WO2014117684A1 - 一种热成型性能优异的无铅易切削耐蚀黄铜合金 - Google Patents

一种热成型性能优异的无铅易切削耐蚀黄铜合金 Download PDF

Info

Publication number
WO2014117684A1
WO2014117684A1 PCT/CN2014/071362 CN2014071362W WO2014117684A1 WO 2014117684 A1 WO2014117684 A1 WO 2014117684A1 CN 2014071362 W CN2014071362 W CN 2014071362W WO 2014117684 A1 WO2014117684 A1 WO 2014117684A1
Authority
WO
WIPO (PCT)
Prior art keywords
alloy
brass
brass alloy
lead
performance
Prior art date
Application number
PCT/CN2014/071362
Other languages
English (en)
French (fr)
Inventor
许传凯
胡振青
周年润
章四琪
龙佳
张华威
Original Assignee
路达(厦门)工业有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=48412637&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2014117684(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 路达(厦门)工业有限公司 filed Critical 路达(厦门)工业有限公司
Priority to DK14746185.9T priority Critical patent/DK2952596T3/en
Priority to JP2015555571A priority patent/JP6335194B2/ja
Priority to US14/765,305 priority patent/US11028464B2/en
Priority to EP14746185.9A priority patent/EP2952596B1/en
Priority to CA2907482A priority patent/CA2907482C/en
Priority to PL14746185T priority patent/PL2952596T3/pl
Priority to ES14746185.9T priority patent/ES2676271T3/es
Publication of WO2014117684A1 publication Critical patent/WO2014117684A1/zh

Links

Classifications

    • 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
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • 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

Definitions

  • the invention belongs to the technical field of alloys, and particularly relates to a lead-free free-cutting corrosion-resistant brass alloy, in particular to a lead-free free-cutting corrosion-resistant brass alloy excellent in thermoforming performance. Background technique
  • Lead brass such as C36000, ZCuZn38Pb2
  • leaded brass can cause environmental pollution during production and use, and endanger human health.
  • Developed countries and regions such as the United States and the European Union have successively formulated standards and decrees such as NSF-ANSI372, AB-1953, and RoHS, and gradually banned the production, sale, and use of lead-containing products.
  • Silicon brass is the focus of today's lead-free free-cutting brass research and there are a number of patents available.
  • Chinese Patent Application No. 200810163930.3 discloses a free-cutting silicon brass alloy and a manufacturing method thereof.
  • the chemical composition of the silicon brass alloy is: copper 59.2 ⁇ 63.5wt%, silicon 0.35 ⁇ 0.9wt%, lead 0.04 ⁇ 0.25wt% , phosphorus 0.22 ⁇ 0.38wt%, other elements: 0.005 ⁇ 1.1 wt%, the balance is zinc and impurities, it has excellent thermoforming properties, cutting performance, but its corrosion resistance, especially stress corrosion resistance is poor, can not
  • the produced valves are cracked when tested by ammonia smoke.
  • Chinese patent application 200580046460.7 discloses a free-cutting copper joint containing a very small amount of lead Gold, the alloy includes: 71.5 ⁇ 78.5wt% Cu, 2.0 - 4.5wt% Si, 0.005 ⁇ 0.02wt% Pb, the balance is Zn, the alloy continuous-cast microstructure is coarse and uneven, so the hot workability is better Poor, can not be applied to the formation of complex products, in actual production, hot extrusion is usually required to improve the as-cast structure, which will inevitably lead to increased costs and waste of energy, making it difficult to promote technology.
  • Cide ZL200580019413.3 discloses a grain-refined copper-based alloy casting composed of the following components: Cu: 69 ⁇ 88wt%, Si: 2 ⁇ 5wt%, Zr: 0.0005 ⁇ 0.4wt%, P : 0.01 - 0.25wt%, the balance is zinc.
  • the alloy improves the properties of alloy castings by adding elemental zirconium to refine grains, but the metal zirconium resources are scarce and expensive.
  • zirconium is extremely easy to melt in the alloy. When it is combined with an oxidizing medium such as oxygen or sulfur to be converted into slag and loses its effect, it causes a large loss of zirconium when the waste is smelted, and the alloy has poor recyclability. Summary of the invention
  • the present invention provides a lead-free, easily-cuttable corrosion-resistant brass alloy excellent in thermoforming properties.
  • the brass alloy of the invention has excellent comprehensive performance and can be used for producing faucets, valves, pipe joints, electronic appliances, automobiles, machinery and the like.
  • a lead-free free-cutting corrosion-resistant brass alloy excellent in thermoforming properties the brass alloy containing: 74.5 ⁇ 76.5wt 0 /c ⁇ Cu, 3.0 ⁇ 3.5wt 0 /c ⁇ Si, 0.11 - 0.2 wt 0 /c ⁇ Fe, 0.04 ⁇ 0.10 wt% P, the balance being Zn and unavoidable impurities.
  • the content of Cu in the brass alloy is: 75-76 wt%.
  • the content of Si in the brass alloy is: 3.1 to 3.4 wt%.
  • the content of P in the brass alloy is: 0.04 to 0.08 wt%.
  • the brass alloy further contains 0.001 to 0.01% by weight of at least one element selected from the group consisting of B, Ag, Ti and RE.
  • the content of B, Ag, Ti and RE in the brass alloy is: 0.001 to 0.005 wt%.
  • the brass alloy further contains at least one element selected from the group consisting of Pb, Bi, Se and Te, wherein the content of Pb is 0.01 to 0.25 wt%, the content of Bi is 0.01 to 0.4 wt%, and the content of Se is for
  • Te content is 0.005 ⁇ 0.4 wt 0 / 0 .
  • the brass alloy further contains 0.05 to 0.2 wt% of at least one element selected from the group consisting of Mn, Al, Sn, and Ni.
  • the brass alloy further contains 0.03 to 0.15 wt% of at least one element selected from the group consisting of As and Sb.
  • the invention controls the copper content to be 74.5 ⁇ 76.5wt% to better solve the corrosion resistance problem of brass. If the copper content exceeds 76.5 wt%, the raw material cost of the product is too high, and the forging property starts to decrease; the copper content is less than 74.5 wt%, and the mechanical properties, especially the elongation, are not ideal.
  • a hard and brittle Si-rich phase can be formed, which can act as chip breaking during cutting and improve the cutting performance of the brass.
  • silicon content is more than 3.5% by weight, the plasticity of the alloy is lowered, and silicon is preferably not more than 3.5% by weight; when the silicon content is less than 3.0% by weight, the cutting property and the forging property are not satisfactory, so the silicon content is not less than 3.0% by weight.
  • Iron and phosphorus are simultaneously added to the alloy of the present invention.
  • Iron and silicon can form a high melting point iron-silicon compound, which is uniformly distributed in the form of particles in the matrix, so that the Si-rich phase is more dispersed and evenly distributed, improving the cutting performance and thermoforming properties of the alloy; on the other hand, the iron-silicon compound can The recrystallization of crystal grains is prevented from growing rapidly during hot working, and the thermoforming property of the alloy is further improved.
  • Phosphorus also improves the distribution of Si-rich phases in the alloy and improves thermoforming properties.
  • the invention simultaneously adds iron and phosphorus to improve the thermoforming performance better than the addition of iron and phosphorus alone.
  • the presence of iron and phosphorus makes the alloy microstructure fine and thick, the strength is improved, and the hot extrusion is not carried out after continuous casting, which can satisfy the application.
  • Claim. The iron content should be controlled within the range of 0.11 ⁇ 0.2wt%, and the phosphorus content should be controlled within the range of 0.04 ⁇ 0.10 wt%. If it is lower than the lower limit of the control content, the improvement of the thermoforming property is not obvious; if the upper limit of the control content is exceeded, the molding property and mechanical properties of the alloy are lowered.
  • One of the selective addition of B, Ag, Ti and RE is to deoxidize and refine the grains to further improve the hot workability.
  • the addition amount is preferably not more than 0.01 wt%, and the excessive content may lower the melt flowability of the alloy.
  • Pb, Bi, Se and Te is a solution that takes into account the recycling of common free-cutting brass scraps on the market, with a Pb content of 0.01 to 0.25 wt% and a Bi content of 0.01 to 0.4 wt%.
  • the content is 0.005 ⁇ 0.4 wt%
  • the content of Te is 0.005 ⁇ 0.4 wt%
  • intermetallic compounds between Mn and Ni and silicon improves the wear resistance of the alloy, and aluminum also improves the strength and wear resistance of the alloy.
  • Sn and A1 is intended to improve the strength and corrosion resistance of the alloy. It is also advantageous to additionally add these alloying elements to resist stress corrosion.
  • the addition amount of these alloying elements is 0.05 - 0.2 wt%. If the content is too low, the effect of improving the wear resistance is not significant, and if the content is too high, the mechanical properties are unfavorable.
  • the addition of As and Sb is to further improve the resistance to dezincification corrosion.
  • the addition of As and Sb is 0.03 - 0.15 wt%. If the content exceeds the upper limit, the metal precipitation will exceed the standard and it cannot be used for drinking water system components.
  • the manufacturing method of the alloy of the present invention comprises: batching, smelting, horizontal continuous casting bar, suede and heated forged product, wherein the horizontal continuous casting temperature is 990 ⁇ 1060 ° C, and the heating forging temperature is 650 ⁇ 760 ° C .
  • the process flow chart of the invention for manufacturing the above brass alloy is shown in FIG.
  • Si, Fe and P are the main additive elements. Fe and Si can form iron-silicon compounds with higher melting point. The compound is uniformly distributed in the matrix in the form of particles, which makes the Si-rich phase more dispersed and evenly distributed, improving the cutting performance and thermoforming of the alloy. Performance, at the same time, the iron-silicon compound can prevent the recrystallization of crystal grains from rapidly growing during hot working, and the thermoforming property of the alloy is further improved.
  • the addition of P also improves the distribution of the Si-rich phase in the alloy and improves the thermoforming properties.
  • the invention simultaneously adds Fe and P to improve the thermoforming performance. Compared with the separate addition of Fe and P, the thermoformability of the alloy is remarkably improved, and the alloy has excellent mechanical properties, cutting performance and corrosion resistance.
  • the alloy of the present invention selectively adds B, Ag, Ti, and RE to further refine the microstructure to further enhance the hot workability of the alloy by adding Si, Fe, and P; selectively adding Mn, Al, Sn, Ni, which realizes a lead-free corrosion-resistant alloy with excellent thermoforming performance, high strength and high wear resistance; on this basis, Pb, Bi, Se, Te are selectively added to achieve a thermoforming property and excellent cutting performance.
  • Lead-free alloy for easy recycling of waste materials; Selective addition of Sb, As, a high-strength wear-resistant lead-free alloy with excellent thermoforming properties and dezincification resistance.
  • the brass alloy of the present invention has at least the following advantageous effects as compared with the prior art:
  • the present invention simultaneously adds iron and phosphorus elements, and the resulting alloy has excellent thermoforming properties and is particularly suitable for molding complex products. Without the need for extrusion, the horizontal continuous casting ingots are used for direct hot forging, which reduces production costs and cylinders.
  • the brass alloy of the present invention does not contain toxic elements such as lead and cadmium, and at the same time, the precipitation amount of the alloying elements in water conforms to the NSF/ANSI 61-2008 standard, and is a lead-free environmentally friendly alloy. At the same time, the existence of micro Pb in the alloy is allowed, which solves the problem of waste recycling.
  • the brass alloy of the invention has excellent performance properties (such as corrosion resistance, wear resistance, mechanical properties, etc.) and process properties (such as molding property, cutting property, welding property, etc.), and can be used for producing faucets, valves, pipe joints , electrical and electronic, automotive and other components, especially suitable for casting, forging and extrusion production of drinking water supply system components, such as faucet products and various types of valves.
  • thermoforming performance of the alloy of the invention is superior to that of the as-cast silicon brass C69300, bismuth brass and the traditional lead brass C36000, and can form a complex shape product, which can meet the demand without hot extrusion, thereby having a market competitive advantage. .
  • the stress corrosion resistance and dezincification corrosion resistance of the alloy of the invention are significantly better than that of the beryllium brass, the lead brass C36000 and other brass alloys.
  • the wear resistance of the alloy of the invention is significantly better than that of the as-cast silicon brass C69300, bismuth brass and conventional lead brass C36000.
  • the alloy of the invention has excellent comprehensive performance, and its chip morphology and cutting performance are comparable to silicon brass C69300, bismuth brass, lead brass C36000, and mechanical properties (including tensile strength and elongation) are slightly higher. For conventional enamel brass and lead brass C36000. At the same time, the precipitation amount of toxic metal elements in the water of the alloy of the invention meets the requirements of the NSF detection standard, and is an environmentally friendly material. Therefore, the alloy of the present invention has a broader market application prospect.
  • FIG. 1 is a process flow diagram for making a brass alloy of the present invention. detailed description
  • the components of the alloy of the present invention are shown in Tables 1 to 4, wherein the specific alloy of the invention is the alloys A01 to A05 of Table 1, and the second embodiment of the invention is the alloys B01 to B05 of Table 2, and the invention alloys are three specific
  • the examples are alloys C01 to C04 of Table 3
  • the fourth embodiment of the invention alloys are alloys D01 to D04 of Table 4
  • Table 5 is the composition of comparative alloys 1 to 11, wherein the composition of the comparative alloy 1 is consistent with the composition of Japanese Sambo C69300.
  • Comparative Alloy 11 is a C36000 alloy composition.
  • Both the alloy of the present invention and the comparative alloy were smelted according to the process shown in Fig. 1 and cast into a circular bar blank of the same specification.
  • the specific preparation process is: batching, smelting, horizontal continuous casting bar, suede and heating forging, wherein the horizontal continuous casting temperature is 990 ⁇ 1060 ° C, and the heating forging temperature is 680 ⁇ 760 ° C.
  • the mechanical properties of the alloy were tested.
  • the alloy of the invention and the comparative alloy were processed into standard specimens with a diameter of 10 mm.
  • Tensile tests were carried out at room temperature to test the mechanical properties of the alloys. The results are shown in Tables 6-10.
  • each alloy is evaluated according to GB/T 16461-1996, where " ⁇ ” stands for needle-shaped chips and unit chips, and “ ⁇ ” stands for curved cutting but no tapered chips, “ ⁇ " Represents a short conical spiral chip, and “X” represents a long conical spiral chip.
  • the cutting performance is based on the value of the cutting force.
  • the C36000 with excellent cutting performance is the standard, that is, according to the formula:
  • the dezincification test was carried out in accordance with GB/T 10119-2008. Three parallel samples were cut from different parts of the ingot made from the inventive alloy and the comparative alloy, and the cross-sectional dimension was 10 mm x l0 mm. The inlaid sample was placed in a copper chloride solution for 24 hours at constant temperature, and then the experimental section was made into a metallographic sample, and the average depth of the dezincification layer was observed and calibrated under an electronic metallurgical microscope. The results are shown in Tables 6-10.
  • Test materials Bars processed from inventive and comparative alloys, forged products: 1/2 inch angle valve.
  • a sample of length (height) of 40 mm was cut from a horizontal continuous casting bar having a diameter of 29 mm, and hot-forged axially compressed at 680 ° C and 750 ° C, and the following cracking rate was observed to observe cracking.
  • the hot forging properties of some of the alloys in Tables 1-4 and Comparative Alloys 1 to 8 were evaluated.
  • Upsetting rate (%) [(40-h)/40] l00% (h is the height of the sample after hot smashing)
  • the precipitation of metal in the alloy of the invention alloy and the comparative alloy is determined according to the NSF/ANSI 61-2008 standard.
  • the experimental sample is a valve forging the rod blank.
  • the detection instrument is: Inductively coupled plasma mass spectrometer (Varian 820-MS Icp. Mass Spectrometer) ), the time is 19 days, the results of the insurance are shown in Table 16.
  • the wear resistance of the alloy is tested in accordance with GB/T12444.1-1990 (Metal Wear Test Method).
  • the upper sample is made of 45# steel.
  • the alloys in Tables 1-5 are made into a ring with a diameter of 30 mm and a center hole diameter of 16 mm.
  • the sample (lower sample) has a length (height) of 10 mm.
  • the sample is uniformly lubricated with ordinary mechanical lubricating oil.
  • the wear test is carried out under the experimental force of 90N. The rotation speed is stable at about 180r/min. When the wear time reaches 30min, the experiment is stopped, the sample is removed, and the sample is cleaned and dried. Comparing the changes in the weight of the sample before and after the wear, see Table 17-18. The less the weight loss after wear, the better the wear resistance of the alloy.
  • composition of the alloy one of the invention (wt%)
  • the average dezincification depth of the first, second and third alloys of the invention is less than ⁇ , which is obviously superior to the comparative alloy 8-11, which is comparable to the comparative alloy 1.
  • the alloy of the invention has excellent dezincification corrosion resistance, and the average dezincification layer depth is within ⁇ , and it can be considered that dezincification corrosion does not occur.
  • the alloy is particularly suitable for an environment where the water quality is weakly acidic or the chloride salt content is high. .
  • the tensile strength of the alloy of the invention is higher than that of the comparative alloys 2, 5, and 10, and the elongation is higher than that of the comparative alloys 3, 4, 6, 7, and 8.
  • the chip morphology and cutting performance of the alloy of the present invention are comparable to those of the comparative alloy 1. It is superior to the comparative alloy 5; the stress corrosion resistance is obviously superior to the comparative alloys 10 and 11; it can be seen that the alloy of the invention has excellent mechanical properties, cutting performance, anti-dezinc corrosion resistance and stress corrosion resistance, and can be better satisfied. Application requirements.
  • the upsetting rate of the alloy of the present invention is significantly higher than that of the comparative alloys 1 to 8 and 10, and not lower than the leaded copper comparative alloy 11 . It can be seen that the alloy of the invention has better hot forging performance than the comparative alloy, and is more suitable for molding products with complicated shapes, and has great market competitive advantages.
  • the alloy of the present invention has excellent comprehensive performance, and its chip morphology and cutting performance are comparable to that of lead brass C36000 and silicon brass C69300, and the corrosion resistance is superior to that of conventional tantalum brass and lead brass C36000.
  • the alloy of the present invention has a greater improvement in hot forming properties and wear resistance than conventional bismuth brass, lead brass C36000, and silicon brass C69300;
  • the amount of toxic metal elements in the water meets the NSF test mark
  • the required requirements are environmentally friendly materials. Therefore, the alloy of the present invention has a broader market application prospect.

Landscapes

  • 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)
  • Forging (AREA)
  • Domestic Plumbing Installations (AREA)
  • Chemically Coating (AREA)
  • Adornments (AREA)
  • Conductive Materials (AREA)

Abstract

本发明提供一种热成型性能优异的无铅易切削耐蚀黄铜合金，该黄铜合金含有：74.5~76.5wt%的Cu、3.0~3.5wt%的Si、0.11~0.2wt%的Fe、0.04~0.10wt%的P，其余为Zn和不可避免的杂质。本发明合金具有良好的冷加工和热加工成型性能、优异的抗脱锌腐蚀及抗应力腐蚀性能，适用于需切削加工和磨削加工成型的水暖卫浴、电子电器、汽车等零部件，尤其适用于生产装配应力不便消除的复杂锻件产品，如水龙头和阀门等。

Description

一种热成型性能优异的无铅易切削耐蚀黄铜合金 技术领域
本发明属于合金技术领域， 具体涉及一种无铅易切削耐蚀黄铜合金， 特 别是涉及一种热成型性能优异的无铅易切削耐蚀黄铜合金。 背景技术
铅黄铜如 C36000、 ZCuZn38Pb2,通过在合金中加入 lwt% ~ 4wt%的铅， 使其具有优异的切削性能、 良好的耐腐蚀性能， 同时成本低廉， 已被作为一 种重要的基础材料用于电气、 机械、 水暖等各个领域。 然而， 含铅黄铜在生 产、 使用过程中会对环境造成污染， 危害人类的健康。 美国、 欧盟等发达国 家和地区已先后制定标准和法令， 如 NSF-ANSI372、 AB-1953、 RoHS等， 逐步禁止生产、 销售和使用含铅产品。
目前， 国内外已对黄铜的无铅化做了大量的研究工作， 主要通过以铋代 铅、 以锑代铅、 以硅代铅来实现黄铜合金的切削性能， 并通过添加适量的其 它元素以改善黄铜合金的综合性能。
然而，一方面，铋、黄铜热加工成型性能差，在热成型过程中易产生缺陷， 成型复杂产品困难， 且铋黄铜焊接性能较差； 另一方面， 铋为稀贵金属， 以 铋替代铅在产业上无法大规模实施。 另外对多家国内外铜材生产商提供的铋 黄铜棒材锻造生产阀门本体， 装配阀门后， 因不便于退火消除装配应力， 进 行氨熏实验时大都出现不同程度的开裂。
近期国内开发了无铅易切削锑黄铜，但锑本身具有毒性，在使用过程中， 锑黄铜中的锑极易溶出， 其龙头、 阀门等过水产品经 NSF 测试锑元素在水 中的溶出量远超过标准规定的 0.6 g/L, 存在环境污染和危害人类健康的隐 患， 不能应用于水暖零部件。
硅黄铜是当今无铅易切削黄铜研究的重点， 目前已有相当数量的专利。 例如中国专利申请 200810163930.3公开了 一种易切削硅黄铜合金及其制造 方法， 该硅黄铜合金的化学成份为： 铜 59.2 ~ 63.5wt%, 硅 0.35 ~ 0.9wt%, 铅 0.04 ~ 0.25wt%, 磷 0.22 ~ 0.38wt%, 其他元素： 0.005 ~ 1.1 wt%, 余量为 锌和杂质， 其具有优良的热成型性能、 切削性能， 但其耐蚀性能特别是抗应 力腐蚀性能较差， 无法满足生产检验需求， 生产的阀门经氨熏测试时均出现 开裂。中国专利申请 200580046460.7公开了一种含有极少量铅的易切削铜合 金， 该合金包括： 71.5 ~ 78.5wt%Cu, 2.0 - 4.5wt%Si, 0.005 ~ 0.02wt%Pb, 余量为 Zn, 该合金连铸态组织较为粗大且不均勾， 因而热加工性能较差， 不能应用于成型复杂产品， 实际生产中通常需要进行热挤压以改善铸态组 织， 势必产生成本的增加和能源的浪费， 难以实现技术推广。 中国专利 ZL200580019413.3公开了一种晶粒细化了的铜基合金铸件，该合金由以下成 分组成： Cu: 69 ~ 88wt%, Si: 2 ~ 5wt%, Zr: 0.0005 ~ 0.4wt%, P: 0.01 - 0.25wt%, 余量为锌， 该合金通过添加元素锆细化晶粒来改善合金铸件的性 能， 但金属锆资源稀少且价格昂贵， 另一方面， 锆在合金的熔炼过程极其容 易与氧、 硫等氧化介质结合转化为炉渣而失去作用， 故在熔炼废料时造成锆 的大量损耗， 合金的可循环利用性差。 发明内容
为了克服现有技术的缺陷， 本发明提供一种热成型性能优异的无铅易切 削耐蚀黄铜合金。 本发明黄铜合金的综合性能优良， 可用于生产水龙头、 阀 门、 管道接头、 电子电器、 汽车、 机械等零部件。
本发明的目的是通过以下技术方案来实现的。
一种热成型性能优异的无铅易切削耐蚀黄铜合金， 该黄铜合金含有： 74.5 ~ 76.5wt0/c^ Cu、 3.0 ~ 3.5wt0/c^ Si、 0.11 - 0.2 wt0/c^ Fe、 0.04 ~ 0.10 wt% 的 P, 其余为 Zn和不可避免的杂质。
优选地， 所述黄铜合金中 Cu的含量为： 75-76wt%。
优选地， 所述黄铜合金中 Si的含量为： 3.1-3.4wt%。
优选地， 所述黄铜合金中 P的含量为： 0.04~0.08wt%。
优选地， 所述黄铜合金还含有 0.001 ~ 0.01wt%选自 B、 Ag、 Ti和 RE中 的至少一种元素。
优选地，所述黄铜合金中 B、 Ag、 Ti和 RE的含量为： 0.001 ~ 0.005wt%。 优选地，所述黄铜合金还含有选自 Pb、 Bi、 Se和 Te中的至少一种元素， 其中 Pb的含量为 0.01 ~ 0.25 wt%, Bi的含量为 0.01 ~ 0.4 wt%, Se的含量为
0.005 ~ 0.4 wt%, Te 含量为 0.005 ~ 0.4 wt0/0。
优选地， 所述黄铜合金还含有 0.05 ~ 0.2 wt%选自 Mn、 Al、 Sn和 Ni中 的至少一种元素。
优选地，所述黄铜合金还含有 0.03 ~ 0.15 wt%选自 As和 Sb中的至少一 种元素。
本发明将铜含量控制为 74.5 ~ 76.5wt%以较好地解决黄铜的耐蚀问题。 铜含量超过 76.5wt%会导致制品的原材料成本过高， 锻造性能开始降低； 铜含量低于 74.5wt%合金的力学性能特别是延伸率不理想。 本发明合金中 加入一定量的硅， 可以形成硬脆的富 Si相， 在切削时可起断屑作用， 改善 黄铜的切削性能。 硅含量大于 3.5wt%时， 合金的塑性降低， 硅以不超过 3.5wt%为宜； 硅含量低于 3.0wt%时， 切削性能、 锻造性能不理想， 因此硅 含量不低于 3.0wt%。
在本发明合金中同时添加铁和磷。 铁与硅可形成熔点较高的铁硅化合 物， 该化合物以颗粒状均匀分布于基体， 使富 Si相更弥散均匀分布， 提升 合金的切削性能和热成型性能； 另一方面， 铁硅化合物能阻止热加工时晶粒 的再结晶迅速长大， 合金的热成型性能进一步改善。 磷也能改善合金中富 Si相的分布状况， 提升热成型性能。 本发明同时添加铁和磷对热成型性能的 改善作用优于单独添加铁和磷， 铁和磷的存在使合金组织细密均勾， 强度提 高， 连铸后不进行热挤压， 即可满足应用要求。 铁的含量应控制在 0.11 ~ 0.2wt%范围内， 磷的含量应控制在 0.04 ~ 0.10 wt%范围内。 若低于控制含量 下限， 其热成型性能的改善作用不明显； 若超过控制含量上限， 则降低合金 的成型性能和力学性能。
选择性添加 B、 Ag、 Ti和 RE中的一种是为了脱氧并细化晶粒， 进一步 改善热加工性能。 加入量以不超过 0.01 wt%为宜， 含量过高会降低合金熔体 流动性。
加入 Pb、 Bi、 Se和 Te是考虑到市场上常见易切削黄铜废料的回收利用 而提供的方案，其中 Pb的含量为 0.01 ~ 0.25 wt%, Bi的含量为 0.01 ~ 0.4 wt%, Se的含量为 0.005 ~ 0.4 wt%, Te的含量为 0.005 ~ 0.4 wt%
Mn和 Ni与硅形成金属间化合物可提高合金的耐磨性，铝也可提高合金 的强度和耐磨性。 添加 Sn和 A1的作用是为了提高合金的强度和耐蚀性。 另 外添加这些合金元素对抗应力腐蚀性能也有利。 这些合金元素添加量为 0.05 - 0.2 wt%, 若含量过低则提高耐磨性的效果不明显， 若含量过高对力学 性能不利。
加入 As和 Sb是为了进一步提升耐脱锌腐蚀性能。 As和 Sb添加量为 0.03 - 0.15 wt%, 若含量超出上限会导致金属析出超标， 不能用于饮用水系 统零部件。
本发明合金的制造方法包括： 配料、 熔炼、 水平连铸棒、 扒皮和加热锻 造产品， 其中所述水平连铸的温度为 990~1060°C , 所述加热锻造的温度为 650~760°C。 本发明制造上述黄铜合金的工艺流程图如图 1所示。
现有的无铅易切削黄铜通过在铜-锌二元体系中添加硅、 铝、 镍、 锰、 锡、 磷等元素， 改善合金的切削性能及耐蚀性能。 本发明的无铅环保黄铜以
Si、 Fe、 P为主要添加元素， Fe与 Si可形成熔点较高的铁硅化合物， 该化合 物以颗粒状均匀分布于基体， 使富 Si相更弥散均匀分布， 提升合金的切削 性能和热成型性能， 同时， 铁硅化合物能阻止热加工时晶粒的再结晶迅速长 大， 合金的热成型性能进一步改善。 添加 P也能改善合金中富 Si相的分布 状况， 提升热成型性能。 本发明同时添加 Fe和 P对热成型性能的改善作用 优于单独添加 Fe和 P, 合金的热成型性能得到显著提升， 同时使合金具有 优异的力学性能、 切削性能及耐蚀性能。 其次， 本发明合金在添加 Si、 Fe、 P的基础上选择性添加了 B、 Ag、 Ti、 RE进一步细化组织以最大化提升合 金的热加工性能； 选择性添加了 Mn、 Al、 Sn、 Ni, 实现了一种热成型性能 优异、 高强度、 高耐磨的无铅耐蚀合金； 在此基础上选择性添加 Pb、 Bi、 Se、 Te, 实现了一种热成型性能、 切削性能优异的便于废料回收利用的无铅 合金； 选择性添加 Sb、 As, 实现了一种热成型性能、 耐脱锌腐蚀性能优异 的高强耐磨的无铅合金。
具体而言，本发明的黄铜合金与现有技术相比，至少具有以下有益效果： 本发明同时添加铁与磷元素， 得到的合金具有优异的热成型性能， 特别 适于成型复杂产品。 不需进行挤压， 采用水平连铸锭直接热锻产品， 降低了 生产成本和筒化了工艺。
本发明的黄铜合金不添加铅、 镉等毒性元素， 同时使合金元素在水中的 析出量符合 NSF/ANSI61-2008标准，是无铅环保型合金。 同时允许合金中微 量 Pb的存在， 较好地解决了废料回收利用问题。
本发明的黄铜合金具有优良的使用性能（如耐蚀性能、 耐磨性能、 力学 性能等）和工艺性能 （如成型性能、 切削性能、 焊接性能等）， 可用于生产 水龙头、 阀门、 管道接头、 电子电器、 汽车等零部件， 尤其适合于铸造、 锻 造和挤压生产饮用水供给系统零部件， 如水龙头产品和各类阀门。
本发明合金的热成型性能优于铸态的硅黄铜 C69300、 铋黄铜及传统铅 黄铜 C36000, 可成型形状复杂的产品， 不实施热挤压即可满足需求， 从而 具有市场竟争优势。
本发明合金的抗应力腐蚀及抗脱锌腐蚀性能明显优于铋黄铜、 铅黄铜 C36000及其它黄铜合金。
本发明合金的耐磨性能明显优于铸态的硅黄铜 C69300、 铋黄铜及传统 铅黄铜 C36000。
本发明合金的综合性能优异， 其切屑形貌、 切削性能与硅黄铜 C69300、 铋黄铜、 铅黄铜 C36000相当， 而力学性能（包括抗拉强度与延伸率）略高 于常规铋黄铜及铅黄铜 C36000。 同时， 本发明合金的水中有毒金属元素析 出量符合 NSF检测标准的要求, 属于环境友好型材料。 因此本发明合金具 有更广泛的市场应用前景。 附图说明
图 1是制造本发明的黄铜合金的工艺流程图。 具体实施方式
以下通过具体的实施例进一步说明本发明的技术方案。 实施例
本发明合金的实施例成分如表 1 ~ 4所示， 其中发明合金一具体实施例 为表 1的合金 A01 ~ A05 , 发明合金二具体实施例为表 2的合金 B01 ~ B05 , 发明合金三具体实施例为表 3的合金 C01 ~ C04, 发明合金四具体实施例为 表 4的合金 D01 ~ D04, 表 5为对比合金 1 ~ 11的成分， 其中对比合金 1的 成分与日本三宝 C69300成分一致， 对比合金 11为 C36000合金成分。
本发明合金和对比合金均按图 1所示工艺经熔炼后铸成规格相同的圆形 棒坯。 具体制备工艺为： 配料、 熔炼、 水平连铸棒、 扒皮和加热锻造， 其中 所述水平连铸的温度为 990~1060°C , 所述加热锻造的温度为 680~760°C。
以下将对上述实施例与对比合金进行性能检测，具体性能检测项目及依 据如下：
1. 力学性能
依据 GB/T228-2010对合金的力学性能进行测试， 将发明合金与对比合 金加工成直径为 10mm的标准试样， 在室温下进行拉伸试验， 测试各合金的 力学性能。 结果如表 6 ~ 10所示。
2. 切削性能
将发明合金与对比合金加工成直径 34 的棒坯后， 每种成分合金截取 3 根长度分别为 200mm的平行试样， 对所有的合金采用相同的刀具、 相同的 切削速度和相同的进刀量。 刀具型号： VCGT160404-AK H01 , 转速： 570r/min , 进给： 0.2mm/r, 背吃刀量： 单边 2mm。 采用北京航空航天大学 研制的 "车、 铣、 钻、 磨通用切削力测试仪 "分别测量发明合金和对比合金的 切削阻力， 并采集切屑。
依据 GB/T 16461-1996对每种合金的切屑进行评价， 其中"〇 "代表以针 形切屑和单元切屑为主， "〇"代表以弧形切削为主但不出现锥形切屑， "Δ" 代表出现短锥形螺旋切屑， " X"代表出现长锥形螺旋切屑。
切削性能评定的依据为切削力数值大小，以公认切削性能优异的 C36000 为标准， 即根据公式：
X= ( C36000的切削力 I实验合金的切削力） X 100%
若比值 "X"≥85% , 认为实验合金的切削性能为优异， 用"〇"表示； 若 85% >"Χ">75% , 认为实验合金的切削性能为中等， 用 "〇，，表示； 若 75% >"Δ">65%,认为实验合金的切削性能为一般，用 "△"表示；若比值 "Χ"< 65%, 认为实验合金的切削性能为较差， 用 " X"表示， 具体结果如表 6-10所示。
3. 抗脱辞腐蚀性能
脱锌试验按照 GB/T 10119-2008进行， 从发明合金与对比合金制得棒坯 上的不同部位切割 3件平行试样， 截面尺寸为 10mmx l0mm。 经镶嵌好的试 样置于氯化铜溶液中恒温腐蚀 24小时， 再将实验切片制成金相试样， 在电 子金相显微镜下观察并标定脱锌层的平均深度。 结果如表 6 ~ 10所示。
4. 抗应力腐蚀性能
试验材料： 发明合金和对比合金加工成的棒坯， 经锻造成型的产品： 1/2 英寸角阀。
外部加载方式： 进出水口用管接头加载， 扭矩 90Nm;
组装产品不经过退火消除装配应力
试验环境： 14%浓度的氨水
试马全时间： 8h
判定方法： 用 15倍的放大观察氨熏试样表面
试样经 8h氨熏后， 取出试样， 先用水冲洗干净， 然后于室温下用 5%的 硫酸溶液清洗试样表面的腐蚀产物， 再用水冲洗并吹干， 最后用 15倍的放 大观察氨熏试样表面是否有裂纹。 若试样表面无裂纹且腐蚀层不明显， 颜色 较光亮， 用"〇"表示； 若表面无明显裂纹， 但有明显的腐蚀层， 用 "〇"表示； 若表面有微小裂紋， 用" Δ"表示； 若表面有明显裂紋， 用 " X"表示。 结果如表 6 ~ 10所示。
5. 热加工性能
从直径 29mm的水平连铸棒上切取长度 (高度） 40mm的试样， 在 680 °C、 750°C两个温度下热锻轴向压缩变形， 并采用下述的镦粗率， 观察产生 裂纹的情况， 对表 1-4中的部分合金及对比合金 1 ~ 8的热锻造性能进行评 价。
镦粗率（％ ) =[(40-h)/40] l00% (h为热镦粗后试样的高度）
锻造试样表面光洁且无裂纹， 则为优， 用 "〇"表示； 试样表面有较粗糙 但无明显裂纹，则为良，用" Δ"表示；试样表面有肉眼可视裂纹则为差，用 "X" 表示。 结果如表 11-15所示。
6. 水中金属析出量
发明合金与对比合金的水中金属析出量测定按 NSF/ANSI 61-2008标准 执行， 实验样品为将棒坯锻造成型的阀门， 检测仪器为： 电感耦合等离子质 谱仪（Varian 820-MS Icp.Mass Spectrometer ), 时间为 19天， 检险结果见表 16
7. 耐磨性能测试
合金的耐磨性实验参考 GB/T12444.1-1990 (金属磨损试验方法 )进行， 上试样采用 45#钢，将表 1-5中的合金制成直径为 30mm, 中心孔直径 16mm 的环形试样（下试样）， 长度（高度） 为 10mm。 试样统一用普通机械润滑 油进行润滑， 在施加 90N 的实验力下进行磨损实验， 转速稳定在 180r/min 左右， 当磨损时间达到 30min时停止实验， 取下试样， 清洗干燥后称重， 对 比磨损前后试样重量的变化， 见表 17-18, 磨损后重量损失越少则说明合金 的耐磨性能越好。
本发明合金一的成分（ wt% )
A令 Cu Si Fe P B Ag Ti RE Zn
A01 75.15 3.23 0.15 0.07 余 f
A02 74.69 3.21 0.19 0.07 0.002 余 f
A03 75.18 3.09 0.12 0.10 0.001 0.001 余 f
A04 76.43 3.42 0.17 0.09 0.01 余 f
A05 75.62 3.48 0.11 0.04 0.01 余 f 表 2 本发明合金二的成分 ( wt% )
A令 Cu Si Fe P Pb Bi Se Te B Zn
B01 74.58 3.29 0.18 0.08 0.14 余 f
B02 76.03 3.44 0.13 0.03 0.29 余 f
B03 76.47 3.05 0.11 0.06 0.07 余 f
B04 75.55 3.29 0.14 0.07 0.08 0.003 余 f
B05 74.87 3.38 0.15 0.09 0.11 0.10 0.002 余 f 表 3 本发明合金三的成分 ( wt% )
A令 Cu Si Fe P Mn Al Sn Ni B Ag RE Zn C01 74.98 3.19 13.15 0.09 0.15 0.12 余 f
C02 75.06 3.07 1 余 f
C03 75.55 3.42 1 3.12 0.08 0.06 0.11 0.01 余 f
C04 0.001 余 f 表 4 本发明合金四的成分（ wt% )
A令 Cu Si Fe P Mn Al B Ag As Sb Zn o o
D01 75.82 3.28 0.13 0 o.03 0.19 0.12
o o 余 f o o
D02 74.96 3.37 0.16 0.06 o 0.18 0.09 0.03 余 f
D03 74.79 3.36 0.12 0.05 0.05 余 f o
D04 74.52 3.12 0.17 o 0.04 余 f o
o
o
表 5 本发明对比合金成分（wt% )
o
o
o
对比 Cu Si Fe P Mn Al Sn B Pb Bi Zn o o
A令 o o o o o
o o o o
O
1 75.51 3.17 0.03 0.05 余 f
2 77.84 3.39 0.02 0.09 余 f
3 74.02 3.32 0.02 0.07 余 f
4 74.97 3.63 0.14 0.06 余 f
5 75.49 2.90 0.16 0.07 余 f
6 75.82 3.47 0.30 0.04 0.31 余 f
7 74.82 3.51 0.17 0.06 0.30 余 f
8 76.34 3.23 0.12 余 f
9 75.85 3.34 0.15 0.09 0.28 余 f
10 63.58 0.83 0.75 余 f
11 61.25 2.75 余 f 表 6 发明合金一的抗脱锌腐蚀性能、 力学性能、 切削性能 及抗应力腐蚀性能
Figure imgf000010_0001
A02 <50 473 24 Θ 〇 〇
A03 <30 431 28 〇 △ 〇
A04 <10 472 31 Θ 〇 Θ
A05 <20 484 29 Θ 〇 Θ 表 7 发明合金二的抗脱锌腐蚀性能、 力学性能、 切削性能
及抗应力腐蚀性能
平均脱锌 力学性能
合金编 切屑形 切削性 抗应力腐蚀性 层 抗拉强度 延伸率
号 貌 能 H 深度 /μηι /MPa /%
B01 <50 483 22 Θ Θ Θ
B02 <20 471 27 Θ Θ Θ
B03 <10 440 32 Θ Θ Θ
B04 <20 452 28 Θ 〇 Θ
B05 <50 475 24 Θ Θ 〇 表 8 发明合金三的抗脱锌腐蚀性能、 力学性能、 切削性能
及抗应力腐蚀性能
平均脱锌 力学性能
合金编 切屑形 切削性 抗应力腐蚀性 层 抗拉强度 延伸率
号 貌 能
深度 /μηι /MPa /%
C01 <150 511 19 Θ 〇 〇
C02 <20 436 18 Θ Θ Θ
C03 <30 458 23 Θ Θ 〇
C04 <30 441 26 〇 〇 〇 表 9 发明合金四的抗脱锌腐蚀性能、 力学性能、 切削性能
及抗应力腐蚀性能
平均脱锌 力学性能
合金编 切屑形 切削性 抗应力腐蚀性 层 抗拉强度 延伸率
号 貌 能
深度 /μηι /MPa /%
D01 <10 458 29 〇 〇 〇
D02 <10 521 22 〇 〇 〇 D03 <10 495 23 Θ Θ Θ
D04 <10 507 29 〇 △ Θ 对比合金的抗脱锌腐蚀性能、力学性能、切削性能及抗应力腐蚀性能
Figure imgf000012_0001
由以上结果可知，发明合金一、二、三的平均脱锌层深度均小于 ΙΟΟμιη, 明显优于对比合金 8-11 , 与对比合金 1相当。 发明合金四的耐脱锌腐蚀性能 非常优异， 其平均脱锌层深度均在 ΙΟμιη以内， 可以认为不发生脱锌腐蚀， 该合金特别适用于水质呈弱酸性或氯化物盐类含量较高的环境。
本发明合金的抗拉强度均高于对比合金 2、 5、 10, 延伸率高于对比合金 3、 4、 6、 7、 8; 本发明合金的切屑形貌、 切削性能与对比合金 1相当， 优 于对比合金 5; 抗应力腐蚀性能明显优于对比合金 10、 11 ; 综合可知， 本发 明合金的力学性能、 切削性能、 抗脱锌腐蚀及抗应力腐蚀性能均很优异， 可 更好的满足应用需求。
表 11 发明合金一的热锻造性能测试结果
Figure imgf000012_0002
A04 〇 〇 Δ Δ 〇 〇 〇 Δ
A05 〇 〇 Δ Δ 〇 〇 〇 〇 表 12 发明合金二的热锻造性能测试结果 热锻造性能
A口令一 ' 镦粗率 （％), 680 °C 镦粗率 （％), 750 °C
60 70 80 90 60 70 80 90
B01 〇 〇 〇 Δ 〇 〇 〇 Δ
B02 〇 〇 Δ X 〇 〇 Δ X
B03 〇 〇 Δ Δ 〇 〇 Δ Δ
B04 〇 〇 〇 Δ 〇 〇 〇 Δ
B05 〇 〇 〇 Δ 〇 〇 〇 Δ 表 13 发明合金三的热锻造性能测试结果
Figure imgf000013_0001
表 14 发明合金四的热锻造性能测试结果
Figure imgf000013_0002
表 15 对比合金的热锻造性能测试结果 对比合金 热锻造性能 镦粗率 （％), 680 °C 镦粗率 （％), 750 °C
60 70 80 90 60 70 80 90
1 〇 〇 Δ X 〇 Δ X X
2 〇 Δ Δ X 〇 Δ X X
3 〇 〇 〇 X 〇 〇 Δ X
4 〇 〇 〇 Δ 〇 Δ Δ X
5 〇 X X X 〇 X X X
6 Δ X X X 〇 Δ X X
7 〇 〇 〇 Δ 〇 Δ X X
8 〇 〇 Δ X 〇 〇 X X
9 〇 〇 〇 Δ 〇 〇 Δ X
10 Δ X X X X X X X
11 〇 〇 〇 Δ 〇 〇 Δ Δ 数据显示， 在同一锻造温度下， 本发明合金的镦粗率均明显高于对比合 金 1 ~ 8和 10,不低于有铅铜对比合金 11。可见本发明合金较对比合金而言， 其热锻造性能更优异， 更适用于成型形状复杂的产品， 具有很大的市场竟争 优势。
表 16 试验合金在水中金属析出量测试结果
Figure imgf000014_0001
以上数据表明， 本发明合金的 Pb在水中的金属析出量远低于 C36000 合金在水中金属的析出量， 其它元素在水中的析出量亦符合 NSF/ANSI 61-2008饮用水标准的要求， 适用于制造饮用水系统零部件， 而合金 C36000 在水中的铅析出量远高于 NSF/ANSI 61-2008饮用水标准， 不适合用于制造 饮用水系统零部件。
表 17 发明合金的磨损试验统计结果
表 18 对比合金的磨损试验统计结果
Figure imgf000015_0002
表 17-18的统计结果用于评价发明合金与 C69300、传统的铋黄铜、铅黄 铜 C36000的耐磨性。 结果表明， 本发明合金的耐磨性明显优于对比合金 10 (常规铋黄铜）、 合金 11 (即 C36000 ), 与对比合金 1 (即 C69300 )相比， 本发明合金在耐磨性上也更具优势。
综合以上性能检测结果可知： 本发明合金综合性能优异， 其切屑形貌、 切削性能与铅黄铜 C36000、硅黄铜 C69300相当， 而耐蚀性能明显优于常规 铋黄铜及铅黄铜 C36000,不低于硅黄铜 C69300;本发明合金与常规铋黄铜、 铅黄铜 C36000、 硅黄铜 C69300相比， 在热加工成型性能及耐磨性能上有较 大的提高； 同时， 本发明合金的水中有毒金属元素析出量符合 NSF检测标 准的要求， 属于环境友好型材料。 因此， 本发明合金具有更广泛的市场应用 前景。
上述实施例用于解释本发明， 而不是对本发明进行限制， 在本发明的精 神和权利要求保护范围内， 对本发明作出的任何修改和改变， 都落入本发明 的保护范围。

Claims

权 利 要 求
1、 一种热成型性能优异的无铅易切削耐蚀黄铜合金， 该黄铜合金含有： 74.5 ~ 76.5wt%的 Cu、 3.0 ~ 3.5wt%的 Si、 0.11 - 0.2 wt%的 Fe、 0.04 ~ 0. 10 wt% 的 P , 其余为 Zn和不可避免的杂质。
2、 根据权利要求 1所述的黄铜合金， 其特征在于， 所述黄铜合金中 Cu 的含量为： 75-76wt%。
3、 根据权利要求 1或 2所述的黄铜合金， 其特征在于， 所述黄铜合金 中 Si的含量为： 3.1-3.4wt%。
4、 根据权利要求 1至 3中任一项所述的黄铜合金， 其特征在于， 所述 黄铜合金中 P的含量为： 0.04~0.08wt%。
5、 根据权利要求 1至 4中任一项所述的黄铜合金， 其特征在于， 所述 黄铜合金还含有 0.001 ~ 0.01wt%选自 B、 Ag、 Ti和 RE中的至少一种元素。
6、 根据权利要求 5所述的黄铜合金， 其特征在于， 所述黄铜合金中 B、 Ag、 Ti和 RE的含量为： 0.001 ~ 0.005wt%。
7、 根据权利要求 1至 6中任一项所述的黄铜合金， 其特征在于， 所述 黄铜合金还含有选自 Pb、 Bi、 Se和 Te中的至少一种元素， 其中 Pb的含量 为 0.01 ~ 0.25 wt% , Bi的含量为 0.01 ~ 0.4 wt% , Se的含量为 0.005 ~ 0.4 wt% , Te的含量为 0.005 ~ 0.4 wt%。
8、 根据权利要求 1至 7中任一项所述的黄铜合金， 其特征在于， 所 述黄铜合金还含有 0.05 ~ 0.2 wt%选自 Mn、 Al、 Sn和 Ni中的至少一种元 素。
9、 根据权利要求 1至 8中任一项所述的黄铜合金， 其特征在于， 所 述黄铜合金还含有 0.03 ~ 0. 15 wt%选自 As和 Sb中的至少一种元素。
PCT/CN2014/071362 2013-02-01 2014-01-24 一种热成型性能优异的无铅易切削耐蚀黄铜合金 WO2014117684A1 (zh)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DK14746185.9T DK2952596T3 (en) 2013-02-01 2014-01-24 EASY TO USE RUST-RESISTANT BRASS ALWAYS WITH GOOD THERMO FORMING EFFECT
JP2015555571A JP6335194B2 (ja) 2013-02-01 2014-01-24 良好な熱成形性を有する、無鉛の、切断が容易な、耐腐食性真鍮合金
US14/765,305 US11028464B2 (en) 2013-02-01 2014-01-24 Lead-free easy-to-cut corrosion-resistant brass alloy with good thermoforming performance
EP14746185.9A EP2952596B1 (en) 2013-02-01 2014-01-24 Lead-free easy-to-cut corrosion-resistant brass alloy with good thermoforming performance
CA2907482A CA2907482C (en) 2013-02-01 2014-01-24 Easy-to-cut corrosion-resistant brass alloy with good thermoforming performance
PL14746185T PL2952596T3 (pl) 2013-02-01 2014-01-24 Bezołowiowy, łatwy w skrawaniu, odporny na korozję stop mosiężny o dobrej jakości kształtowania termicznego
ES14746185.9T ES2676271T3 (es) 2013-02-01 2014-01-24 Aleación de latón resistente a la corrosión fácil de cortar sin plomo con buen rendimiento de termoformación

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310044722.2A CN103114220B (zh) 2013-02-01 2013-02-01 一种热成型性能优异的无铅易切削耐蚀黄铜合金
CN201310044722.2 2013-02-01

Publications (1)

Publication Number Publication Date
WO2014117684A1 true WO2014117684A1 (zh) 2014-08-07

Family

ID=48412637

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/071362 WO2014117684A1 (zh) 2013-02-01 2014-01-24 一种热成型性能优异的无铅易切削耐蚀黄铜合金

Country Status (11)

Country Link
US (1) US11028464B2 (zh)
EP (1) EP2952596B1 (zh)
JP (1) JP6335194B2 (zh)
CN (1) CN103114220B (zh)
CA (1) CA2907482C (zh)
DK (1) DK2952596T3 (zh)
ES (1) ES2676271T3 (zh)
PL (1) PL2952596T3 (zh)
PT (1) PT2952596T (zh)
TR (1) TR201808044T4 (zh)
WO (1) WO2014117684A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2952596B1 (en) 2013-02-01 2018-04-11 Xiamen Lota International Co., Ltd. Lead-free easy-to-cut corrosion-resistant brass alloy with good thermoforming performance

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013012288A1 (de) 2013-07-24 2015-01-29 Wieland-Werke Ag Korngefeinte Kupfer-Gusslegierung
CN103740974A (zh) * 2014-01-27 2014-04-23 苏州乾雄金属材料有限公司 一种实用金属材料
CN104513913B (zh) * 2014-11-13 2016-08-24 无锡信大气象传感网科技有限公司 传感器用高强度铜合金材料
CN105039777B (zh) * 2015-05-05 2018-04-24 宁波博威合金材料股份有限公司 一种可切削加工黄铜合金及制备方法
CN106893883A (zh) * 2015-12-18 2017-06-27 九牧厨卫股份有限公司 一种铸造用低铅易切削硅黄铜合金及其制备方法
DE102016001994A1 (de) * 2016-02-19 2017-08-24 Wieland-Werke Ag Gleitelement aus einer Kupfer-Zink-Legierung
KR102021723B1 (ko) 2016-08-15 2019-09-16 미쓰비시 신도 가부시키가이샤 쾌삭성 구리 합금 주물, 및 쾌삭성 구리 합금 주물의 제조 방법
CN109937267B (zh) * 2016-10-28 2021-12-31 同和金属技术有限公司 铜合金板材及其制造方法
CN106636792B (zh) * 2016-12-29 2018-10-23 宁波市胜源技术转移有限公司 一种高导电性的复合金属
MX2017001955A (es) * 2017-02-10 2018-08-09 Nac De Cobre S A De C V Aleaciones de cobre bajas en plomo.
JP2018130507A (ja) * 2017-02-15 2018-08-23 株式会社小泉製作所 乾杯等に用いる飲用容器
US11155909B2 (en) 2017-08-15 2021-10-26 Mitsubishi Materials Corporation High-strength free-cutting copper alloy and method for producing high-strength free-cutting copper alloy
CN108060324B (zh) * 2017-12-13 2020-03-27 宁波金田铜业(集团)股份有限公司 一种高强耐蚀耐磨阀件用铜合金棒材及其制备方法
CN110144492A (zh) * 2018-07-11 2019-08-20 鹤山麦瑟文卫浴有限公司 一种应用于水龙头的环保型无铅铜合金
ES2940703T3 (es) 2019-06-25 2023-05-10 Mitsubishi Materials Corp Aleación de cobre de fácil corte y método para fabricar aleación de cobre de fácil corte
US20220275479A1 (en) 2019-06-25 2022-09-01 Mitsubishi Materials Corporation Free-cutting copper alloy casting, and method for producing free-cutting copper alloy casting
CA3157545A1 (en) 2019-12-11 2021-06-17 Mitsubishi Materials Corporation Free-cutting copper alloy and method for manufacturing free-cutting copper alloy
CN113502408B (zh) * 2021-06-17 2022-06-07 四川科派新材料有限公司 一种含碲镍的高导铜合金及其制备方法
GB2614752A (en) * 2022-01-18 2023-07-19 Conex Ipr Ltd Components for drinking water pipes, and method for manufacturing same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002180165A (ja) * 2000-12-18 2002-06-26 Dowa Mining Co Ltd プレス打ち抜き性に優れた銅基合金およびその製造方法
CN1524970A (zh) * 2003-02-28 2004-09-01 ������-�ֿ˹����ɷ����޹�˾ 无铅铜合金和其应用
CN1570164A (zh) * 2003-07-11 2005-01-26 马健鹉 铸花件用铜合金
CN101386931A (zh) * 2008-10-21 2009-03-18 中铝洛阳铜业有限公司 环保易切削无铅铜合金材料及加工工艺
CN103114220A (zh) * 2013-02-01 2013-05-22 路达(厦门)工业有限公司 一种热成型性能优异的无铅易切削耐蚀黄铜合金

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4120499C1 (en) 1991-06-21 1992-11-19 Wieland-Werke Ag, 7900 Ulm, De Low cost copper@ alloy for e.g. semiconductor carrier - contains zinc@, silicon, iron@, aluminium@, phosphorus@ and copper@
JPH0768595B2 (ja) * 1991-11-14 1995-07-26 三宝伸銅工業株式会社 耐蝕性銅基合金材
DE695372T1 (de) * 1993-04-22 1998-01-02 Federalloy Inc Kupfer-wismut-gusslegierungen
JPH111736A (ja) * 1997-06-09 1999-01-06 Chuetsu Gokin Chuko Kk 加熱装置用黄銅合金材料
JP2000169919A (ja) * 1998-12-04 2000-06-20 Sanbo Copper Alloy Co Ltd 無鉛銅基合金材
JP3465108B2 (ja) * 2000-05-25 2003-11-10 株式会社神戸製鋼所 電気・電子部品用銅合金
JP2002030364A (ja) * 2000-07-19 2002-01-31 Sumitomo Light Metal Ind Ltd 高強度快削黄銅
JP2002069551A (ja) * 2000-09-04 2002-03-08 Sumitomo Light Metal Ind Ltd 快削性銅合金
JP4296344B2 (ja) * 2003-03-24 2009-07-15 Ｄｏｗａメタルテック株式会社 銅合金材
DE202004020395U1 (de) 2004-10-11 2005-09-08 Diehl Metall Stiftung & Co.Kg Kupfer-Zink-Silizium-Legierung
DE102005024037A1 (de) * 2004-10-11 2006-04-13 Diehl Metall Stiftung & Co.Kg Kupfer-Zink-Silizium-Legierung, deren Verwendung und deren Herstellung
BRPI0516067B1 (pt) * 2004-10-11 2014-10-14 Diehl Metall Stiftung & Co Kg Liga de cobre/zinco/silício, e seu processo de produção
JP4813073B2 (ja) * 2005-03-25 2011-11-09 三菱電線工業株式会社 中心コンタクト、アンカーコネクタ、及びそれらのコネクタ構造
KR100982611B1 (ko) * 2005-07-28 2010-09-15 산에츠긴조쿠가부시키가이샤 동합금 압출재 및 그 제조 방법
RU2398904C2 (ru) 2005-09-22 2010-09-10 Мицубиси Синдох Ко, Лтд Легкообрабатываемый резанием медный сплав, содержащий очень мало свинца
MXPA06002911A (es) * 2005-09-22 2007-04-12 Sanbo Shindo Kogyo Kabushiki Kaisha Aleacion de cobre de corte expedito que contiene muy bajo contenido de plomo.
DE102007013806B4 (de) * 2007-03-22 2009-02-19 Wieland-Werke Ag Elektrischer Leiter mit Messwiderstand
CN100595301C (zh) * 2008-06-30 2010-03-24 中铝洛阳铜业有限公司 一种易切削铜合金材料的加工工艺
WO2011066581A1 (en) * 2009-11-30 2011-06-03 Moen Incorporated Copper corrosion resistant, machinable brass alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002180165A (ja) * 2000-12-18 2002-06-26 Dowa Mining Co Ltd プレス打ち抜き性に優れた銅基合金およびその製造方法
CN1524970A (zh) * 2003-02-28 2004-09-01 ������-�ֿ˹����ɷ����޹�˾ 无铅铜合金和其应用
CN1570164A (zh) * 2003-07-11 2005-01-26 马健鹉 铸花件用铜合金
CN101386931A (zh) * 2008-10-21 2009-03-18 中铝洛阳铜业有限公司 环保易切削无铅铜合金材料及加工工艺
CN103114220A (zh) * 2013-02-01 2013-05-22 路达(厦门)工业有限公司 一种热成型性能优异的无铅易切削耐蚀黄铜合金

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2952596A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2952596B1 (en) 2013-02-01 2018-04-11 Xiamen Lota International Co., Ltd. Lead-free easy-to-cut corrosion-resistant brass alloy with good thermoforming performance

Also Published As

Publication number Publication date
TR201808044T4 (tr) 2018-06-21
US11028464B2 (en) 2021-06-08
CA2907482C (en) 2021-05-18
JP6335194B2 (ja) 2018-05-30
JP2016511792A (ja) 2016-04-21
EP2952596A1 (en) 2015-12-09
ES2676271T3 (es) 2018-07-18
DK2952596T3 (en) 2018-06-14
EP2952596A4 (en) 2016-10-19
US20160068931A1 (en) 2016-03-10
PT2952596T (pt) 2018-05-29
EP2952596B1 (en) 2018-04-11
PL2952596T3 (pl) 2018-08-31
CA2907482A1 (en) 2014-08-07
CN103114220A (zh) 2013-05-22
CN103114220B (zh) 2015-01-21

Similar Documents

Publication Publication Date Title
WO2014117684A1 (zh) 一种热成型性能优异的无铅易切削耐蚀黄铜合金
JP5383730B2 (ja) 環境に優しいマンガン黄銅合金およびそれらの製造方法
CA2850053C (en) Leadless free-cutting copper alloy and method for producing the same
JP5383633B2 (ja) 優れた応力腐食耐性を有する黄銅合金およびその製造方法
CN101619404B (zh) 一种适于锻造用易切削无铅黄铜合金及其制备方法
CN102776409B (zh) 一种耐蚀铜合金的制备工艺
WO2006136065A1 (fr) Nouvel alliage de laiton écologique sans plomb à découpe libre qui présente une faible teneur en antimoine et bismuth, et sa préparation
WO2015100872A1 (zh) 低铅无铋无硅黄铜
CN101307403B (zh) 一种高强度易切削铝合金
CN111655878A (zh) 不含有铅和铋的易切割无铅铜合金
CN102286674B (zh) 一种适合锻造用环保硅锡黄铜及其制造方法
JP4620963B2 (ja) 黄銅およびその製造方法ならびにこれを用いた部品
CN101812611A (zh) 一种无铅耐腐蚀黄铜合金及其制造方法
CN101921926B (zh) 一种低钙易切削硅黄铜合金及其制备方法
CN100547097C (zh) 一种换热器内翅片的铝合金材料的生产方法
CN101423905A (zh) 一种无铅易切削锑镁黄铜合金
CN110791679B (zh) 一种黄铜合金及其生产方法
CN101289714B (zh) 一种无铅的易切削镁铋黄铜合金
CN102400011A (zh) 一种锻造用低铅耐腐蚀黄铜合金及其制造方法
CA2687452C (en) Brass alloy
TW201408793A (zh) 低收縮耐腐蝕的黃銅合金

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14746185

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015555571

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2014746185

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2907482

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 14765305

Country of ref document: US