WO2006136065A1 - Nouvel alliage de laiton écologique sans plomb à découpe libre qui présente une faible teneur en antimoine et bismuth, et sa préparation - Google Patents

Nouvel alliage de laiton écologique sans plomb à découpe libre qui présente une faible teneur en antimoine et bismuth, et sa préparation Download PDF

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WO2006136065A1
WO2006136065A1 PCT/CN2005/001399 CN2005001399W WO2006136065A1 WO 2006136065 A1 WO2006136065 A1 WO 2006136065A1 CN 2005001399 W CN2005001399 W CN 2005001399W WO 2006136065 A1 WO2006136065 A1 WO 2006136065A1
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alloy
lead
free
brass
zinc
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PCT/CN2005/001399
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English (en)
Chinese (zh)
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Ming Zhang
Xiao Xie
Jihua Cai
Xianqi Meng
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Ningbo Powerway Group Co., Ltd.
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Publication of WO2006136065A1 publication Critical patent/WO2006136065A1/fr

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    • 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 present invention relates to a lead-free brass alloy, and more particularly to a lead-free, low-cut brass alloy (PWEHSCBRASS) having excellent cutting properties, mechanical properties and corrosion resistance. It is especially suitable for connectors for electronics, telecommunications equipment, computers; household electrical; light components for lamps and photographic equipment; children's toys and parts for machinery and automotive manufacturing; water supply system pipe castings, wide parts, switch connectors Manufacturing and other fields. It is a new type of metal material that is conducive to human health and environmental protection. It is also a new and ideal alternative to lead brass, which is widely used to cause adverse effects on the human body and the environment. Background technique
  • Lead brass has excellent cold and hot workability, excellent cutting performance and self-lubricating characteristics, and can meet the machining of various shapes and components. Therefore, lead-containing brass is widely recognized as an important basic material in the world. It is used in a wide range of fields such as wire castings and accessories for electronics, telecommunications, computer components, civil water systems, parts for home appliances and children's toys, optoelectronic components for lamps and photographic equipment, and parts manufacturing for automotive and machinery manufacturing.
  • lead is an element harmful to the environment and to the human body.
  • Lead can cause irreversible damage to human blood and nervous system, especially to children's kidney and brain nerves. It can cause blood lead, brain lead poisoning and nerve blockage.
  • Mental retardation In recent years, medical experts from all over the world have found that lead-containing brass poses a threat to human health and environmental health. Medical research institutions in Northern Europe, the United States, Japan and China have all reported that lead brass has caused harm to the human environment. In February 2004, the World Health Organization Children's Cooperative Center conducted a lead poisoning investigation on 17,000 children in 15 cities in China. Among them, children's toys were listed as one of the risk factors for lead poisoning in children, so governments have also introduced them. Government restrictions on the application of leaded copper alloys. The Chinese government has also recently issued mandatory regulations such as the “Measures for the Administration of Pollution Prevention and Control of Electronic Information Products” that are consistent with international restrictions.
  • the lead-free free-cutting brass alloy material invented by Metal Corporation has the following composition and manufacturing method:
  • the alloy contains 4% by weight: copper: 60.0 ⁇ 62.0%, ⁇ : 0.5-2.2%, aluminum: 0.01-0.1%, Tin: 0.5 ⁇ 1.6%, phosphorus: 0.04-0.15%, the rest is zinc and inevitable impurity components, heat treatment at 460 ⁇ 600 °C for 30 minutes to 4 hours, slow cooling at a cooling rate of 70 ⁇ / hr or less .
  • Another invention is the "lead-free copper alloy and its application" developed by the German company Wieland, 200410004293, which consists of the following components: copper: 70.0 ⁇ 83.0%, silicon: 1 ⁇ 5%, tin- 0.01 to 2%, iron: 0.01 to 0.3% and/or cobalt: 0.01 to 0.3%, nickel: 0.01 to 0.3%, manganese: 0.01 to 0.3%, and the amount of niobium is zinc and unavoidable impurities.
  • the object of the present invention is to provide a lead-free and excellent machinability, cold moldability and good weldability, and excellent mechanical properties, and at the same time, have excellent corrosion resistance and can replace lead-containing copper alloys. It is a new type of lead-free, low-cut brass alloy that does not cause environmental pollution and is beneficial to human health. It is also different from foreign bismuth-containing brass alloys and their manufacturing methods.
  • the object of the present invention is achieved by providing a lead-free, low-cut brass alloy having the following alloy composition:
  • the alloy composition of one of the lead-free free-cutting low-yield brass alloys of the present invention is: copper: 55-65 wt%, ⁇ : 0.3-1.5 wt%, ⁇ : 0.05-L0 wt%, boron: 0.0002-0.05 wt%, Other elements: 0.2 ⁇ 1.2 wt%, the balance is zinc and unavoidable impurities; the content of lead in the unavoidable impurities is less than 0.1 wt%; the alloy composition is copper plus zinc plus lanthanum plus lanthanum plus more than 97 wt %, and wherein zinc is greater than 35.5 wt% ; the other element is at least two elements selected from the group consisting of titanium, nickel, iron, tin, phosphorus, and rare earth metals.
  • the preferred composition of one of the lead-free free-cutting low-yield brass alloys is: copper: 58 to 63 wt%, ⁇ : 0.4 to 1.4 wt%, ⁇ : 0.06 to 0.8 wt%, boron: 0.0006 to 0.03 Wt%, other elements: 0.2 ⁇ 1.0 wt%, the balance is zinc and unavoidable impurities; the content of lead in the unavoidable impurities is less than 0.1 wt%; the alloy composition is copper plus zinc plus lanthanum plus boron More than 97.5 % and no more than 99.8 wt%, wherein zinc is greater than 35.5 wt%; the other element is at least two elements selected from the group consisting of titanium, nickel, iron, tin, phosphorus, rare earth metals.
  • the phase composition of one of the lead-free free-cutting low-yield brass alloys is:
  • the ⁇ -phase is mainly composed of a ruthenium phase in which the free state is uniformly distributed in the crystal and the grain boundary, and a small amount of a hard and brittle phase of the solid solution-containing intermetallic compound uniformly distributed at the grain boundary.
  • One of the lead-free free-cutting low-ruthenium brass alloys is that the lead is replaced by bismuth and antimony, and the bismuth is mainly used to further improve the cutting performance of the alloy by using bismuth and bismuth; and boron is mainly used for bismuth, tin, etc. Auxiliary boron to improve the anti-dezincification performance of the alloy.
  • niobium improves the machinability of the alloy.
  • the solid solubility of bismuth in copper is extremely low. Even at 800 ⁇ , the solubility is only 0.01%, but the solubility in the melt is very large.
  • strontium precipitates and forms dispersed second phase particles.
  • the diffuse phase of the crucible has a low melting point (271.3 ° C), which is locally heated by the contact between the tip and the chip and melts instantaneously. This melting effect helps to change the shape of the chip and lubricate the tool, thereby enabling the alloy to be machined.
  • the medium easy to form short chip breaking points, reduce the bonding and welding between the cutter head and the workpiece and improve the cutting speed, so that the alloy has satisfactory cutting performance.
  • the content of niobium is more than 1.5%, it will lead to an increase in brittleness.
  • the alloy is easy to form short chip breaking points during machining, which effectively increases the comprehensive performance of the alloy's cutting performance and corrosion resistance and dezincification resistance, so that the high-low brass alloy is obtained like lead brass.
  • Such excellent cutting performance, excellent cold forming properties, casting properties, weldability and mechanical properties. Can be widely used in electronics, telecommunications, computers, drinking water engineering, hardware, machinery, photographic equipment, optoelectronic components, home appliances, automotive parts casting and cold forming, free cutting parts manufacturing.
  • Tantalum and niobium are the elements that strengthen and improve the cutting performance of the alloy.
  • this alloy When the content is less than 0.3%, the machinability requirement is not satisfied, and when the niobium content is more than 1.5%, the cold and hot forming properties of the alloy are lowered and the mechanical properties of the alloy are drastically lowered, and the cost is also increased.
  • the content of niobium in the alloy is 0.3 to 1.5%.
  • Such content control can only make the cutting coefficient of the alloy reach about 80% under the condition of no other cutting elements such as niobium, but also add an auxiliary niobium element on the basis of the niobium content of 0.3 ⁇ 1.5%. It assists in the enthalpy and works together with hydrazine to obtain better cutting performance (cutting coefficient of 86 ⁇ 95%) and excellent corrosion resistance and mechanical properties, thus meeting the requirements of environmental protection, health and new alloy materials.
  • niobium element is mainly used to assist the crucible to further improve the cutting performance of the alloy and the unique effect of inhibiting dezincification.
  • addition content of niobium is less than 0.05%, the effect of improving the cutting performance of the auxiliary niobium is not obvious, and the effect of improving the anti-dezincification property is not obvious, and when the auxiliary addition content is more than 1.0%, although the auxiliary niobium improves the cutting performance, The plasticity reduction of the alloy is also very significant, while also increasing the cost.
  • the auxiliary ruthenium content is 0.05 ⁇ 1.0%, which can play an auxiliary role in improving the cutting performance of the alloy, so that the alloy has superior cutting performance (cutting coefficient of 86 ⁇ 95%) and resistance. Dezincification performance and excellent cold forming properties, weldability and good mechanical properties.
  • niobium Low levels of niobium have a certain solubility in both copper and zinc. Therefore, niobium is present in the alloy in a low-content, non-toxic solid solution state, insoluble in water, rather than being present in the alloy in a toxic free state like lead. Observed by electron probe and transmission electron microscopy, in this alloy, niobium preferentially forms a solid solution with zinc and accumulates near the grain boundary to form a short cutting point that is easy to cut, so that the embrittlement phase of the metal compound containing niobium is uniformly distributed in the grain boundary. Further, the cutting performance of the alloy is further improved.
  • the alloy is mainly boron, and boron is assisted by bismuth, tin and the like to improve the anti-dezincification performance of the alloy.
  • the addition of boron mainly serves to suppress dezincification and improve corrosion resistance, and also has functions of deoxidizing, refining grains, and enhancing cutting performance. Since the radius of the boron atom is smaller than the radius of the zinc atom, the boron atom is more easily diffused than the zinc atom when the brass is corroded, so that the vacancy can be preferentially blocked to block the diffusion channel of the zinc atom, and the resistance of the zinc diffusion is increased to form a corrosion-resistant protective film. The effect of suppressing dezincification corrosion like arsenic.
  • bismuth is also easy to form a solid solution compound with zinc, which can also inhibit dezincification, thereby assisting boron and cooperating with it to improve the anti-zinc removal property of the alloy.
  • the amount of boron added is preferably 0.0002 to 0.05%. When the boron content is less than 0.0002%, the X-inhibition effect of dezincification and corrosion resistance is not obvious; when the boron content is more than 0.05%, the boride is easily precipitated at the grain boundary, resulting in "boron brittleness" and lowering the alloy forming property.
  • the addition of trace amounts of tin and other elements to the brass further enhances the resistance to dezincification to the leaching standards of the relevant elements in the copper alloys specified by the International Drinking Water Authority and the ISO 6509 dezincification standard.
  • a zinc content greater than 35.5% contributes to improved cutting performance and enhanced wear resistance, but too high a temperature affects cold formability and alloy strength.
  • the addition of at least two of titanium, nickel, iron, tin, phosphorus, and rare earth metals in the other elements one is deoxidation and refinement of crystal grains; the second is to form a metal compound with lead in the impurity, The grain boundary is strengthened, and the embrittlement phase of the metal compound containing ruthenium is more finely distributed on the grain boundary, and the metal ruthenium is uniformly distributed in the crystal grain and the grain boundary, and the ⁇ phase and the ⁇ -containing embrittlement are also suppressed.
  • the phase is biased to be brittle, which satisfies the excellent cutting performance, excellent cold and hot forming properties and welding performance required by the industry.
  • the third is to suppress dezincification, enhance corrosion resistance and stress crack resistance.
  • the total content of the other elements is less than 0.2%, which does not achieve satisfactory cutting performance and grain boundary strengthening; the total amount of other elements is more than 1.2%, which can further refine the alloy and inhibit dezincification, but will form other more Hard and brittle phase, can not meet the cold forming performance of the latter step, but also increase the cost, affecting the promotion effect.
  • the addition of titanium mainly acts to deoxidize and refine the grains. Generally, the addition amount is 0.001 to 0.15%, and the effect is less than 0.001%. The effect is not obvious, and more than 0.15% increases the cost and lowers the casting performance.
  • Nickel is a matrix that strengthens and prevents dezincification, while inhibiting grain growth, increasing alloy strength, plasticity and corrosion resistance, while also improving the ability of the alloy to resist stress corrosion. If the nickel content is less than 0.1%, it is difficult to meet the various performance requirements required by the industry. If the nickel content is more than 0.6%, the alloy manufacturing cost is increased and the cutting performance is lowered. Therefore, the nickel content should be controlled at 0.1 to 0.6%.
  • Iron and rare earth metals mainly function to refine grains, prevent grain growth, and control the number of ⁇ phase transitions, which can improve the softening point, enhance the strength, and improve the cold and hot forming properties. Another important role of rare earth metals is deoxidation.
  • the iron content is generally controlled at 0.1 to 0.3%, the iron content is less than 0.1%, and the grain refining effect is not significant; the iron content is more than 0.3%, which lowers the corrosion resistance and the electroplatability.
  • Rare earth metal is an excellent modifier and refining agent. It is hardly soluble in copper. It forms a high melting point metal compound with lead in the alloy. It is distributed in the crystal to improve the plasticity and wear resistance of the alloy and promote the grain.
  • Tin is an element that solid solution strengthens and inhibits dezincification. It strengthens the matrix together with bismuth, boron and phosphorus, which is beneficial to the uniform dispersion of the phases and the formation of strengthening phases, which is beneficial to the improvement of strength, wear resistance and cutting performance, especially It is beneficial to the anti-dezincification performance and the improvement of thermoforming performance.
  • Phosphorus content is generally controlled at
  • 0.005 ⁇ 0.2% is suitable.
  • the tin content is generally controlled at 0.1 to 0.4%, and too high will reduce the cutting performance.
  • Lead and cadmium even as an inevitable impurity element, must have a lead content of less than 0.1% and a cadmium content of less than 0.001%. According to the results of the leaching test of the relevant testing standards in the international drinking water project, the lead and cadmium content meets the requirements of international environmental protection restrictions, and does not cause pollution to the environment and human health.
  • One of the above-mentioned lead-free free-cutting low-ruthenium brass alloys of the present invention is advantageous in that it has excellent cutting performance, dezincification resistance, stress corrosion resistance, excellent mechanical properties, cold and hot forming properties and excellent welding properties.
  • Environmentally friendly and healthy new lead-free free-cutting brass alloy. Can be widely used in electronics, telecommunications, computers, drinking water engineering, hardware, machinery, photographic equipment, optoelectronic components, home appliances, automotive parts casting and hot and cold forming, free cutting parts manufacturing.
  • the alloy composition of the lead-free free-cutting low-yield brass alloy of the present invention is: copper: 55 to 63 wt%, ⁇ : 0.3 to 1.5 wt%, ⁇ : 0.05 to 1.0 wt%, nickel: 0.1 to 0.6 wt% Boron: 0.0002 ⁇ 0.05 wt%, other elements: 0.2-1.5 wt%, the balance is zinc and unavoidable impurities; the content of lead in the unavoidable impurity is less than 0.1 wt%; the alloy composition is copper plus Zinc plus lanthanum plus boron is greater than 97 wt%, and wherein zinc is greater than 36.5 wt% ; the other element is at least two elements selected from the group consisting of titanium, iron, silicon, tin, phosphorus, rare earth metals.
  • the preferred composition of the lead-free free-cutting low-cut brass alloy is: copper: 57-62 wt%, secret: 0.4-1.4 t%, ⁇ : 0.06-0.8 wt%, nickel: 0.1-0.5 Wt%, boron: 0.0006 ⁇ 0.03 wt%, other elements: 0.2 ⁇ 1.2 wt%, the balance is zinc and unavoidable impurities; the content of lead in unavoidable impurities is less than 0.1 wt%; the alloy composition is copper Zinc plus lanthanum plus boron is greater than 97.5 ⁇ % and no greater than 99.8 wt%, wherein zinc is greater than 36.5 wt ; the other elements are at least two elements selected from the group consisting of titanium, iron, silicon, tin, Phosphorus, rare earth metals.
  • the phase composition of the lead-free free-cutting low-cut brass alloy is as follows: the two phases are mainly composed of ⁇ and P, and the ⁇ phase is uniformly distributed in the crystal and the grain boundary in a free state, and a small amount is finely distributed uniformly at the grain boundary.
  • the hard-brittle phase of the solid solution-containing ruthenium-containing intermetallic compound is mainly composed of ⁇ and P, and the ⁇ phase is uniformly distributed in the crystal and the grain boundary in a free state, and a small amount is finely distributed uniformly at the grain boundary.
  • the second lead-free low-cut brass alloy is replaced by bismuth and antimony, mainly bismuth, and further improves the cutting performance of the alloy by using bismuth and bismuth.
  • boron is mainly used for bismuth, tin, etc. Auxiliary boron to improve the anti-dezincification of the alloy Performance.
  • niobium improves the machinability of the alloy.
  • the solid solubility of bismuth in copper is extremely low. Even at 800 °C, the solubility is only 0.01%, but the solubility in the melt is very large.
  • strontium precipitates and forms dispersed second phase particles.
  • the melting phase of the crucible has a low melting point (271.3 °C), and is locally melted at the contact surface between the cutter head and the chip. This melting effect helps to change the shape of the chip and lubricate the tool, thereby causing the alloy to It is easy to form short chip breaking points during machining, reduce the bonding and welding between the cutter head and the workpiece, and improve the cutting speed, so that the alloy has satisfactory cutting performance.
  • Tantalum and niobium are the elements that strengthen and improve the cutting performance of the alloy.
  • the niobium content of the alloy is less than 0.3%, the machinability is not satisfied, and when the niobium content is more than 1.5%, the cold and hot forming properties of the alloy are lowered and the mechanical properties of the alloy are drastically lowered, and the cost is also increased.
  • the content of antimony in the alloy is 0.3 to 1.5%.
  • Such content control can only make the cutting coefficient of the alloy reach about 80% under the condition of no other cutting elements such as niobium, but also add an auxiliary niobium element on the basis of the niobium content of 0.3 ⁇ 1.5%. It assists in the enthalpy and works together with hydrazine to obtain better cutting performance (cutting coefficient of 86 ⁇ 95%) and excellent corrosion resistance and mechanical properties, thus meeting the requirements of environmental protection, health and new alloy materials.
  • the addition of an appropriate amount of niobium element is mainly used to assist the crucible to further improve the cutting performance of the alloy and the unique effect of inhibiting dezincification.
  • the addition content of cerium is less than 0.05%, the effect of improving the cutting performance of auxiliary enthalpy is not obvious, and the effect of improving the anti-dezincification is not obvious, while the auxiliary addition content is more than 1.0%, although the auxiliary enthalpy improves the cutting performance. Large, but the plasticity of the alloy is also reduced significantly, while also increasing costs.
  • the auxiliary strontium content is 0.05 ⁇ 1.0%, which can play an auxiliary role in improving the cutting performance of the alloy, so that the alloy has superior cutting performance (cutting coefficient is 86 ⁇ 95%) and resistance. Dezincification performance and excellent thermoforming properties, weldability and good mechanical properties.
  • niobium Low levels of niobium have a certain solubility in both copper and zinc. Therefore, niobium is present in the alloy in a low-content, non-toxic solid solution state, insoluble in water, rather than being present in the alloy in a toxic free state like lead. Observed by electron probe and transmission electron microscopy, in this alloy, niobium preferentially forms a solid solution with zinc and accumulates near the grain boundary to form a short cutting point that is easy to cut, so that the embrittlement phase of the metal compound containing niobium is uniformly distributed in the grain boundary. Further, the cutting performance of the alloy is further improved.
  • Nickel is a matrix that strengthens and prevents dezincification, while inhibiting grain growth, increasing alloy strength, plasticity and corrosion resistance, while also improving the ability of the alloy to resist stress corrosion. If the nickel content is less than 0.1%, it is difficult to meet the various performance requirements required by the industry. If the nickel content is more than 0.6%, the alloy manufacturing cost is increased and the cutting performance is lowered. Therefore, the nickel content should be controlled at 0.1 to 0.6%.
  • the alloy is mainly boron, and boron is assisted by bismuth, tin and the like to improve the anti-dezincification performance of the alloy.
  • the addition of boron mainly serves to suppress dezincification and improve corrosion resistance, and also has functions of deoxidizing, refining grains, and enhancing cutting performance. Since the radius of the boron atom is smaller than the radius of the zinc atom, the boron atom is more easily diffused than the zinc atom when the brass is corroded, so that the vacancy can be preferentially blocked to block the diffusion channel of the zinc atom, and the resistance of the zinc diffusion is increased to form a corrosion-resistant protective film. The effect of suppressing dezincification corrosion like arsenic. At the same time, bismuth is also easy to form a solid solution compound with zinc, which can also inhibit dezincification, thereby assisting boron and cooperating with it to improve the anti-dezincification effect of the alloy.
  • the amount of boron added is preferably from 0.0002 to 0.05%.
  • the boron content is less than 0.0002%, the effect of inhibiting dezincification and corrosion resistance is not obvious; when the boron content is more than 0.05%, the boride is easily precipitated at the grain boundary, resulting in "boron brittleness" and lowering the alloy forming property.
  • the addition of trace amounts of tin and other elements to the brass further enhances the resistance to dezincification to the leaching standards of the relevant elements in the copper alloys specified by the International Drinking Water Authority and the ISO 6509 dezincification standard.
  • a zinc content of more than 36.5% is advantageous for the improvement of the cutting performance and the improvement of the wear resistance, but too high a temperature affects the cold forming property and the strength of the alloy.
  • the other elements of the other elements are added by at least two elements of titanium, iron, silicon, tin, phosphorus, and rare earth metals, one is deoxidizing and refining crystal grains; the second is forming a metal compound with lead in the impurities, strengthening The grain boundary, and the embrittlement phase of the ruthenium-containing metal compound is more finely distributed on the grain boundary, and the metal ruthenium is evenly distributed in the crystal and the grain boundary, and the ⁇ phase and the ⁇ -containing embrittlement phase are also suppressed.
  • the tendency of segregation is brittle, which satisfies the excellent cutting performance, thermoforming performance and good welding performance required by the industry. Thirdly, it suppresses dezincification, corrosion resistance and stress crack resistance.
  • the total content of the other elements is less than 0.2%, which does not achieve satisfactory cutting performance and grain boundary strengthening; the total amount of other elements is more than 1.5%, which can further refine the alloy and inhibit dezincification, but will form other more
  • the hard and brittle phase can not meet the cold forming performance of the latter step, and also increases the cost, affecting the promotion effect.
  • the addition of titanium mainly acts to deoxidize and refine the grains. Generally, the addition amount is 0.001 to 0.15%, and the effect is less than 0.001%. The effect is not obvious, and more than 0.15% increases the cost and lowers the casting performance.
  • Iron and rare earth metals mainly function to refine grains, prevent grain growth, and control the number of ⁇ phase transitions, which can improve softening point, enhance strength, and improve cold and hot forming properties. Another important role of rare earth metals is deoxidation.
  • the iron content is generally controlled at 0.1 to 0.3%, the iron content is less than 0.1%, and the grain refining effect is not significant; the iron content is more than 0.3%, which lowers the corrosion resistance and the electroplatability.
  • Rare earth metal is an excellent modifier and refining agent. It is hardly soluble in copper. It forms a high melting point metal compound with lead in the alloy. It is distributed in the crystal to improve the plasticity and wear resistance of the alloy and promote the grain. Refinement, promote the finer and evenly distributed metal compounds on the grain boundary, generally adding 0.003 ⁇ 0.4%, adding cerium-based mixed rare earth effect is better, can increase conductivity and resistance to dezincification, too high Reduce the fluidity of the alloy.
  • silicon can also inhibit zinc evaporation and oxide inclusion; second, to enhance the density and pressure resistance of the alloy, Wear resistance and cutting performance, rather than making the alloy produce a high-silicon ⁇ hard and brittle phase.
  • the amount of addition is 0.1 ⁇ 0.7%.
  • tin and phosphorus is also auxiliary boron to enhance the resistance to dezincification and stress cracking and to improve the hot forming properties, so as to meet the international environmental health and safety standards.
  • adding tin and phosphorus to the brass can also deoxidize, increase the fluidity of the alloy, and improve the cutting performance and strength of the alloy.
  • Tin is an element that solid solution strengthens and inhibits dezincification. It strengthens the matrix together with bismuth, boron and phosphorus, which is beneficial to the uniform dispersion of the phases and the formation of strengthening phases, which is beneficial to the improvement of strength, wear resistance and cutting performance, especially It is beneficial to the anti-dezincification performance and the improvement of the cold and hot forming properties.
  • the phosphorus content is generally controlled to be 0.005 to 0.2%.
  • the tin content is generally controlled to be 0.1 to 0.4%, and too high may deteriorate the cutting performance.
  • Lead and cadmium even as an inevitable impurity element, must have a lead content of less than 0.1% and a cadmium content of less than 0.001%. According to the results of the leaching test of the relevant testing standards in the international drinking water project, the lead and cadmium content meets the requirements of international environmental protection restrictions, and does not cause pollution to the environment and human health.
  • the second lead-free low-cut brass alloy of the present invention has excellent cutting performance, dezincification resistance, thermoforming property and excellent casting property, and good mechanical properties and welding properties are beneficial to environmental protection and health. Safe new lead-free free-cutting brass alloy. Can be widely used in electronics, telecommunications, computers, drinking water engineering, hardware, machinery and electrical appliances, automotive parts casting and hot forging hot stamping, cutting parts manufacturing.
  • the alloy composition of the lead-free free-cutting low-cut brass alloy of the present invention is: copper: 55 to 64 wt%, ⁇ : 0.3 to 1.5 wt%, ⁇ : 0.05 to 1.0 wt%, boron: 0.0002 to 0.05 wt% , Other elements: 0.2 ⁇ 1.6 wt%, the balance is zinc and unavoidable impurities; the content of lead in the inevitable impurities is less than 0.03 wt%; the alloy composition is copper plus zinc plus lanthanum plus lanthanum plus more than 97 Wt%, and wherein zinc is greater than 35.5 wt%; the other element is at least two elements selected from the group consisting of titanium, nickel, iron, tin, phosphorus, rare earth metals.
  • the preferred composition of the lead-free free-cutting low-cut brass alloy is: copper: 58-63 wt%, ⁇ : 0.4-1.4 wt%, ⁇ : 0.06-0.8 wt%, boron: 0 fine 6 ⁇ 0.03 wt%, other elements: 0.2-1.3 wt% > balance is zinc and unavoidable impurities; lead content in unavoidable impurities is less than 0.03 wt%; copper and zinc in the alloy composition are added and twisted Boron is added more than 97.5% and not more than 99.8 wt%, wherein zinc is greater than 35.5 wt%; the other elements are at least two elements selected from the group consisting of titanium, nickel, iron, tin, phosphorus, rare earth metals .
  • phase composition of the lead-free free-cutting low-yield brass alloy is as follows: the two phases of ", ⁇ two phases are uniformly distributed in the free state in the crystal and the grain boundary, and a small amount is finely distributed uniformly in the grain boundary.
  • the hard-brittle phase of the solid solution-containing ruthenium-containing intermetallic compound is as follows: the two phases of ", ⁇ two phases are uniformly distributed in the free state in the crystal and the grain boundary, and a small amount is finely distributed uniformly in the grain boundary.
  • the hard-brittle phase of the solid solution-containing ruthenium-containing intermetallic compound is as follows: the two phases of ", ⁇ two phases are uniformly distributed in the free state in the crystal and the grain boundary, and a small amount is finely distributed uniformly in the grain boundary.
  • the hard-brittle phase of the solid solution-containing ruthenium-containing intermetallic compound is as follows: the two phases of ", ⁇ two phases are uniformly distributed in the free state in the crystal and
  • the third lead-free low-cut brass alloy is replaced by bismuth and antimony, mainly bismuth, and further improves the cutting performance of the alloy by bismuth.
  • boron is mainly used for bismuth, tin, etc. Auxiliary boron to improve the anti-dezincification performance of the alloy.
  • niobium improves the machinability of the alloy.
  • the solid solubility of bismuth in copper is extremely low. Even at 800 ⁇ , the solubility is only 0.01%, but the solubility in the melt is very large.
  • strontium precipitates and forms dispersed second phase particles.
  • the diffuse phase of the crucible has a low melting point (271.3 ° C), which is locally heated by the contact between the tip and the chip and melts instantaneously. This melting effect helps to change the shape of the chip and lubricate the tool, thereby enabling the alloy to be machined. It is easy to form short chip breaking points, reduce the bonding and welding between the cutter head and the workpiece, and improve the cutting speed. Have satisfactory cutting performance.
  • niobium when the content of niobium is more than 1.5%, it will lead to an increase in brittleness. For this reason, we use an alloying scheme based on the addition of a low content of rhodium and the addition of niobium which is easy to form a solid solution, so as to The bismuth metal compound (presented in the alloy in a solid solution, non-toxic, and health-promoting form) also accumulates in the vicinity of the grain boundary, which gives the alloy excellent cutting performance and other comprehensive properties, thus achieving The main purpose of the alloy is to further improve the cutting performance of the alloy, so that the alloy has excellent cutting performance like lead brass.
  • Tantalum and niobium are the elements that strengthen and improve the cutting performance of the alloy.
  • the niobium content of the alloy is less than 0.3%, the machinability is not satisfied, and when the niobium content is more than 1.5%, the cold and hot forming properties of the alloy are lowered and the mechanical properties of the alloy are drastically lowered, and the cost is also increased.
  • the content of niobium in the alloy is 0.3 to 1.5%.
  • Such content control can only make the cutting coefficient of the alloy reach about 80% under the condition of no other cutting elements such as niobium, but also add an auxiliary niobium element on the basis of the niobium content of 0.3 ⁇ 1.5%. It assists in the enthalpy and works together with hydrazine to obtain better cutting performance (cutting coefficient of 86 ⁇ 95%) and excellent corrosion resistance and mechanical properties, thus meeting the requirements of environmental protection, health and new alloy materials.
  • niobium element is mainly used to assist the crucible to further improve the cutting performance of the alloy and the unique effect of inhibiting dezincification.
  • addition content of niobium is less than 0.05%, the effect of improving the cutting performance of the auxiliary niobium is not obvious, and the effect of improving the anti-dezincification property is not obvious, and when the auxiliary addition content is more than 1.0%, although the auxiliary niobium improves the cutting performance, The plasticity reduction of the alloy is also very significant, while also increasing the cost.
  • the auxiliary strontium content is 0.05 ⁇ 1.0%, which can play an auxiliary role in improving the cutting performance of the alloy, so that the alloy has superior cutting performance (cutting coefficient is 86 ⁇ 95%) and resistance. Dezincification performance and excellent cold forming properties, weldability and good mechanical properties.
  • niobium Low levels of niobium have a certain solubility in both copper and zinc. Therefore, niobium is present in the alloy in a low-content, non-toxic solid solution state, insoluble in water, rather than being present in the alloy in a toxic free state like lead. Observed by electron probe and transmission electron microscopy, in this alloy, niobium preferentially forms a solid solution with zinc and accumulates near the grain boundary to form a short cutting point that is easy to cut, so that the embrittlement phase of the metal compound containing niobium is uniformly distributed in the grain boundary. Further, the cutting performance of the alloy is further improved.
  • the alloy is mainly boron, and boron is assisted by bismuth, tin and the like to improve the anti-dezincification performance of the alloy.
  • the addition of boron mainly serves to suppress dezincification and improve corrosion resistance, and also has functions of deoxidizing, refining grains, and enhancing cutting performance. Since the radius of the boron atom is smaller than the radius of the zinc atom, the boron atom is more easily diffused than the zinc atom when the brass is corroded, so that the vacancy can be preferentially blocked to block the diffusion channel of the zinc atom, and the resistance of the zinc diffusion is increased to form a corrosion-resistant protective film. The effect of suppressing dezincification corrosion like arsenic. At the same time, bismuth is also easy to form a solid solution compound with zinc, which can also inhibit dezincification, thereby assisting boron and cooperating with it to improve the anti-dezincification effect of the alloy.
  • the amount of boron added is preferably from 0.0002 to 0.05%.
  • the boron content is less than 0.0002%, the effect of inhibiting dezincification and corrosion resistance is not obvious; when the boron content is more than 0.05%, the boride is easily precipitated at the grain boundary, resulting in "boron brittleness" and lowering the alloy forming property.
  • the addition of trace amounts of tin and other elements to the brass further enhances the resistance to dezincification to the leaching standards of the relevant elements in the copper alloys specified by the International Drinking Water Authority and the ISO 6509 dezincification standard.
  • a zinc content greater than 35.5% contributes to improved cutting performance and enhanced wear resistance, but too high a temperature affects cold formability and alloy strength.
  • the other elements of the other elements are added by at least two elements of titanium, nickel, iron, tin, phosphorus, and rare earth metals, one is deoxidizing and refining crystal grains; the second is forming a metal compound with lead in impurities, strengthening The grain boundary, and the embrittlement phase of the ruthenium-containing metal compound is more finely and evenly distributed on the grain boundary, and at the same time, the tendency of the ⁇ phase and the ⁇ -containing embrittlement phase to be brittle and fractured can be suppressed, thereby satisfying the industrially demanding excellent Cutting performance, good cold forming performance and welding performance; Third, inhibiting dezincification, enhancing corrosion resistance and stress crack resistance.
  • the total content of the other elements is less than 0.2%, which does not achieve satisfactory cutting performance and grain boundary strengthening; the total amount of other elements is more than 1.6%, which can further refine the alloy and inhibit dezincification, but will form other more Hard and brittle phase, can not meet the cold forming performance of the latter step, but also increase the cost, affecting the promotion effect.
  • the addition of titanium mainly acts to deoxidize and refine the grains, and the amount of addition is generally 0.001 to 0.15%, preferably less than 0.001%. The effect is not obvious, more than 0.15% will increase the cost and reduce the casting performance.
  • Nickel is a matrix that strengthens and prevents dezincification, while inhibiting grain growth, increasing alloy strength, plasticity and corrosion resistance, while also improving the ability of the alloy to resist stress corrosion. If the nickel content is less than 0.1%, it is difficult to meet the various performance requirements required by the industry. If the nickel content is more than 0.6%, the alloy manufacturing cost will be increased and the cutting performance will be lowered. Therefore, the nickel content should be controlled at 0.1 to 0.6%.
  • Iron and rare earth metals are mainly used to refine grains, prevent grain growth, and control the number of ⁇ phase transitions. They can improve softening point, enhance strength, and improve hot and cold forming properties. Another important role of rare earth metals is deoxidation.
  • the iron content is generally controlled at 0.1 to 0.3%, the iron content is less than 0.1%, and the grain refining effect is not significant; the iron content is more than 0.3%, which lowers the corrosion resistance and the electroplatability.
  • Rare earth metal is an excellent modifier and refining agent. It is hardly soluble in copper. It forms a high melting point metal compound with lead in the alloy. It is distributed in the crystal to improve the plasticity and wear resistance of the alloy. Refinement, promote the finer and evenly distributed metal compounds on the grain boundary, generally adding 0.003 ⁇ 0.4%, adding cerium-based mixed rare earth effect is better, can increase conductivity and resistance to dezincification, too high Reduce the fluidity of the alloy.
  • tin and phosphorus is also auxiliary boron to enhance the resistance to dezincification and stress cracking and to improve the hot forming properties to meet the international environmental health and safety standards.
  • adding tin and phosphorus to the brass can also deoxidize, increase the fluidity of the alloy, and improve the cutting performance and strength of the alloy.
  • Tin is an element that solid solution strengthens and inhibits dezincification. It strengthens the matrix together with ⁇ > boron and phosphorus, which is beneficial to the uniform dispersion of each phase and the formation of strengthening phase, which is beneficial to the improvement of strength, wear resistance and cutting performance, especially It is beneficial to the anti-dezincification performance and the improvement of thermoforming performance.
  • the phosphorus content is generally controlled to be 0.005 to 0.2%.
  • the tin content is generally controlled to be 0.1 to 0.4%, which may reduce the cutting performance.
  • Lead and cadmium even as an inevitable impurity element, must have a lead content of less than 0.03% and a cadmium content of less than 0.001%. This lead and cadmium content meets the requirements of international environmental protection restrictions, and does not cause pollution to the environment and human health, and adapts to the future development trend of new environmentally friendly materials.
  • the above-mentioned third lead-free free-cutting brass alloy of the present invention has excellent cutting performance, excellent resistance to dezincification corrosion, stress corrosion resistance, good cold-hot forming property, mechanical property and welding property.
  • a new lead-free free-cutting brass alloy that is environmentally friendly and healthy with more stringent requirements for hygienic safety. It can be widely used in the electronics, telecommunications, computer, drinking water engineering, hardware, machinery, photographic equipment, optoelectronic components, children's toys, home appliances, automotive parts casting and cold forming, free cutting parts manufacturing.
  • the alloy of the present invention is produced by weight copper: 55 to 65 wt%, ⁇ : 0.3 to 1.5 wt%, ⁇ : 0.05 to 1.0 wt%, boron: 0.0002 to 0.05 wt%, and other elements: 0.2 to 1.2 wt%.
  • the remainder is an alloy composition composed of zinc and unavoidable impurities.
  • the alloying and covering protection method is used to melt the low-barium brass alloy, so that boron and bismuth are rapidly dissolved into the intermetallic compound in the brass melt, and
  • the metal ruthenium is evenly distributed in the crystal and grain boundary, and is continuously cast into an ingot at 1040 ° C (the maximum temperature of the brass in the whole smelting process is 1080 ° C, far below the boiling point temperature of 1675 ⁇ for evaporating the metal ruthenium) And the boiling point temperature of the metal lanthanum is 1680 ° C, so it will not cause harm to humans and the environment.
  • the extrusion is performed at a temperature of 680-760 ° C.
  • the intermediate heat treatment is in the cold working condition at 500 ⁇ 700 °. Performing at C temperature, stress relief annealing can be performed at temperatures below 400 ⁇ .
  • the advantages of the invention are as follows: 1. Excellent cutting performance, excellent dezincification resistance, good welding performance, excellent corrosion resistance and mechanical properties, and is particularly suitable for cutting and forming. Parts, forgings, castings and parts and components as other manufacturing methods; 2. Low manufacturing cost, which is equivalent to the manufacturing cost of lead brass of the prior art, and thus has a competitive advantage in the market; 3. It can fully meet international environmental protection, Health and safety standards and requirements, and provide another new environmentally friendly and healthy lead-free free-cutting low-brass brass alloy material for the world's circular economy.
  • Fig. 1 Schematic diagram of the shape of the scrap of the alloy of the present invention, the turning back knife is 0.5 mm, the spindle speed is 900 rpm/min, and the feed rate is 0.1 mm/rev.
  • the lead-free free-cutting low-yield brass alloy of the present invention is ingot, extruded, and drawn into a round bar according to the alloy composition in the following tables; the comparative sample is a lead-containing brass grade C36000 alloy of the United States, which is The world's recognized machinability (100%) of the best leaded brass is also processed in the same way.
  • the production process is as follows: Raw material preparation and ingredients - alloying treatment smelting - continuous ingot casting - ingot heating one by one extrusion - stretching - heat treatment - pickling - stretching - straightening polishing - stress relief annealing - - Inspection of finished packaging.
  • the alloying treatment and the cover protection method are used to melt the low-barium brass alloy, so that boron and bismuth are rapidly dissolved into the intermetallic compound in the brass melt, and the metal ruthenium is uniformly distributed in the crystal and Grain boundary, and continuous casting into ingot at 1040 °C, large extrusion ratio extrusion at 680 ⁇ 760 °C, intermediate heat treatment according to cold working conditions at 500 ⁇ 70 (TC temperature, below Stress relief annealing is possible at a temperature of 400 °C.
  • the process of transferring the heat treatment process proves that the stress relief annealing with heat treatment below 400 °C can be carried out, and the intermediate heat treatment needs to be performed at 500 ⁇ 70 according to the cold working conditions (it should be avoided at TC temperature, but should be avoided) Open medium temperature brittle zone annealing (the process is generally the same as conventional lead brass alloy production).
  • the ingot of various series of inventive alloys of the lead-free free-cutting low-yield brass alloy of the invention has a size of ⁇ 170*400 ⁇ 500 mm, under the same equipment conditions and different extrusion temperatures of 680 ° C to 760 ° C Next, the wire is extruded into ⁇ 9 and ⁇ 10 mm, and the specific composition contents thereof are shown in Table 11, Table 12, and Table 13.
  • Table 11 Example composition of one of the inventions of the lead-free free-cutting low-yield brass alloy of the present invention: (% by weight)
  • Table 12 Example of composition of the second invention of the lead-free free-cutting low-yield brass alloy of the present invention: (% by weight)
  • Example composition composition of the third invention of the lead-free free-cut low-yield brass alloy of the present invention (% by weight) 0. 2, (where -012 60. 23 1. 26 0. 14 0. 0018 balance 01. 106 0. 110 0. 139 0. 0123 Pb ⁇ 0. 03, Cd
  • each cutting resistance is based on the average value of the cutting force measured by the experiment.
  • the machinability of the alloy of the invention can reach more than 88% of the conventional lead-containing brass C36000, and the cutting performance is excellent.
  • the alloy of the present invention is also combined with the Cu-Zn-Bi alloy of the United States NAKAYAMA company, The Cu-Zn-Si alloy of this Sambo company was compared, and the comprehensive machining performance of the alloy of the invention was obtained by cutting and drilling. The results are shown in Table 16. Comparison of Machining Comprehensive Cutting Performance between Invented Alloy and Comparative Alloy
  • the lead-free, low-cut brass alloy of the present invention is superior to C36000 lead-containing yellow copper in dezincification resistance.
  • the stress corrosion test of the lead-free free-cutting low-ruthness brass alloy of the present invention was carried out, and the comparative sample was C36000 lead-containing brass.
  • the lead-free low-cut brass alloy and the C36000 lead-containing brass of the present invention were tested for room temperature conductivity.
  • the test results are shown in Table 19: The lead-free free-cutting low-ruthenium brass alloy and the C36000 lead-containing brass of the present invention. Room temperature conductivity comparison
  • the melting point is shown in Table 20. Comparison of the melting points of the lead-free free-cutting low-ruthenium brass alloy and the C36000 lead-containing brass of the present invention
  • the above various experimental results also prove that the lead-free free-cut low-brass brass alloy of the present invention is excellent in cutting performance, mechanical strength and corrosion resistance.
  • the raw material cost is 5% or more lower than the same type of lead-free brass alloy (Cu-Zn-Bi alloy) in the United States; it is 11% lower than the same type of lead-free brass alloy (Cu-Zn-Si alloy) of Japan Sambo; But it costs 2% more than the traditional C36000 leaded brass material.
  • the lead-free free-cutting low-yarn brass alloy of the present invention is a lead-free free-cutting brass alloy having excellent cutting properties, corrosion resistance, dezincification resistance, and excellent mechanical properties.
  • the faucets, parts of the automobile and instrument manufacturing industry, heat exchanger connectors, luminaire parts, gas nozzles, etc. all have high use value, and also meet the international ecological environmental health, safety and hygiene standards.

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Abstract

La présente invention concerne un nouvel alliage en laiton écologique sans plomb à découpe libre qui présente une faible teneur en antimoine et bismuth, et sa préparation. L’alliage en laiton contient : du Cu dont les valeurs sont comprises entre 55 et 65 wt%, du Bi dont les valeurs sont comprises entre 0,3 et 1,5 wt%, du Sb dont les valeurs sont comprises entre 0,05 et 1,0 wt%, du B dont les valeurs sont comprises entre 0,0002 et 0,05 wt%, d’autres éléments dont les valeurs sont comprises entre 0,2 et 1,2 wt%, le reste étant du Zn et des impuretés inévitables ; les impuretés inévitables ont une teneur en Pb inférieure à 0,1 wt% ; la teneur totale en Cu, Zn, Bi, Sb et B est supérieure à 97 wt%, et la part de Zn dans cette teneur totale est supérieure à 35,5 wt% ; les autres éléments comprennent au moins deux éléments sélectionnés dans le groupe constitué par le Ti, le Ni, le Fe, le Sn, le P et les métaux de terre rares. La préparation de l’alliage consiste à : faire fondre l’alliage en laiton présentant une faible teneur en antimoine et bismuth en le soumettant à un traitement d’alliage, à des procédés de recouvrement et de protection afin d’obtenir rapidement des solutés solides de B et Sb pour former un composé intermétallique, et distribuer uniformément le Bi dans le grain et aux limites du grain ; faire couler le composé de manière continue dans un lingot de laiton à 1040 °C ; effectuer une extrusion à une température comprise entre 680 et 760 °C et à un coefficient d’extrusion élevé ; effectuer le traitement thermique intermédiaire à une température comprise entre 500 et 700 °C, valeurs correspondant aux conditions d’écrouissage ; et recuire à une température inférieures à 400 °C pour éliminer les contraintes. L’alliage de la présente invention possède une excellente performance de découpe, une excellente résistance à la dézincification, une bonne résistance aux fissures par contrainte et une bonne performance mécanique, et est spécialement adapté lors d’une découpe de parties façonnées, de parties forgées, lors d’un coulage, etc. En outre, l’alliage de la présente invention présente un faible coût de production, et répond aux exigences des normes internationales ainsi qu’aux spécifications écologiques et sanitaires.
PCT/CN2005/001399 2005-06-24 2005-09-05 Nouvel alliage de laiton écologique sans plomb à découpe libre qui présente une faible teneur en antimoine et bismuth, et sa préparation WO2006136065A1 (fr)

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WO2011020468A1 (fr) * 2009-08-18 2011-02-24 Aurubis Stolberg Gmbh & Co. Kg Alliage de laiton
US8097208B2 (en) 2009-08-12 2012-01-17 G&W Electric Company White copper-base alloy
US8273192B2 (en) 2008-06-11 2012-09-25 Xiamen Lota International Co., Ltd. Lead-free, bismuth-free free-cutting phosphorous brass alloy
CN113802038A (zh) * 2021-09-03 2021-12-17 中信戴卡股份有限公司 一种车轮用镁合金及其制备方法
DE112021004805T5 (de) 2020-11-13 2023-07-27 T.C. Marmara Üni̇versi̇tesi̇ Herstellung einer bleifreien messinglegierung mit verbesserter bearbeitbarkeit

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CN101812609B (zh) * 2009-03-20 2011-09-21 河南科技大学 一种导电耐磨材料及其制备方法
CN102477498A (zh) * 2010-11-26 2012-05-30 摩登岛股份有限公司 易切削的环保黄铜合金
CN102560190B (zh) * 2012-01-30 2013-09-18 九星控股集团有限公司 一种高锌无铅黄铜合金及制备方法
CN104726743B (zh) * 2013-12-18 2017-08-04 财团法人金属工业研究发展中心 黄铜合金及其制造方法
CN105886836A (zh) * 2016-06-23 2016-08-24 龙岩市鸿航金属科技有限公司 无铅易切削黄铜管的生产方法
CN105925837A (zh) * 2016-06-23 2016-09-07 龙岩市鸿航金属科技有限公司 抗脱锌易切削黄铜棒及其生产方法
CN105886835A (zh) * 2016-06-23 2016-08-24 龙岩市鸿航金属科技有限公司 无铅易切削硅铋黄铜及其制备方法
WO2021134210A1 (fr) * 2019-12-30 2021-07-08 华亿轴承科技（江苏）有限公司 Procédé de préparation de matériau de palier sans huile
CN113504100B (zh) * 2021-06-23 2024-03-12 宁波金田铜业(集团)股份有限公司 一种黄铜光谱标样的制备方法

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US8273192B2 (en) 2008-06-11 2012-09-25 Xiamen Lota International Co., Ltd. Lead-free, bismuth-free free-cutting phosphorous brass alloy
US8097208B2 (en) 2009-08-12 2012-01-17 G&W Electric Company White copper-base alloy
WO2011020468A1 (fr) * 2009-08-18 2011-02-24 Aurubis Stolberg Gmbh & Co. Kg Alliage de laiton
DE112021004805T5 (de) 2020-11-13 2023-07-27 T.C. Marmara Üni̇versi̇tesi̇ Herstellung einer bleifreien messinglegierung mit verbesserter bearbeitbarkeit
CN113802038A (zh) * 2021-09-03 2021-12-17 中信戴卡股份有限公司 一种车轮用镁合金及其制备方法
US11905577B2 (en) 2021-09-03 2024-02-20 Citic Dicastal Co., Ltd. Magnesium alloy for wheel and preparation method thereof

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