CN101994025A - Copper alloy with low lead content - Google Patents
Copper alloy with low lead content Download PDFInfo
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Abstract
The invention relates to a copper alloy with low lead content, which comprises 0.05-0.3wt% of lead, 0.3-0.8wt% of aluminum, 0.01-0.3wt% of bismuth, 1-4wt% of silicon, 0.1-1wt% of tin and more than 93.6wt% of copper and zinc, wherein the content of the copper in the copper alloy with low lead content is 61-78wt%. The copper alloy with low lead content of the invention has good toughness and processing property and can improve the corrosion resistance to the chloride ion environment.
Description
Technical field
The present invention relates to an Albatra metal-, especially, the present invention relates to a kind of copper alloy of low lead.
Background technology
The major ingredient of brass is copper and zinc, and both ratios are generally about 7: 3 or 6: 4, comprises small amount of impurities in addition usually.In order to improve brass character, known brass is leaded (mostly being 1-3wt%) reaching the required mechanical characteristics of industry, and therefore becomes industrial important materials, is widely used in goods such as the metal device of pipeline, water tap, water supply/water exhaust system or metal valve.
Yet 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.States such as Japan, the U.S. revise relevant laws and regulations successively, do one's utmost to promote to reduce the leaded rate in the environment, contain the lead-containing alloy material that is used for the peripheral product of household electrical appliances, automobile, water, special requirement can not be from this product stripping lead to tap water, and must avoid Lead contamination in the processing and preparing process.
In addition, the corrosion phenomenon of dezincify (dezincification) taking place easily when the zinc content in the brass surpasses 20 weight %, particularly when the environment of this brass contact high chloride ion, for example during briny environment, can quicken the generation of Dezincification corrosion phenomenon.Because the structure of dezincification meeting havoc brass alloys reduces the surface strength of brass ware, even causes the brazed copper tube perforation, shortens the work-ing life of brass ware greatly, and causes the problem in the application.
At above-mentioned high lead tolerance and dezincify problem, industry continues exploitation copper alloy prescription, except the neccessary composition of copper and zinc, the Pb-free copper-alloy prescription of disclosed interpolation silicon (Si) such as TW421674, US7354489, US20070062615, US20060078458, US2004023441, US2002069942 and other element for example, but that the shortcoming of above-mentioned alloy is a machinability is not good.It is the Pb-free copper-alloy prescription of main alloy element that CN10144045 discloses with aluminium, silicon, phosphorus, though can be used for casting, machinability is relatively poor, and working (machining) efficiency is unsuitable for large quantities of volume productions far below leaded brass.It is the Pb-free copper-alloy prescription of main alloy element that CN101285138 and CN101285137 disclose with phosphorus, but it is used for casting and then is easy to generate defectives such as crackle, slag inclusion.For example US7297215, US6974509, US6955378, US6149739, US5942056, US5653827, US5487867, US5330712, US20060005901, US20040094243, US5637160, US20070039667 etc. disclose the brass alloys that add bismuth (Bi), the bi content of above-mentioned alloy formula is contained the scope of 0.5wt% to 7wt% approximately, defectives such as the bi content height easily cracks, slag inclusion, and cost is too high, is unfavorable for commercialization.US6413330 discloses the Pb-free copper-alloy prescription that comprises compositions such as bismuth, silicon, and CN101440444 discloses the no lead brass alloy of high zinc silicon, and because of its silicon content height but copper content is lower, the molten soup of alloy is mobile poor, the difficult slow type chamber of filling easily produces casting flaws such as misrun in metal pattern.CN101403056 discloses the no lead brass alloy comprise bismuth and manganese, but defectives such as high bi content easily cracks, slag inclusion, and the low manganese height of bismuth is the hardness height then, is difficult for chip breaking and machinability is poor.Above-mentioned brass alloys prescription still has shortcomings such as castability is poor, material embrittlement.
In addition, at the prescription of anti-dezincify, except the neccessary composition of copper and zinc, existing at present US4417929 discloses and comprises compositions such as iron, aluminium and silicon; US5507885 and US6395110 disclose and comprise compositions such as phosphorus, tin and nickel; US5653827 discloses and comprises compositions such as iron, nickel and bismuth; U 6974509 discloses the composition that comprises tin, bismuth, iron, nickel and phosphorus; US6787101 discloses and comprises phosphorus, tin, nickel, iron, aluminium, silicon and arsenic simultaneously; And patents exposure such as US6599378 and US5637160 are added into brass alloys to reach anti-dezincify effect with compositions such as selenium and phosphorus.Yet the brass lead tolerance of known anti-dezincify higher usually (mostly being 1-3wt%) is beneficial to the cold/hot-work of brass material, but does not meet environmental requirement, the lead release height, and be easy to produce in the preparation process Lead contamination.
Therefore, industry is desired most ardently the new brass material of exploitation, seek alternative Winn bronze, and can reach anti-Dezincification corrosion, but still must take into account castability, machinability, erosion resistance, with the alloy formula of mechanical properties.
Summary of the invention
For reaching above-mentioned and other purpose, the invention provides a kind of copper alloy of low lead, comprising: the lead of 0.05 to 0.3 weight %; 0.3 aluminium to 0.8 weight %; 0.01 bismuth to 0.3 weight %; The silicon of 1 to 4 weight %; 0.1 tin to 1 weight %; And above copper and the zinc of 93.6 weight %, wherein, the content of copper in the copper alloy of this low lead is 61 to 78 weight %.
In one embodiment, the copper that is comprised in the copper alloy of low lead of the present invention and the total content of zinc are 93.6 to 98.54 weight %, are preferably more than the 94 weight %.In one embodiment, the content of copper in the copper alloy of described low lead is 61 to 78 weight %, is preferably 62 to 74 weight %, more preferably 66 to 72 weight %.Therefore the copper alloy of low lead of the present invention, compares with known plumbiferous brass because of comprising the silicon composition, and the copper alloy of low lead of the present invention need have higher copper content so that the excellent toughness of alloy material to be provided.
In the copper alloy of low lead of the present invention, plumbous content is 0.05 to 0.3 weight %.In a preferred embodiment, plumbous content is 0.1 to 0.25 weight %, and more preferably 0.15 to 0.20 weight % adds the machinability that suitable lead can improve brass alloys.
In the copper alloy of low lead of the present invention, the content of bismuth is below the 0.3 weight %.In an embodiment, the content of bismuth is 0.01 to 0.3 weight %, preferred 0.05 to 0.25 weight %, more preferably 0.1 to 0.2 weight %.Add suitable bismuth and help to promote the alloy machinability.
In the copper alloy of low lead of the present invention, the content of aluminium is 0.3 to 0.8 weight %.In a preferred embodiment, the content of aluminium is 0.4 to 0.7 weight %, more preferably 0.5 to 0.65 weight %.Add an amount of aluminium and can increase the flowability of copper water, and improve the castability of this alloy material.
In the copper alloy of low lead of the present invention, the content of silicon is 1 to 4 weight %.In a preferred embodiment, the content of silicon is 1.5 to 3.5 weight %, more preferably 2 to 3 weight %.Add an amount of silicon and can increase the brass machinability, and can improve erosion resistance and the anti-stress corrosiveness of this alloy material high chloride ion environment (as seawater).
In the copper alloy of low lead of the present invention, the content of tin is 0.1 to 1 weight %.In a preferred embodiment, the content of tin is 0.2 to 0.9 weight %, more preferably 0.4 to 0.8 weight %.Add an amount of tin and can significantly improve the erosion resistance of alloy material, and can promote the intensity of alloy material high chloride ion environment (as seawater).
In addition, in copper alloy, add silicon and bismuth, can under the condition of low lead content, keep the cutting ability of alloy material, strengthen the erosion resistance of alloy material in the environment (as seawater) of high chloride ion content simultaneously.
The copper alloy of low lead of the present invention can be used as the equivalent material of known Winn bronze, has good castability, good machinability and mechanical properties, and comprises extremely low lead content, meets environmental protection requirement.Simultaneously, the copper alloy of low lead of the present invention has good anti-Dezincification corrosion, particularly has the anti-Dezincification corrosion of anti-high chloride ion, can be applicable in the higher environment of chlorine ion concentration such as seawater, swimming pool for example.
Description of drawings
Fig. 1 is the mechanical property of copper alloy and the graph of a relation of zinc content;
Fig. 2 A is the metallographic structure distribution plan of H59 leaded brass test piece;
Fig. 2 B is the metallographic structure distribution plan of low-lead brass test piece of the present invention;
Fig. 3 A is the metallographic structure distribution plan of the anti-Dezincification corrosion test of H59 leaded brass test piece;
Fig. 3 B is the metallographic structure distribution plan of the anti-Dezincification corrosion test of low-lead brass test piece of the present invention; And
Fig. 4 is the synoptic diagram of inlaying sample of electro-chemical test.
The primary clustering nomenclature
1 inlays sample
11 brass test pieces
12 resin layers
13 leads
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 by the content that this specification sheets disclosed.
In this manual, except as otherwise noted, otherwise the low plumbous composition that copper alloy comprised is a benchmark with this alloy gross weight all, and represents with weight percent (wt%).
The graph of a relation of the zinc content of the mechanical property of brass material and brass material as shown in Figure 1.For (alpha+beta) two-phase brass, before the zinc content in the alloy reached 45%, along with the increase of zinc content, this alloy strength at room temperature also improved thereupon; In case zinc content surpasses 45%, then, make and organize fragility to increase owing to the γ phase occurs in the metallographic structure of alloy, then alloy strength sharply reduces.On the other hand, for the brass alloys prescription that comprises complicated ingredient, then " the zinc equivalent " with the contained element of filling a prescription calculates zinc content, because copper alloy of the present invention comprises silicon, and the zinc equivalent of silicon is 10, that is, add 1% silicon in the Cu-Zn alloy, its metallographic structure is equivalent to the metallographic structure of the zinc content of increase by 10% in the Cu-Zn alloy, therefore, in brass alloys, add silicon, so that α/(alpha+beta) phase boundary in the Cu-Zn system is significantly shifted to the copper side, dwindled alpha phase zone strongly.Therefore, the silicone content in this alloy should not be higher than 4wt%, and silicone content is higher than the γ phase that 4wt% easily makes alloy occur making to organize fragility to increase, and copper alloy of the present invention need comprise good strength and toughness that higher copper content just can be kept this alloy material.In the low plumbous copper alloy of the present invention, the zinc equivalent of ingredient is: the zinc equivalent of silicon is 10, and the zinc equivalent of aluminium is 6, and the zinc equivalent of tin is 2, and plumbous zinc equivalent is 1, and the zinc equivalent of bismuth is 1.
Copper alloy prescription according to low lead of the present invention can make the lead content of alloy be reduced to 0.05 to 0.3 weight %, meets the world regulation for the lead content of the piping material that contacts with water.Therefore, help making the application of water tap and bathroom spare part, tap water pipeline, waterworks etc. according to the copper alloy of low lead of the present invention.
In an embodiment, the copper alloy of low lead of the present invention comprises: the copper of 61 to 78 weight %; 0.05 lead to 0.3 weight %; 0.3 aluminium to 0.8 weight %; 0.01 bismuth to 0.3 weight %; The silicon of 1 to 4 weight %; 0.1 tin to 1 weight %; And surplus is a zinc.
In an embodiment, the copper alloy of low lead of the present invention comprises: the copper of 62 to 74 weight %; 0.1 lead to 0.25 weight %; 0.4 aluminium to 0.7 weight %; 0.05 bismuth to 0.25 weight %; 1.5 silicon to 3.5 weight %; 0.2 tin to 0.9 weight %; And surplus is a zinc; Wherein, unavoidable impurities is lower than 0.1 weight %.
In an embodiment, the copper alloy of low lead of the present invention comprises: the copper of 66 to 72 weight %; 0.15 lead to 0.25 weight %; 0.5 aluminium to 0.65 weight %; 0.2 bismuth to 0.3 weight %; The silicon of 2 to 3 weight %; 0.4 tin to 0.8 weight %; And surplus is a zinc; Wherein, unavoidable impurities is lower than 0.1 weight %.
Below, will elaborate the present invention with exemplary embodiments.
The present invention who is used for aftermentioned test example hangs down the composition of plumbous copper alloy, and as described below, wherein, each components in proportions is a benchmark with the alloy gross weight:
Embodiment 1:
Cu：72.21wt％ Al：0.594wt％
Bi：0.178wt％ Si：2.732wt％
Sn：0.498wt％ Pb：0.141wt％
Zn: surplus
Embodiment 2:
Cu：74.23wt％ Al：0.451wt％
Bi：0.169wt％ Si：2.941wt％
Sn：0.645wt％ Pb：0.184wt％
Zn: surplus
Embodiment 3:
Cu：69.91wt％ Al：0.554wt％
Bi：0.183wt％ Si：2.421wt％
Sn：0.762wt％ Pb：0.136wt％
Zn: surplus
Embodiment 4:
Cu：62.47wt％ Al：0.684wt％
Bi：0.187wt％ Si：2.123wt％
Sn：0.417wt％ Pb：0.193wt％
Zn: surplus
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 low-lead brass alloy 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 1100-1150 ℃ temperature in induction furnace, and the refining slag-cleaning agent of interpolation 0.2wt%, in fusion process, material is fully stirred, 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, and, pouring temperature is maintained between 1060-1080 ℃ 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.By the mode that above-mentioned high melt and lower temperature are cast fast, can effectively avoid the segregation phenomena of silicon in alloy structure.
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.Be 30-36 ℃ in order to the temperature of the graphite water of cooling die and be 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 test analysis and calculate the total qualification rate of production:
Produce total qualification rate=salable product number/all prods number * 100%
The total qualification rate of the production of preparation process system reflection production preparation process quality stability, quality stability is high more, can guarantee ordinary production more.
In addition as a comparative example, prepare goods with preparation process same as described above with known H59 leaded brass.The composition of each alloy, processing characteristics and to produce total qualification rate as shown in table 1.
Table 1
The material flowability of low-lead brass of the present invention has low embrittlement susceptibility near known H59 leaded brass, can keep the material machinability, defective such as is difficult for cracking simultaneously, can satisfy the demand of production preparation process really.
As shown in Table 1, according to low-lead brass of the present invention is the sample group of raw material, qualification rate can reach more than 80%, its material flowability is near known H59 leaded brass, the production qualification rate is also suitable with the H59 leaded brass, really can be used as the equivalent material of H59 leaded brass, and have more the advantage of low lead content, meet environmental protection requirement.
Test example 2:
The metallographic structure of the test piece of brass material being observed material under optical metallographic microscope distributes, and its result who amplifies 100 times is shown in Fig. 2 A-2B.
Fig. 2 A is that the metallographic structure of H59 leaded brass (comparative example 2) distributes, and the measured value of its main component is: Cu:61.1wt%, Al:0.589wt%, Pb:1.54wt%, Bi:0.0089wt%, Si:0.0002wt%.Alloy is the α phase, and crystal grain is round shaped grain shape form.
The composition measured value of the low-lead brass of embodiment 1 is Cu:72.21wt%, Al:0.594wt%, Pb:0.141wt%, Bi:0.178wt%, Si:2.732wt%, Sn:0.498wt%.Tissue distribution forms the dendritic crystal phase constitution that waits with low embrittlement susceptibility shown in Fig. 2 B, and reaches particulate state mutually because of crystal grain is dendroid, can make material can provide good machinability than easy chip breaking.
Test example 3:
Brass alloys with embodiment 1 and comparative example 1 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.1% the CuCl2 solution of testing liquid for now joining, test temperature is 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 is shown in Fig. 3 A-3B.
The average dezincify degree of depth of comparative example 1 is 372.54 μ m, as shown in Figure 3A.The average dezincify degree of depth of embodiment 1 is 37.67 μ m, shown in Fig. 3 B, confirms that low-lead brass of the present invention has anti-preferably Dezincification corrosion.
Test example 4:
The brass alloys of embodiment 1 and comparative example 1 are carried out the average extent of corrosion test of material with electrochemical method, to determine the anti-average corrodibility of brass alloys.Make with brass test piece polishing and with reference to Fig. 4 and to inlay sample 1, wherein, the length that brass test piece 11 is exposed to this surface of inlaying sample 1 is about 10mm, and the degree of depth that brass test piece 11 is embedded in resin layer 12 is about 4mm, and connects and be equipped with lead 13.
This is inlayed sample, and to be soaked in concentration be in 5% sodium-chlor (NaCl) solution, records the polarization curve that comprises polarized potential and current density with linear polarization method, and as shown in the formula calculating polarization resistance Rp.Particularly, polarization resistance Rp value is big more, represents that the anti-average corrodibility of this material is good more.
Rp＝ΔE/ΔI
Wherein, Rp represents polarization resistance, and Δ E represents polarized potential, and Δ I represents impressed current density.
Table 2
According to table 2 as can be known, the Rp value (16.17K Ω/cm of low-lead brass of the present invention
2), far above H59 leaded brass (5.83K Ω/cm
2), confirm that the copper alloy of low lead of the present invention has excellent anti-average corrodibility, particularly in the environment of high chloride ion.Therefore, the copper alloy of low lead of the present invention can be used as the material of the article that contact with the high chloride ion environment, for example but unrestricted, and as piping material as swimming pool, or as the pipeline that contacts with ocean environment etc.
Test example 5:
Carry out the measuring mechanical property of brass alloys according to ISO6998-1998 " metallic substance tensile tests at room " standard, the result is as shown in table 3:
Table 3
As known from Table 3, the tensile strength of the copper alloy of low lead of the present invention is higher than known H59 leaded brass, and unit elongation is then roughly suitable with the H59 leaded brass, represents that low-lead brass alloy of the present invention possesses the mechanical property that is equivalent to the H59 leaded brass; But the lead tolerance of low-lead brass of the present invention is low, and compliance with environmental protection requirements can replace the H59 leaded brass really and is used to manufacture a product.
Test example 6:
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 4:
Table 4
As shown in table 4, each metal amount of separating out of low-lead brass 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 is when washing plumbous the processing, lead content substantially exceeds standard value, and embodiment 1 need not be a conformance with standard through washing plumbous the processing, and the scorification output of embodiment 1 still significantly is lower than through washing the plumbous comparative example of handling 1, compliance with environmental protection requirements more, and help HUMAN HEALTH.
In sum, the copper alloy of low lead of the present invention has and the suitable machining property of known H59 leaded brass, better tensile strength, the production qualification rate of preparation process is good, and reduce the scorification output of product greatly, the utmost point is suitable as the alloy material that replaces known leaded brass and be used to manufacture a product (for example sanitaryware is first-class as the fire hose).In addition, the copper alloy of low lead of the present invention has excellent resisting corrosion of chlorine ion, the brass work that is beneficial to make the waterworks in the high chloride ion environment or contacts with ocean environment.
The foregoing description is copper alloy and its goods preparation method of illustrative low lead of the present invention only, but not is 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 as described later claims scope put down in writing.
Claims (7)
1. one kind is hanged down plumbous copper alloy, comprising:
0.05 lead to 0.3 weight %;
0.3 aluminium to 0.8 weight %;
0.01 bismuth to 0.3 weight %;
The silicon of 1 to 4 weight %;
0.1 tin to 1 weight %; And
Copper more than 93.6% and zinc, wherein, the content of copper in the copper alloy of described low lead is 61 to 78 weight %.
2. the copper alloy of low lead as claimed in claim 1, wherein, plumbous content is 0.15 to 0.25 weight %.
3. the copper alloy of low lead as claimed in claim 1, wherein, the content of aluminium is 0.5 to 0.65 weight %.
4. the copper alloy of low lead as claimed in claim 1, wherein, the content of bismuth is 0.1 to 0.2 weight %.
5. the copper alloy of low lead as claimed in claim 1, wherein, the content of silicon is 2 to 3 weight %.
6. the copper alloy of low lead as claimed in claim 1, wherein, the content of tin is 0.4 to 0.8 weight %.
7. the copper alloy of low lead as claimed in claim 1, wherein, the content of copper is 62 to 74 weight %.
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| CN110584248A (en) * | 2019-09-25 | 2019-12-20 | 铜陵铜官府文化创意股份公司 | Method for simulating ultrathin flower and leaf plants by using copper process |
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| CN110584248A (en) * | 2019-09-25 | 2019-12-20 | 铜陵铜官府文化创意股份公司 | Method for simulating ultrathin flower and leaf plants by using copper process |
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Application publication date: 20110330 |