ℃ and forms foundry goods, carries out the foundry goods demoulding subsequently.After every die casting took out, cleaning mold guaranteed that the core print position is clean, row immersion cooling again behind die surface spray graphite.Being used for the temperature of graphite water of cooling die is 30-36 ℃ and is advisable that proportion is 1.05～1.06.
The refrigerative foundry goods is carried out self check and send into the cleaning of sand cleaning machine cylinder pottery sand.Then, carry out blank and handle (thermal treatment (recovery) of casting blank is to eliminate the internal stress that casting produces).Blank is carried out follow-up mechanical workout and polishing, so that core cavity is not with sand, scrap metal or other impurity.Carry out the quality inspection analysis and calculate the total qualification rate of production:
Produce total qualification rate=salable product number/all prods number * 100%
The total qualification rate reflection of the production of preparation process production preparation process quality stability, quality stability is high more, could guarantee ordinary production.
In addition with the anti-dezincify brass of the CW602N that knows (being called for short DR brass sometimes, is the anti-dezincify brass through Australian AS2345-2006 authentication) and 59 leaded brasss known as a comparative example, prepare object with preparation process same as described above.The composition of each alloy, processing characteristics and to produce total qualification rate as shown in table 1.
Table 1
As shown in Table 1, be that the qualification rate that studies group of raw material can reach more than 90% according to the brass alloys of the anti-dezincify of low lead of the present invention, with to know 59 leaded brasss and DR brass (CW602N) suitable, can be used as alternative brass material really.And the brass alloys of the anti-dezincify of low lead of the present invention can significantly reduce the lead content in the alloy, the Lead contamination of effectively avoiding in the processing procedure being produced, and reduce plumbous emission when using this cast object, when taking into account material behavior, more can reach environmental protection requirement.
Test example 2:
Material is inspected in the test piece of the brass alloys (embodiment 3) of the anti-dezincify of low lead of the present invention, CW602N brass (comparative example 1), 59 leaded brasss (comparative example 4) under optical metallographic microscope tissue distribution, amplify 100 times result, respectively shown in accompanying drawing 1A-1C.
The measured value of the alloy main component of embodiment 3 is: Cu:62.6%, Zn:36.43%, Pb:0.159%, Sb:0.1137%, Al:0.627% and As:0.147%, its tissue distribution is shown in accompanying drawing 1A.
Shown in accompanying drawing 1A-1C, the α phase constitution of the metallographic of CW602N brass (accompanying drawing 1B) is thicker, and the machinability of expression material is relatively poor; And the metallographic of the brass alloys of the anti-dezincify of low lead of the present invention and 59 leaded brasss is similar, all form the dendritic crystal phase constitution that can form single-size, but the crystal grain of the α phase of the brass alloys of the anti-dezincify of low lead of the present invention is more tiny, organize more fine and close, this expression material have good mechanical properties.
Test example 3:
Brass alloys with embodiment 3, comparative example 1 and comparative example 4 carry out the dezincify test, to detect the solidity to corrosion of brass.The dezincify test is to carry out according to Australian AS2345-2006 " the anti-dezincify of copper alloy " standard.Set cured edge sample with phenolic aldehyde before the corrosion experiment. making its exposed area is 100mm
2, all test pieces are all ground smooth through the 600# abrasive paper for metallograph, and clean, dry with distilled water.The 1%CuCl of testing liquid for now joining
2Solution, test temperature are 75 ± 2 ℃.With test piece and CuCl
2Solution placed the constant temperature water bath effect 24 ± 0.5 hours, longitudinally cut after the taking-up, after the section polishing with test piece, measured its depth of corrosion and with digital metallographic electron microscope observation, the result as shown in Figure 2.
The average dezincify degree of depth of the low plumbous anti-dezincify brass of the present invention of embodiment 3 is 77.6 μ m, shown in accompanying drawing 2A.The average dezincify degree of depth of the CW602N brass of comparative example 1 is 82.28 μ m, shown in accompanying drawing 2B figure.The average dezincify degree of depth of 59 leaded brasss of comparative example 4 is 336.72 μ m, shown in accompanying drawing 2C.
The above results confirms that the anti-dezincify brass of low lead of the present invention meets the anti-dezincify standard of Australian AS2345-2006 (the dezincify layer depth can not surpass 100 μ m), and has better anti-dezincify ability.
Test example 4:
Present embodiment carries out the test of mechanical property according to ISO6998-1998 " metallic substance tensile tests at room " standard, and the result is as shown in table 2 below.
Table 2
As known from Table 2, the tensile strength of the anti-dezincify brass of low lead of the present invention and elongation are suitable with CW602N brass with 59 leaded brasss of knowing, and represent that low-lead brass alloy of the present invention possesses the mechanical property that is equivalent to 59 leaded brasss and CW602N brass; But the lead tolerance of the anti-dezincify brass of low lead of the present invention is low, and compliance with environmental protection requirements can replace 59 leaded brasss and CW602N brass really and is used to manufacture a product.
Test example 5:
Allow the amount of separating out standard to test according to NSF 61-2007a SPAC single product metal, check with environment that water contacts in the metal amount of separating out of brass alloys, test result is as shown in table 3 below:
Table 3
As shown in table 3, the amount of separating out of each metallic element of the anti-dezincify brass of low lead of the present invention all is lower than upper limit standard value, meets the requirement of NSF 61-2007a SPAC.The material of comparative example 1 and comparative example 4 is when washing plumbous the processing, lead content is the value of being above standard significantly all, it need not be conformance with standard through washing plumbous the processing that embodiment 1 is only arranged, and the amount of separating out of the heavy metal lead of the anti-dezincify brass alloys of low lead of the present invention still significantly is lower than through washing plumbous 59 leaded brasss and the CW602N brass of handling, more meet environmental protection, and help HUMAN HEALTH.
In sum, the brass alloy material of the anti-dezincify of low lead of the present invention has good castability, has excellent toughness, machinability is good, defective such as be difficult for cracking or be mingled with, be unlikely to produce casting flaw, can reach the material behavior that leaded brass possesses, be beneficial to alloy material and be applied to successive process.The brass alloys of the anti-dezincify of low lead of the present invention need not be washed plumbous the processing and promptly have the effect that low scorification goes out, and can reduce the production cost of processing procedure, go up very advantageous for commercial large quantities of volume productions and application.
The foregoing description is the brass alloys of the anti-dezincify of illustrative low lead of the present invention only, but not are used to limit the present invention.Any those skilled in the art all can be under spirit of the present invention and category, and the foregoing description is modified and changed.Therefore, the scope of the present invention such as following claim book are put down in writing.
Claims (8)
1. the brass alloys of an anti-dezincify comprise:
0.3 the lead that weight % is following;
0.02 antimony to 0.15 weight %;
0.02 arsenic to 0.25 weight %;
0.4 aluminium to 0.8 weight %;
1 to 20ppm boron; With with
Copper and zinc that 97 weight % are above, wherein, the content of copper in the brass alloys of described anti-dezincify is 58 to 70 weight %.
2. the brass alloys of anti-dezincify as claimed in claim 1, wherein, the content of described copper is 61 to 65 weight %.
3. the brass alloys of anti-dezincify as claimed in claim 1, wherein, the content of described antimony is 0.04 to 0.12 weight %.
4. the brass alloys of anti-dezincify as claimed in claim 1, wherein, the content of described arsenic is 0.13 to 0.17 weight %.
5. the brass alloys of anti-dezincify as claimed in claim 1, wherein, the content of described boron is 8 to 14ppm.
6. the brass alloys of anti-dezincify as claimed in claim 1 also comprise at least a element in nickel and the tin of being selected from of 0.2 to 1.25 weight %.
7. the brass alloys of anti-dezincify as claimed in claim 6, wherein, the content of described tin is 0.1 to 1 weight %.
8. the brass alloys of anti-dezincify as claimed in claim 6, wherein, the content of described nickel is 0.1 to 0.25 weight %.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205596A (en) * | 2012-01-16 | 2013-07-17 | 摩登岛股份有限公司 | Lead-free antimony-titanium-brass alloy |
| CN103205597A (en) * | 2012-01-16 | 2013-07-17 | 摩登岛股份有限公司 | Lead-free antimony-nickel-brass alloy |
| CN104109772A (en) * | 2013-04-18 | 2014-10-22 | 鹤山市金洲铜材实业有限公司 | Anti-dezincification corrosion-resistant DR brass and preparation method thereof |
| CN104745863A (en) * | 2015-04-08 | 2015-07-01 | 九牧厨卫股份有限公司 | Low-lead dezincification-resistant brass alloy suitable for being cast |
| EP2963134A1 (en) * | 2014-06-23 | 2016-01-06 | Jiangxi Audy Brasswork Inc. | Low-lead brass alloy |
| CN106170569A (en) * | 2014-01-30 | 2016-11-30 | 北欧古苏姆冶金公司 | There are resistance to dezincification and the brass alloys of machining property of improvement |
| CN107855481A (en) * | 2017-11-22 | 2018-03-30 | 龙岩市鸿航金属科技有限公司 | A kind of unleaded low silicon of anti-dezincification draws the production method of casting arsenic yellow copper ingot |
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2009
- 2009-08-06 CN CN2009101641168A patent/CN101988164A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205596A (en) * | 2012-01-16 | 2013-07-17 | 摩登岛股份有限公司 | Lead-free antimony-titanium-brass alloy |
| CN103205597A (en) * | 2012-01-16 | 2013-07-17 | 摩登岛股份有限公司 | Lead-free antimony-nickel-brass alloy |
| CN104109772A (en) * | 2013-04-18 | 2014-10-22 | 鹤山市金洲铜材实业有限公司 | Anti-dezincification corrosion-resistant DR brass and preparation method thereof |
| CN106170569A (en) * | 2014-01-30 | 2016-11-30 | 北欧古苏姆冶金公司 | There are resistance to dezincification and the brass alloys of machining property of improvement |
| EP2963134A1 (en) * | 2014-06-23 | 2016-01-06 | Jiangxi Audy Brasswork Inc. | Low-lead brass alloy |
| EP2963134B1 (en) | 2014-06-23 | 2018-05-23 | Jiangxi Audy Brasswork Inc. | Low-lead brass alloy |
| CN104745863A (en) * | 2015-04-08 | 2015-07-01 | 九牧厨卫股份有限公司 | Low-lead dezincification-resistant brass alloy suitable for being cast |
| CN107855481A (en) * | 2017-11-22 | 2018-03-30 | 龙岩市鸿航金属科技有限公司 | A kind of unleaded low silicon of anti-dezincification draws the production method of casting arsenic yellow copper ingot |
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Application publication date: 20110323 |