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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French (fr)
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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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NINGBO POWERWAY GROUP CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/04Alloys based on copper with zinc as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing 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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Description

生态环保新型无铅易切削低锑铋黄铜合金及其制造方法 技术领域
本发明涉及一种不含铅的黄铜合金, 尤其涉及一种具有优异的切削性能、机械性能 和耐腐蚀性能的无铅易切削低锑铋黄铜合金 (PWEHSCBRASS)。 它特别适用于电子、 电 讯器械、 电脑的接插件; 家用电气; 灯具和照相器材的光 ¾部件; 儿童玩具以及机械与 汽车制造业中的零部件; 供水系统管道铸件、 阔件、 开关连接件制造等领域。 它是一种 有利于人类健康与环境保护的新型金属材料,也是目前广泛应用的会引起对人体和环境 有恶劣影响的铅黄铜的又一新型理想替代品。 背景技术
铅黄铜具有优良的冷热加工性能、极好的切削性能和自润滑等特点, 能满足各种形状 零部件的机加工, 因此含铅黄铜也就被世界公认为重要的基础材料而广泛应用到电子、 电 讯、 电脑部件、 民用供水系统的管路铸件及配件、家电与儿童玩具的零部件、灯具和照相 器材的光电部件、 汽车及机械制造业的零部件制造等广泛领域。
然而铅是一种对环境和对人体有害的元素,铅对人体血液和神经系统特别是对儿童的 肾和脑神经会造成不可逆转的损伤,严重的会造成血铅、脑铅中毒、神经受阻、智力迟钝。 近年来世界各国的医学专家已发现含铅黄铜对人类健康和环境卫生构成了威胁, 北欧、美 国、 日本和中国等医学研究机构均已做出了铅黄铜对人类环境造成危害的报告, 2004年 2 月世界卫生组织儿童合作中心在中国 15个城市对 1.7万名儿童进行了铅中毒调查,其中儿 童玩具被列为导致儿童铅中毒的危险因素之一,因而各国政府也相继出台了对含铅铜合金 应用的政府限令。 中国政府近期也相继出台了与国际限令相一致的《电子信息产品污染防 治管理办法》等强制性法规。
鉴于上述原因, 近几年特别是 2003年以来, 美国、 欧共体、 日本、 中国等国家对铜 合金中的铅含量(其中电子信息产品铅的含量必须小于 0.1%)和在饮用水中铅的浸出量 分别做出了严格控制的限令, 并将不断减少其中的铅含量, 因而含铅黄铜的应用将面临严 格的限制和挑战, 因此相继开发无铅易切削铜合金来替代含铅铜合金, 是当今世界金属材 料制造业所面临的刻不容缓的重大课题, 也是国际实施 EHS计划 (E: 环保, H: 健康, S: 安全) 的世界循环经济所必须解决的重大课题。
目前国外如美国、德国和日本也发明了不含铅的黄铜合金, 其中例如中国专利申请号 02121991.5说明书中已公开的《无铅易切削黄铜合金材料和它的制造方法》, 是日本三越 金属株式会社发明的无铅易切削黄铜合金材料, 其成分及制造方法分别是: 该合金含有重 4%: 铜: 60.0〜62.0%、铋: 0.5-2.2%,铝: 0.01-0.1 % ,锡: 0.5〜1.6%、磷: 0.04- 0.15%、其余为锌和不可避免的杂质成分,在 460〜600°C温度下进行 30分〜 4小时热处理, 以 70Ό/小时以下的冷却速度缓冷。 另一个发明是德国威兰德公司研发的专利申请号为 200410004293的《无铅铜合金和其应用》,该合金由下列成分组成:铜: 70.0〜83.0%、硅: 1〜5%、锡- 0.01〜2%、铁: 0.01〜0.3%和/或钴: 0.01〜0.3%、镍: 0.01〜0.3%、锰: 0.01- 0.3%, 佘量为锌和不可避免的杂质。 发明内容
本发明的目的是为了提供一种不含铅的具有优异切削性、冷热成型性和良好的焊接性 及优良的机械性能, 同时又具有优异的耐蚀性能, 并可替代含铅铜合金且不会造成环境污 染和有利于人类健康的新型无铅易切削低锑铋黄铜合金,同时又不同于国外的含铋黄铜合 金及其制造方法。
本发明的目的是通过提供具有如下各列合金组成的无铅易切削低锑铋黄铜合金而实 现的:
本发明无铅易切削低锑铋黄铜合金之一的合金组成为: 铜: 55~65wt%、 铋: 0.3〜 1.5 wt%、锑: 0.05〜L0 wt%、 硼: 0.0002〜0.05 wt%、其它元素: 0.2〜1.2 wt%、 余量 为锌和不可避免的杂质; 不可避免的杂质中铅的含量小于 0.1 wt% ; 所述的合金组成中 铜加锌加铋加锑加硼大于 97 wt%, 且其中锌大于 35.5 wt% ; 所述的其它元素是选自以 下元素中的至少两种元素: 钛、 镍、 铁、 锡、 磷、 稀土金属。 所述的无铅易切削低锑铋黄铜合金之一的较佳组成为:铜: 58〜63 wt%、 铋: 0.4〜 1.4 wt%、 锑: 0.06〜0.8 wt%、 硼: 0.0006〜0.03 wt%、 其它元素: 0.2〜1.0 wt%、 余量 为锌和不可避免的杂质; 不可避免的杂质中铅的含量小于 0.1 wt% ; 所述的合金组成中 铜加锌加铋加锑加硼大于 97.5 ^%且不大于 99.8 wt%, 其中锌大于 35.5 wt%; 所述的 其它元素是选自以下元素中的至少两种元素: 钛、 镍、 铁、 锡、 磷、 稀土金属。
所述的无铅易切削低锑铋黄铜合金之一的相组成为: 以。、 β两相为主, 以游离态均 勾分布于晶内和晶界的铋相,少量细小均匀分布于晶界的固溶态的含锑金属间化合物的硬 脆相。
所述的无铅易切削低锑铋黄铜合金之一是利用铋和锑替代铅, 以铋为主, 用锑辅助 铋进一步提高合金的切削性能; 同时以硼为主, 用锑、锡等辅助硼来提高合金的抗脱锌 性能。
铋的加入可改进合金的切削性。 铋在铜中的固溶度极低, 即使 800Ό时的溶解度也 只不过 0.01%, 但熔液中的溶解度却很大, 在凝固过程中铋发生沉淀, 形成弥散的第二 相粒子, 这种铋的弥散相熔点较低 (271.3°C ), 在刀头与屑的接触面局部受热而瞬间熔 化, 这种熔化效应有助于改变切屑的形状并润滑刀具, 从而起到使合金在机加工中易形 成短断屑点, 减少刀头和工件之间的粘结和焊合及提高切削速度的作用, 进而使合金具 有了满意的切削性能。 但铋含量大于 1.5%时, 会导致脆断性增大, 为此我们采用以加 低含量的铋为主和以加入易形成固溶体的锑为辅的合金化方案,使易切削断屑的含锑的 金属化合物(以固溶无毒、 有利健康的形态存在于合金中)脆化相也聚集在晶界附近, 使本合金获得了更优异的切削性能和其它综合性能, 从而达到了以铋为主, 用锑辅助铋 来进一步提高合金的切削性能的目的, 使本合金获得了象铅黄铜一样优异的切削性能。 同时又添加一些细化晶粒、抑制脱锌和控制合金脆断倾向的微量其它元素,进而使含锑的 金属化合物更加细小均勾地分布在晶界上, 并使金属铋均匀分布于晶内和晶界, 使合金在 机加工中易形成短断屑点, 有效地增加了合金的切削性能和耐蚀抗脱锌性等综合性能, 从 而偉低锑铋黄铜合金获得了象铅黄铜那样优异的切削性能、优良的冷热成型性能、铸造性 能、 焊接性能和机械性能。 可广泛应用在电子、 电讯、 电脑、 饮用水工程、 五金、 机械、 照相器材的光电部件、 家电、 汽车零部件的铸造和冷热成型、 易切削零部件制造业。
铋和锑是强化和改善合金切削性能的元素, 以铋为主, 用锑辅助铋。在本合金中铋 含量小于 0.3%时, 满足不了切削性要求, 铋含量大于 1.5%时, 将降低合金的冷、 热成 型性能并使合金的机械性能急剧下降, 同时也增加了成本。 为充分利用铋能提高切削性 能的特性, 同时还要防止过量铋会导致冷、 热成型性能和机械性能下降的脆断倾向, 在 合金中铋的含量为 0.3〜1.5%。 这样的含量控制在不含锑等其它切削元素的条件下, 只 能使该合金的切削系数达到 80%左右, 但在铋含量为 0.3〜1.5%的基础上还同时添加了 辅助的锑元素,使之辅助铋并与铋共同作用获得了更优异的切削性能(切削系数为 86〜 95%)和优良的耐蚀性能、 机械性能, 进而达到环保、 健康、 新型合金材料的要求。
辅助添加适当含量的锑元素,主要是起辅助铋进一步提高合金的切削性能和特有的抑 制脱锌性能的作用。 当锑的添加含量小于 0.05%时, 对辅助铋提高切削性能效果不明显, 且对提高抗脱锌性作用不明显, 而辅助添加含量大于 1.0%时, 虽辅助铋提高切削性能较 大, 但本合金的塑性降低也非常明显, 同时还增加了成本。故经实践证明辅助添加锑的含 量为 0.05〜1.0%,就可以起到辅助铋提高本合金的切削性能的作用,使该合金更具有优异 的切削性能(切削系数为 86~95%)、 抗脱锌性能和优良的冷热成型性能、 焊接性能及良 好的机械性能。
铋在铜中的溶解度极低, 铋也是以游离态存在于合金中。但与铅不同的是, 铋是以无 毒的游离态存在于合金中, 而不是象铅那样以有毒的游离态存在于合金中。 WHO (世界 卫生组织)饮用水水质控制标准中没有对铋的限制值, 也还没有人指出铋是对人体有害的 物质。
低含量的锑在铜和锌中均有一定的溶解度,因此锑是以低含量无毒的固溶态存在于合 金中, 不溶于水, 而不是象铅那样以有毒的游离态存在于合金中。经电子探针和透射电镜 观察, 在本合金中锑优先与锌形成固溶体, 并聚集在晶界附近, 形成易切削的短断屑点, 使得含锑的金属化合物脆化相均匀分布在晶界上, 进一步提高了该合金的切削性能。
本合金以硼为主, 用锑、锡等辅助硼来提高合金的抗脱锌性能。添加硼元素主要是起 抑制脱锌、 提高耐蚀性能的作用, 同时也有脱氧、 细化晶粒、 增强切削性能的功能。 由于 硼原子半径比锌原子半径小, 黄铜被腐蚀时硼原子比锌原子更易扩散, 因此可优先夺取空 位进而堵塞锌原子的扩散通道, 增加锌扩散的阻力, 形成耐蚀保护膜, 从而达到象砷一样 的抑制脱锌腐蚀的效果。 同时锑也容易和锌形成固熔体化合物, 同样可抑制脱锌, 从而起 到辅助硼并与之共同作用提高合金抗脱锌性的效果。 硼的加入量在 0.0002〜0.05%为宜。 硼含量小于 0.0002%时, X寸抑制脱锌和耐蚀效果 不明显; 硼含量大于 0.05%时, 硼化物易在晶界析出, 造成 "硼脆 ", 降低合金成型性能。
除了加硼外, 在该黄铜中添加微量锡等其它元素可进一步提高抗脱锌性能, 使之达到 国际饮用水机构所规定的铜合金中相关元素的浸出标准和 ISO6509脱锌标准。
锌含量大于 35.5%有利于切削性能的提高和耐磨性能的增强, 但过高会影响冷成型性 能和合金强度。 - 所述的其它元素中的钛、 镍、 铁、 锡、 磷、 稀土金属中的至少两种元素加入的作用, 一是脱氧、细化晶粒; 二是与杂质中的铅形成金属化合物, 强化晶界, 并使含锑的金属化 合物脆化相更加细小均勾地分布在晶界上, 并使金属铋均匀分布于晶内和晶界, 同时还可 抑制铋相和含锑的脆化相偏聚脆断倾向,进而满足工业上需要的优异的切削性能、优良的 冷热成型性能和焊接性能; 三是抑制脱锌、增强耐蚀性能和抗应力裂性能。所述的其它元 素总含量小于 0.2%达不到满意的切削性能和晶界强化作用; 其它元素总量大于 1.2%, 虽 能使合金进一步细化, 抑制脱锌, 但会形成其它更多的硬脆相, 满足不了后步的冷成型性 能, 同时也增加了成本, 影响推广使用效果。
添加钛主要是起脱氧和细化晶粒作用,一般添加量为 0.001〜0.15%为宜,小于 0.001% 效果不明显, 大于 0.15%会增加成本, 并使铸造性能降低。
镍是基体强化和阻止脱锌元素,同时抑制晶粒长大,增加合金强度、塑性和耐蚀性, 同时还可提高合金抗应力腐蚀的能力。 镍含量少于 0.1 %, 难以满足工业上需要的各项 性能要求, 镍含量大于 0.6%又会增加合金的制造成本并降低切削性能, 故镍含量应控 制在 0.1〜0.6%。
铁和稀土金属主要是起细化晶粒、 阻止晶粒长大、控制 β相转变数量的作用, 能提高 软化点、增强强度, 提高冷热成型性能。稀土金属的另一个重要作用是脱氧。铁含量一般 控制在 0.1〜0.3%, 铁含量小于 0.1%,细化晶粒效果不明显; 铁含量大于 0.3%,会降低耐 蚀性能和可电镀性能。稀土金属是优良的变质剂和精炼净化剂, 几乎不固溶于铜, 它会与 合金中的杂质铅形成高熔点金属化合物, 分布在晶内, 提高合金的塑性、耐磨性, 促使晶 粒细化, 促成晶界上的金属化合物更加细小均匀分布, 一般加入量为 0.003〜0.4%, 加入 以镧为基的混合稀土效果更好, 可增加导电率和抗脱锌能力, 过高会降低合金的流动性。
与锑一样, 添加锡、磷也是辅助硼来增强抗脱锌、抗应力裂的性能和提高热加工成型 性能, 使之达到国际环保健康安全规定的标准。 其次在该黄铜中添加锡、 磷还可以脱氧、 增加合金的流动性,提髙合金的切削性能和强度。锡是固溶强化和抑制脱锌的元素,和锑、 硼、磷一起强化基体, 有利于各相的分散均匀和强化相的形成, 有利于强度、耐磨性和切 削性能的提高, 特别是有利于抗脱锌性能和热成型性能的提高。 磷的含量一般控制在
0.005〜0.2%为宜。 锡的含量一般控制在 0.1〜0.4%为宜, 过高会降低切削性能。
铅和镉即使是作为不可避免的杂质元素, 杂质中的铅含量也必须是小于 0.1%, 镉含 量必须是小于 0.001%。 根据国际饮用水工程中的相关检测标准的浸出量检测结果, 这种 铅、 镉含量既符合国际环保限令要求, 又不会给环境和人类健康造成公害。
上述的本发明无铅易切削低锑铋黄铜合金之一是具有优异的切削性能、 抗脱锌性能、 抗应力腐蚀性能,优良的机械性能和冷热成型性能及优良的焊接性能的有利于环保、健康 的新型无铅易切削黄铜合金。可广泛应用在电子、 电讯、 电脑、饮用水工程、五金、机械、 照相器材的光电部件、 家电、 汽车零部件的铸造和冷热成型、 易切削零部件制造业。
本发明无铅易切削低锑铋黄铜合金之二的合金组成为:铜: 55〜63 wt%、 铋: 0.3〜 1.5 wt% , 锑: 0.05〜1.0 wt%、 镍: 0.1〜0.6 wt%、 硼: 0.0002〜0.05 wt%、 其它元素: 0.2-1.5 wt% ,余量为锌和不可避免的杂质; 不可避 '免的杂质中铅的含量小于 0.1 wt% ; 所述的合金组成中铜加锌加铋加锑加硼大于 97 wt%, 且其中锌大于 36.5 wt% ; 所述的 其它元素是选自以下元素中的至少两种元素: 钛、 铁、 硅、 锡、 磷、 稀土金属。
所述的无铅易切削低锑秘黄铜合金之二的较佳组成为:铜: 57〜62 wt%、 秘: 0.4〜 1.4 t%、 锑: 0.06〜0.8 wt%、 镍: 0.1〜0.5 wt%、 硼: 0.0006〜0.03 wt%、 其它元素: 0.2〜1.2 wt%、余量为锌和不可避免的杂质; 不可避免的杂质中铅的含量小于 0.1 wt% ; 所述的合金组成中铜加锌加铋加锑加硼大于 97.5 ^%且不大于 99.8 wt% , 其中锌大于 36.5 wt ; 所述的其它元素是选自以下元素中的至少两种元素: 钛、 铁、 硅、 锡、 磷、 稀土金属。
所述的无铅易切削低锑秘黄铜合金之二的相组成为: 以^、 P两相为主, 以游离态均 匀分布于晶内和晶界的铋相,少量细小均匀分布于晶界的固溶态的含锑金属间化合物的硬 脆相。
所述的无铅易切削低锑铋黄铜合金之二是利用铋和锑替代铅, 以铋为主, 用锑辅助 铋进一步提高合金的切削性能; 同时以硼为主, 用锑、锡等辅助硼来提高合金的抗脱锌 性能。
铋的加入可改进合金的切削性。 铋在铜中的固溶度极低, 即使 800°C时的溶解度也 只不过 0.01%, 但熔液中的溶解度却很大, 在凝固过程中铋发生沉淀, 形成弥散的第二 相粒子, 这种铋的弥散相熔点较低 (271.3 °C ), 在刀头与屑的接触面局部受热而瞬间熔 化, 这种熔化效应有助于改变切屑的形状并润滑刀具, 从而起到使合金在机加工中易形 成短断屑点, 减少刀头和工件之间的粘结和焊合及提高切削速度的作用, 进而使合金具 有了满意的切削性能。 但铋含量大于 1.5%时, 会导致脆断性增大, 为此我们采用以加 低含量的铋为主和以加入易形成固溶体的锑为辅的合金化方案,使易切削断屑的含锑的 金属化合物 (以固溶无毒、 有利健康的形态存在于合金中)脆化相也聚集在晶界附近, 使本合金获得了更优异的切削性能和其它综合性能, 从而达到了以铋为主, 用锑辅助铋 来进一步提高合金的切削性能的目的, 使本合金获得了象铅黄铜一样优异的切削性能。 同时又添加一些细化晶粒、抑制脱锌和控制合金脆断倾向的微量其它元素,进而使含锑的 金属化合物更加细小均匀地分布在晶界上, 并使金属铋均匀分布于晶内和晶界, 使合金在 机加工中易形成短断屑点, 有效地增加了合金的切削性能和耐蚀抗脱锌性等综合性能, 从 而使低锑铋黄铜合金获得了象铅黄铜那样优异的切削性能、优良的热成型性能、铸造性能、 焊接性能和机械性能。 可广泛应用在电子、 电讯、 电脑、 饮用水工程、 五金、 机械、 照枏 器材的光电部件、 家电、 汽车零部件的铸造和热成型、 易切削零部件制造业。
铋和锑是强化和改善合金切削性能的元素, 以铋为主, 用锑辅助铋。在本合金中铋 含量小于 0.3%时, 满足不了切削性要求, 铋含量大于 1.5%时, 降低合金的冷、 热成型 性能并使合金的机械性能急剧下降, 同时也增加了成本。 为充分利用铋能提高切削性能 的特性, 同时还要防止过量铋会导致冷、 热成型性能和机械性能下降的脆断倾向, 在合 金中铋的含量为 0.3〜1.5%。 这样的含量控制在不含锑等其它切削元素的条件下, 只能 使该合金的切削系数达到 80%左右, 但在铋含量为 0.3〜1.5%的基础上还同时添加了辅 助的锑元素, 使之辅助鉍并与铋共同作用获得了更优异的切削性能 (切削系数为 86〜 95%)和优良的耐蚀性能、 机械性能, 进而达到环保、 健康、 新型合金材料的要求。
辅助添加适当含量的锑元素,主要是起辅助鉍进一步提高合金的切削性能和特有的抑 制脱锌性能的作用。 当锑的添加含量小于 0.05%时, 对辅助铋提高切削性能效果不明显, 且对提高抗脱锌性作用不明显, 而辅助添加含量大于 1.0%时, 虽辅助铋提高切削性能较 大, 但本合金的塑性降低也非常明显, 同时还增加了成本。故经实践证明辅助添加锑的含 量为 0.05〜1.0%,就可以起到辅助铋提高本合金的切削性能的作用,使该合金更具有优异 的切削性能(切削系数为 86〜95%)、 抗脱锌性能和优良的热成型性能、 焊接性能及良好 的机械性能。
铋在铜中的溶解度极低, 铋也是以游离态存在于合金中。但与铅不同的是,铋是以无 毒的游离态存在于合金中, 而不是象铅那样以有毒的游离态存在于合金中。 WHO (世界 卫生组织)饮用水水质控制标准中.没有对铋的限制值, 也还没有人指出铋是对人体有害的 物质。
低含量的锑在铜和锌中均有一定的溶解度,因此锑是以低含量无毒的固溶态存在于合 金中, 不溶于水, 而不是象铅那样以有毒的游离态存在于合金中。经电子探针和透射电镜 观察, 在本合金中锑优先与锌形成固溶体, 并聚集在晶界附近, 形成易切削的短断屑点, 使得含锑的金属化合物脆化相均匀分布在晶界上, 进一步提高了该合金的切削性能。
镍是基体强化和阻止脱锌元素,同时抑制晶粒长大,增加合金强度、塑性和耐蚀性, 同时还可提高合金抗应力腐蚀的能力。 镍含量少于 0.1 %, 难以满足工业上需要的各项 性能要求, 镍含量大于 0.6%又会增加合金的制造成本并降低切削性能, 故镍含量应控 制在 0.1〜0.6%。
本合金以硼为主, 用锑、锡等辅助硼来提高合金的抗脱锌性能。添加硼元素主要是起 抑制脱锌、提高耐蚀性能的作用, 同时也有脱氧、 细化晶粒、增强切削性能的功能。 由于 硼原子半径比锌原子半径小,黄铜被腐蚀时硼原子比锌原子更易扩散, 因此可优先夺取空 位进而堵塞锌原子的扩散通道, 增加锌扩散的阻力, 形成耐蚀保护膜, 从而达到象砷一样 的抑制脱锌腐蚀的效果。 同时锑也容易和锌形成固熔体化合物, 同样可抑制脱锌, 从而起 到辅助硼并与之共同作用提高合金抗脱锌性的效果。
硼的加入量在 0.0002〜0.05%为宜。硼含量小于 0.0002%时, 对抑制脱锌和耐蚀效果 不明显; 硼含量大于 0.05%时, 硼化物易在晶界析出, 造成 "硼脆", 降低合金成型性能。
除了加硼外, 在该黄铜中添加微量锡等其它元素可进一步提高抗脱锌性能, 使之达到 国际饮用水机构所规定的铜合金中相关元素的浸出标准和 ISO6509脱锌标准。
锌含量大于 36.5%有利于切削性能的提高和耐磨性能的增强, 但过高会影响冷成型性 能和合金强度。 所述的其它元素中的钛、铁、硅、锡、磷、稀土金属中的至少两种元素加入的作用, 一是脱氧、细化晶粒; 二是与杂质中的铅形成金属化合物, 强化晶界, 并使含锑的金属化 合物脆化相更加细小均勾地分布在晶界上, 并使金属铋均匀分布于晶内和晶界, 同时还可 抑制铋相和含锑的脆化相偏聚脆断倾向,进而满足工业上需要的优异的切削性能、热成型 性能和良好的焊接性能; 三是抑制脱锌、增强耐蚀性能和抗应力裂性能。所述的其它元素 总含量小于 0.2%达不到满意的切削性能和晶界强化作用; 其它元素总量大于 1.5%, 虽能 使合金进一步细化,抑制脱锌,但会形成其它更多的硬脆相,满足不了后步的冷成型性能, 同时也增加了成本, 影响推广使用效果。
添加钛主要是起脱氧和细化晶粒作用,一般添加量为 0.001〜0.15%为宜,小于 0.001% 效果不明显, 大于 0.15%会增加成本, 并使铸造性能降低。
铁和稀土金属主要是起细化晶粒、 阻止晶粒长大、控制 β相转变数量的作用, 能提高 软化点、 增强强度, 提高冷热成型性能。稀土金属的另一个重要作用是脱氧。铁含量一般 控制在 0.1〜0.3%,铁含量小于 0.1%, 细化晶粒效果不明显; 铁含量大于 0.3%,会降低耐 蚀性能和可电镀性能。稀土金属是优良的变质剂和精炼净化剂, 几乎不固溶于铜, 它会与 合金中的杂质铅形成高熔点金属化合物, 分布在晶内, 提高合金的塑性、耐磨性, 促使晶 粒细化, 促成晶界上的金属化合物更加细小均勾分布, 一般加入量为 0.003〜0.4%, 加入 以镧为基的混合稀土效果更好, 可增加导电率和抗脱锌能力, 过高会降低合金的流动性。
添加硅, 一是用于改善铸造和焊接流动性, 提高该合金的焊接工艺性能, 特别是在焊 接过程中硅还可以抑制锌蒸发及氧化物夹杂;二是增强合金的致密度和耐压、耐磨性能以 及切削性能, 而不是使合金生成高硅的 Υ硬脆相。 一般加入量为 0.1〜0.7%, 当硅含量小 于 0.1%时上述的作用效果不明显; 当硅含量大于 0.7%会生成较多的硅化铁等脆化相, 并 使合金脆断性增强, 切削阻力增大。
与锑一样, 添加锡、磷也是辅助硼来增强抗脱锌、抗应力裂的性能和提高热加工成型 性能, 使之达到国际环保健康安全规定的标准。 其次在该黄铜中添加锡、 磷还可以脱氧、 增加合金的流动性,提高合金的切削性能和强度。锡是固溶强化和抑制脱锌的元素,和锑、 硼、磷一起强化基体, 有利于各相的分散均匀和强化相的形成, 有利于强度、 耐磨性和切 削性能的提高, 特别是有利于抗脱锌性能和冷热成型性能的提高。 磷的含量一般控制在 0.005〜0.2%为宜。 锡的含量一般控制在 0.1〜0.4%为宜, 过高会降低切削性能。 铅和镉即使是作为不可避免的杂质元素, 杂质中的铅含量必须是小于 0.1%, 镉含量 必须是小于 0.001%。 根据国际饮用水工程中的相关检测标准的浸出量检测结果, 这种铅、 镉含量既符合国际环保限令要求, 又不会给环境和人类健康造成公害。
上述的本发明无铅易切削低锑铋黄铜合金之二是具有优异的切削性能、抗脱锌腐蚀性 能、热成型性能和优良的铸造性能, 良好的机械性能和焊接性能的有利于环保健康、安全 的新型无铅易切削黄铜合金。可广泛应用在电子、 电讯、 电脑、饮用水工程、五金、机械 家电、 汽车零部件的铸造和热锻热冲成型、 易切削零部件制造业。
本发明无铅易切削低锑秘黄铜合金之三的合金组成为: 铜: 55〜64 wt%、 铋: 0.3〜 1.5 wt%、锑: 0.05〜1.0 wt%、 硼: 0.0002〜0.05 wt%、 其它元素: 0.2〜1.6 wt%、余量 为锌和不可避免的杂质;不可避免的杂质中铅的含量小于 0.03 wt% ;所述的合金组成中 铜加锌加铋加锑加硼大于 97 wt%, 且其中锌大于 35.5 wt% ; 所述的其它元素是选自以 下元素中的至少两种元素: 钛、 镍、 铁、 锡、 磷、 稀土金属。
所述的无铅易切削低锑祕黄铜合金之三的较佳组成为:铜: 58〜63 wt%、 铋: 0.4〜 1.4 wt% , 锑: 0.06〜0.8 wt%、硼: 0細6〜0.03 wt%、其它元素: 0.2-1.3 wt% > 余量 为锌和不可避免的杂质;不可避免的杂质中铅的含量小于 0.03 wt% ;所述的合金组成中 铜加锌加铋加锑加硼大于 97.5 \^%且不大于 99.8 wt% , 其中锌大于 35.5 wt% ; 所述的 其它元素是选自以下元素中的至少两种元素: 钛、 镍、 铁、 锡、 磷、 稀土金属。
所述的无铅易切削低锑铋黄铜合金之三的相组成为: 以《、 β两相为主, 以游离态均 匀分布于晶内和晶界的铋相,少量细小均匀分布于晶界的固溶态的含锑金属间化合物的硬 脆相。
所述的无铅易切削低锑铋黄铜合金之三是利用铋和锑替代铅, 以铋为主, 用锑辅助 铋进一步提高合金的切削性能; 同时以硼为主, 用锑、锡等辅助硼来提高合金的抗脱锌 性能。
铋的加入可改进合金的切削性。 铋在铜中的固溶度极低, 即使 800Ό时的溶解度也 只不过 0.01%, 但熔液中的溶解度却很大, 在凝固过程中铋发生沉淀, 形成弥散的第二 相粒子, 这种铋的弥散相熔点较低(271.3°C ), 在刀头与屑的接触面局部受热而瞬间熔 化, 这种熔化效应有助于改变切屑的形状并润滑刀具, 从而起到使合金在机加工中易形 成短断屑点, 减少刀头和工件之间的粘结和焊合及提高切削速度的作用, 进而使合金具 有了满意的切削性能。 但铋含量大于 1.5%时, 会导致脆断性增大, 为此我们采用以加 低含量的铋为主和以加入易形成固溶体的锑为辅的合金化方案,使易切削断屑的含锑的 金属化合物(以固溶无毒、 有利健康的形态存在于合金中)脆化相也聚集在晶界附近, 使本合金获得了优异的切削性能和其它综合性能, 从而达到了以铋为主, 用锑辅助铋来 进一步提高合金的切削性能的目的, 使本合金获得了象铅黄铜一样优异的切削性能。 同 时又添加一些细化晶粒、抑制脱锌和控制合金脆断倾向的微量其它元素,进而使含锑的金 属化合物更加细小均匀地分布在晶界上, 并使金属铋均勾分布于晶内和晶界,使合金在机 加工中易形成短断屑点, 有效地增加了合金的切削性能和耐蚀抗脱锌性等综合性能, 从而 使低锑铋黄铜合金获得了象铅黄铜那样优异的切削性能、优良的冷热成型性能、铸造性能、 焊接性能和机械性能以及更严格要求的卫生安全性。可广泛应用在电子、 电讯、 电脑、饮 用水工程、 五金、 机械、 照相器材的光电部件、 家电、 汽车零部件的铸造和冷热成型、 易 切削零部件制造业。
铋和锑是强化和改善合金切削性能的元素, 以铋为主, 用锑辅助铋。 在本合金中铋 含量小于 0.3%时, 满足不了切削性要求, 铋含量大于 1.5%时, 降低合金的冷、 热成型 性能并使合金的机械性能急剧下降, 同时也增加了成本。 为充分利用铋能提髙切削性能 的特性, 同时还要防止过量铋会导致冷、热成型性能和机械性能下降的脆断倾向, 在合 金中铋的含量为 0.3〜1.5%。 这样的含量控制在不含锑等其它切削元素的条件下, 只能 使该合金的切削系数达到 80%左右, 但在铋含量为 0.3〜1.5%的基础上还同时添加了辅 助的锑元素, 使之辅助铋并与铋共同作用获得了更优异的切削性能 (切削系数为 86〜 95%)和优良的耐蚀性能、 机械性能, 进而达到环保、 健康、 新型合金材料的要求。
辅助添加适当含量的锑元素,主要是起辅助铋进一步提高合金的切削性能和特有的抑 制脱锌性能的作用。 当锑的添加含量小于 0.05%时, 对辅助铋提高切削性能效果不明显, 且对提高抗脱锌性作用不明显, 而辅助添加含量大于 1.0%时, 虽辅助铋提高切削性能较 大, 但本合金的塑性降低也非常明显, 同时还增加了成本。故经实践证明辅助添加锑的含 量为 0.05〜1.0%,就可以起到辅助铋提高本合金的切削性能的作用,使该合金更具有优异 的切削性能(切削系数为 86〜95%)、 抗脱锌性能和优良的冷热成型性能、 焊接性能及良 好的机械性能。
铋在铜中的溶解度极低, 铋也是以游离态存在于合金中。但与铅不同的是, 铋是以无 毒的游离态存在于合金中, 而不是象铅那样以有毒的游离态存在于合金中。 WHO (世界 卫生组织)饮用水水质控制标准中没有对铋的限制值, 也还没有人指出铋是对人体有害的 物质。
低含量的锑在铜和锌中均有一定的溶解度,因此锑是以低含量无毒的固溶态存在于合 金中, 不溶于水, 而不是象铅那样以有毒的游离态存在于合金中。经电子探针和透射电镜 观察, 在本合金中锑优先与锌形成固溶体, 并聚集在晶界附近, 形成易切削的短断屑点, 使得含锑的金属化合物脆化相均匀分布在晶界上, 进一步提高了该合金的切削性能。
本合金以硼为主, 用锑、锡等辅助硼来提高合金的抗脱锌性能。添加硼元素主要是起 抑制脱锌、提高耐蚀性能的作用, 同时也有脱氧、 细化晶粒、 增强切削性能的功能。 由于 硼原子半径比锌原子半径小, 黄铜被腐蚀时硼原子比锌原子更易扩散, 因此可优先夺取空 位进而堵塞锌原子的扩散通道, 增加锌扩散的阻力, 形成耐蚀保护膜, 从而达到象砷一样 的抑制脱锌腐蚀的效果。 同时锑也容易和锌形成固熔体化合物, 同样可抑制脱锌, 从而起 到辅助硼并与之共同作用提高合金抗脱锌性的效果。
硼的加入量在 0.0002〜0.05%为宜。 硼含量小于 0.0002%时, 对抑制脱锌和耐蚀效果 不明显; 硼含量大于 0.05%时, 硼化物易在晶界析出, 造成 "硼脆", 降低合金成型性能。. 除了加硼外,在该黄铜中添加微量锡等其它元素可进一步提高抗脱锌性能, 使之达到 国际饮用水机构所规定的铜合金中相关元素的浸出标准和 ISO6509脱锌标准。
锌含量大于 35.5%有利于切削性能的提高和耐磨性能的增强, 但过高会影响冷成型性 能和合金强度。
所述的其它元素中的钛、镍、 铁、 锡、 磷、稀土金属中的至少两种元素加入的作用, 一是脱氧、细化晶粒; 二是与杂质中的铅形成金属化合物, 强化晶界, 并使含锑的金属化 合物脆化相更加细小均匀地分布在晶界上,同时还可抑制铋相和含锑的脆化相偏聚脆断倾 向, 进而满足工业上需要的优良的切削性能、 良好的冷热成型性能和焊接性能; 三是抑制 脱锌、 增强耐蚀性能和抗应力裂性能。 所述的其它元素总含量小于 0.2%达不到满意的切 削性能和晶界强化作用; 其它元素总量大于 1.6%, 虽能使合金进一步细化, 抑制脱锌, 但会形成其它更多的硬脆相, 满足不了后步的冷成型性能, 同时也增加了成本, 影响推广 使用效果。
添加钛主要是起脱氧和细化晶粒作用,一般添加量为 0.001〜0.15%为宜,小于 0.001% 效果不明显, 大于 0.15%会增加成本, 并使铸造性能降低。
镍是基体强化和阻止脱锌元素,同时抑制晶粒长大,增加合金强度、塑性和耐蚀性, 同时还可提高合金抗应力腐蚀的能力。 镍含量少于 0.1 % , 难以满足工业上需要的各项 性能要求, 镍含量大于 0.6%又会增加合金的制造成本并降低切削性能, 故镍含量应控 制在 0.1〜0.6%。
铁和稀土金属主要是起细化晶粒、 阻止晶粒长大、控制 β相转变数量的作用, 能提髙 软化点、增强强度, 提高冷热成型性能。稀土金属的另一个重要作用是脱氧。铁含量一般 控制在 0.1〜0.3%,铁含量小于 0.1%,细化晶粒效果不明显; 铁含量大于 0.3%,会降低耐 蚀性能和可电镀性能。稀土金属是优良的变质剂和精炼净化剂, 几乎不固溶于铜, 它会与 合金中的杂质铅形成高熔点金属化合物, 分布在晶内, 提高合金的塑性、 耐磨性, 促使晶 粒细化, 促成晶界上的金属化合物更加细小均勾分布, 一般加入量为 0.003〜0.4%, 加入 以镧为基的混合稀土效果更好, 可增加导电率和抗脱锌能力, 过高会降低合金的流动性。
与锑一样, 添加锡、磷也是辅助硼来增强抗脱锌、抗应力裂的性能和提高热加工成型 性能, 使之达到国际环保健康安全规定的标准。 其次在该黄铜中添加锡、 磷还可以脱氧、 增加合金的流动性,提高合金的切削性能和强度。锡是固溶强化和抑制脱锌的元素,和锑 > 硼、磷一起强化基体, 有利于各相的分散均匀和强化相的形成, 有利于强度、 耐磨性和切 削性能的提高, 特别是有利于抗脱锌性能和热成型性能的提高。 磷的含量一般控制在 0.005〜0.2%为宜。 锡的含量一般控制在 0.1〜0.4%为宜, 过髙会降低切削性能。
铅和镉即使是作为不可避免的杂质元素, 杂质中的铅含量必须是小于 0.03%, 镉含量 必须是小于 0.001%。 这种铅、 镉含量既符合国际环保限令要求, 又不会给环境和人类健 康造成公害, 并适应将来的环保新材料发展趋势。
上述的本发明无铅易切削低锑秘黄铜合金之三是具有优良的切削性能、优异的抗脱锌 腐蚀性能、 抗应力腐蚀性能, 良好的冷热成型性能、 机械性能及焊接性能的有利于环保、 健康的具有更严格要求的卫生安全性的新型无铅易切削黄铜合金。可广泛应用在电子、 电 讯、 电脑、 饮用水工程、 五金、 机械、 照相器材的光电部件、 儿童玩具、 家电、汽车零部 件的铸造和冷热成型、 易切削零部件制造业。
从上述的本发明无铅易切削低锑铋黄铜合金之一到上述的本发明无铅易切削低锑铋 黄铜合金之三的三种无铅易切削低锑铋黄铜合金发明中添加铋、锑、硼等元素后,切削性、 耐蚀性和抗脱锌性大大地提高。这些含铜量较低的黄铜合金含有 α相、 β相、铋的弥散相 粒子和其它少量的含锑金属间化合物硬脆相,细小均匀分布在晶界和晶内并有沉淀强化作 用, 提髙了合金的切削性能, 增加了短屑的断屑点, 同时也增强了合金的耐蚀性、抗脱锌 性、 耐磨性、 机械性能和冷热成型性能。
本发明合金的制造方法是将重量 铜: 55〜65 wt%、铋: 0.3〜1.5 wt%、锑: 0.05〜 1.0 wt%、 硼: 0.0002〜0.05 wt%、 其它元素: 0.2〜1.2 wt%, 其余为锌和不可避免的杂 质所构成的合金成分, 采用合金化处理和覆盖保护方法熔炼低锑铋黄铜合金, 使硼、锑在 黄铜熔液中快速固溶为金属间化合物,并使金属铋均匀分布于晶内和晶界,并在 1040°C下 连续铸造成铸锭(该黄铜的整个熔炼过程最高温度为 1080°C,远远达不到使金属锑蒸发的 沸点温度 1675Ό和使金属铋蒸发的沸点温度 1680°C, 故不会给人类和环境造成危害),在 680~760°C温度下进行大挤压比挤压,中间热处理按冷加工的条件在 500〜700°C温度下进 行, 在低于 400Ό的温度下可进行消除应力的退火。
与现有技术相比,本发明的优点在于: 1.具有极优异的切削性能、优异的抗脱锌性能、 良好的焊接性能、 优良的耐蚀性、 机械性能, 特别适用于切削加工成型的零部件、 锻件、 铸件和作为其它制造方法的零部件材料; 2.制造成本低,仅相当于现有技术的铅黄铜的制 造成本, 因而具有市场竞争优势; 3.可完全达到国际环保、健康、 安全标准规范要求, 并 为世界循环经济提供了又一新型环保、 健康的无铅易切削低锑铋黄铜合金材料。
附图说明
图 1、 为本发明合金的车屑形貌示意图, 车削背吃刀量为 0.5mm, 主轴转速为 900rpm/min, 进给量为 0.1mm/rev。
具体实施方式
以下结合实施例对发明作进一步详细描述:
实施例对本发明无铅易切削低锑铋黄铜合金按下列各表中的合金成份组成铸锭、挤 压、 拉伸成圆棒; 对比样是美国的含铅黄铜牌号 C36000合金, 它是世界公认的切削性 ( 100% )最好的含铅黄铜, 也进行同样的加工成形。
其生产工艺流程方法如下: 原材料准备及配料——合金化处理熔炼——连续铸锭——铸锭加热一一挤压—— 拉伸——热处理——酸洗——拉伸——矫直抛光——消除应力退火——检验成品包装。
具体可表述如下: 采用合金化处理和覆盖保护方法熔炼低锑铋黄铜合金, 使硼、 锑 在黄铜熔液中快速固溶为金属间化合物, 并使金属铋均勾分布于晶内和晶界, 并在 1040 °C下连续铸造成铸锭,在 680〜760°C温度下进行大挤压比挤压,中间热处理按冷加工的 条件在 500〜70(TC温度下进行, 在低于 400°C的温度下可进行消除应力的退火。
其中转入热处理的工艺流程实施过程证明, 热处理低于 400 °C的消除应力退火是可 以进行的,而中间热处理需根据冷加工的条件在 500〜70(TC温度下退火为宜,但应尽量 避开中温脆性区退火(其流程大体与常规的铅黄铜合金生产相同)。
本发明无铅易切削低锑铋黄铜合金的各种系列发明合金的铸锭其尺寸为 Φ 170*400〜500毫米,在相同的设备条件与不同的挤压温度 680°C〜760°C下,挤压成 Φ 9、 Φ 10毫米的线材, 其具体成份含量见表 11、 表 12、 ·表 13所示。
表 11 : 本发明无铅易切削低锑铋黄铜合金的发明之一的成份组成实例: (重量%)
\元素
主元素 其它元素 其它杂质 总和 编号 \ Cu Bi Sb B Zn Ti Fe Ni Sn P
0. 2, (其 中 Pb<
1-001 57. 76 0. 49 0. 18 0. 0088 余量 ——― 0. 129 0. 201 0. 377 —―
0. 1 , Cd< 0. 001) 0. 2,(其 中 Pb<
1-002 59. 82 1. 02 0. 09 0. 0019 余量 一一一 0. 211 0. 101 0. 198 0. 0101
0. 1, Cd< 0. 001) 0. 2,(其 中 Pb<
1-003 59. 93 1. 12 0. 12 0. 0033 余量 0. 0011 0. 108 0. 105 -— 0. 0109
0. 1, Cd< 0. 001) 0. 2, (其 中 Pb<
1-004 60. 28 1. 24 0. 25 0. 0009 余量 0. 0013 —― 0. 217 —―
0. 1, Cd< 0. 001) 0.2' (其 中 Pb<
1-005 63.38 0.92 0.55 0.0193 余量 0.0010 —― —一 0.124 0.141 0.1, Cd<
0.001) 表 12: 本发明无铅易切削低锑铋黄铜合金的发明之二的成份组成实例: (重量%)
Figure imgf000018_0002
表 13: 本发明无铅易切削低锑铋黄铜合金的发明之三的成份组成实例: (重量%)
Figure imgf000018_0001
0. 2,(其中-012 60. 23 1. 26 0. 14 0. 0018 余量 一一 0. 106 0. 110 0. 139 0. 0123 Pb<0. 03, Cd
<0. 001) 0. 2, (其中-013 1. 23 0. 11 0. 0023 余量 0. 0013 —― 0. 203 ―— 0. 0130 Pb<0. 03, Cd
<0. 001) 0. 2,(其中-014 61. 06 1. 19 0. 09 0. 0050 余量 —― 0. 109 —― 0. 101 一一 Pb<0. 03, Cd
<0. 001) 0. 2, (其中-015 63. 65 1. 01 0. 58 0. 0079 余量 —- —一 ―—— 0. 218 0. 0086 Pb<0. 03, Cd
<0. 001 = 本发明无铅易切削低锑铋黄铜合金的性能测试如下:
1.切削性实验
通过车削评价切削性的实验是这样进行的:
在相同的机械加工条件下(见表 14),采用切削力实验仪测得各发明合金的切削力, 并由此计算出各发明合金相对于 C36000的切削性指数, C36000是世界公认的切削性 最好的含铅黄铜, 其切削性被认为是 100%。 结果见表 15, 得到的对应的车屑形貌如图 1所示。 评价切削性的机械加工条件
车床型 工件直 背吃刀 进给量 切削速度 主轴转速 切削点 切削
号 径 (mm) 量 (mm) (mm/r) (m/min) (r/min) 数 (点) 状态
CA6140 Φ7.3 0.5 0.1 20.64 900 3 干的 表 15 切削性评定结果
a 金 切削性指数(%)
C36000 100
发明一口 ^89
发明二口 ^88
发明三合全 ^95
注: [切削性指数 HC36000的切削阻力] /各发明合金的切削阻力 xI00%,各切削阻力是依据实验所测 得的切削力平均值取值。
可见,本发明合金的切削性可达传统含铅黄铜 C36000的 88%以上,切削性能优异。 除了 C36000外, 本发明合金还与美国 NAKAYAMA公司的 Cu-Zn-Bi系合金、 日 本三宝公司的 Cu-Zn-Si系合金进行了对比, 通过切削、钻孔加工, 得到发明合金的机加 工综合切削性能, 结果见表 16。 发明合金与对比合金的机加工综合切削性能对比
Figure imgf000020_0001
2.热压缩实验
从第一到第三发明合金挤制品上各取 Φ9*20ιηηι做试样, 另外对比样 C36000也取 相同规格, 作热压縮试验。 试样在 670°C加热 30分钟, 然后轴向加载, 变形量为 70%, 长度由 20mm减少为 6mm, 在 5〜10倍放大镜下观察其变形后表面裂纹情况。
我们可以看到, 经热压缩实验后, 发明合金与 C36000合金的表面均无裂纹。 可见 发明合金的热加工性与 C36000相当或更好, 适合工业加工。 3.脱锌实验
从本发明无铅易切削低锑铋黄铜合金发明之一到发明之三按照 ISO6509脱锌实验 方法进行了脱锌实验, 对比样为 C36000含铅黄铜, 测得的最大脱锌腐蚀深度见表 17- 表 17: 本发明无铅易切削低锑铋黄铜合金和 C36000含铅黄铜的最大脱锌腐蚀深度对比
Figure imgf000021_0001
从表 17可见,本发明无铅易切削低锑鉍黄铜合金的抗脱锌性均优于 C36000含铅黄 铜。
4.应力腐蚀实验
根据 IS06957 实验方法, 对本发明无铅易切削低锑铋黄铜合金进行了应力腐蚀实 验, 对比样为 C36000含铅黄铜。
经过 24小时的氨熏试验后, 取出试样, 先在蒸馏水水中漂洗, 然后于室温下在 5% 的硫酸溶液中充分清洗几分钟, 最后再在蒸馏水中洗涤并吹干。 经过 10倍的放大观察 氨熏后的试样表面, 可以看到, 经应力腐蚀实验后, 本发明无铅易切削低锑铋黄铜合金 及 C36000含铅黄铜表面均无明显肉眼可见裂纹。
5.常温抗拉实验
取本发明无铅易切削低锑铋黄铜合金之一到本发明无铅易切削低锑铋黄铜合金之 三的规格为 5.0*140mm的半硬态成品,进行常温抗拉试验, 对比样为同状态同规格的 C36000含铅黄铜。 测试了各发明合金的延伸率和抗拉强度, 结果见表 18。 表 18: 本发明无铅易切削低锑铋黄铜合金与 C36000含铅黄铜的常温机械性能对比 合 金 规格 状态 延伸率 (%) 抗拉强度 (MPa)
C36000 Φ 5.0 Y/2 7 ^450 发明之一 Φ 5.0 Y/2 6 450 发明之二 Φ 5.0 Y/2 5 450 发明之三 Φ 5.0 Y/2 6 450 从表 18 可见, 本发明无铅易切削低锑铋黄铜合金的机械性能与传统含铅黄铜 C36000基本相当。
6.导电率测试
取本发明无铅易切削低锑铋黄铜合金及 C36000含铅黄铜, 测试其室温导电率, 试结果如表 19: 本发明无铅易切削低锑铋黄铜合金与 C36000含铅黄铜的室温导电率对比
Figure imgf000022_0001
7.差热分析(DTA)
取本发明无铅易切削低锑铋黄铜合金及 C36000作差热分析, 测得熔点见表 20: 本发明无铅易切削低锑铋黄铜合金与 C36000含铅黄铜的熔点对比
Figure imgf000022_0002
8.卫生安全性检验
根据《生活饮用水输配水设备及防护材料卫生安全评价规范》(2001 ), 对本发明无 铅易切削低锑铋黄铜合金之三进行了卫生安全性检验, 检验结果见表 21 : 表 21 无铅易切削黄同一低锑铋黄铜饮用水浸泡实验增测项目结果 序号 分析项目 卫生规范要求 检验结果
1 铜 增加量 0.2mg/L 合格
2 锌 增加量 0.2mg/L 合格
3 锑 增加量 0.0005mg/L 合格 综合考虑各种实验结果,我们认为本发明的无铅易切削低锑铋黄铜合金与传统的含 铅黄铜切削性能相近, 比国外近期研发的含铋黄铜、 含硅 3 %黄铜的切削性能优异, 同 时本发明合金的切削强化形成机理、 合金主成分及合金中相组成也有其独特之处。
上述各种实验结果还证明, 本发明无铅易切削低锑铋黄铜合金的切削性能、机械强 度与耐蚀性能优异。 而原料成本比美国的同类别无铅黄铜合金(Cu-Zn-Bi合金)低 5% 以上; 比日本三宝的同类别无铅黄铜合金(Cu-Zn-Si合金)低 11 %以上; 但是比传统的 C36000含铅黄铜原料成本略高 2%。
因此本发明无铅易切削低锑铋黄铜合金是一种具有优异切削性能、 耐蚀性能、抗脱 锌性能、优良的机械性能的无铅易切削黄铜合金。 能广泛应用于电子、 电讯、 电脑、 家 电、 五金切削零部件、锻、铸件和其它用途的高强度耐磨性的紧固件以及液压装置的零 部件、 民用供水系统的铸件和阀、 开关、 水龙头、 汽车与仪表制造业的零部件、 热交换 器连接件、 灯具件、 煤气喷嘴等, 均具有很高的使用价值, 同时也满足了国际生态环保 健康安全卫生规范的标准要求。

Claims

权 利 要 求 书
1. 一种生态环保新型无铅易切削低锑铋黄铜合金, 其特征在于: 它由铜、 锌及铋、 硼、 锑等合金元素和不可避免的杂质成分组成, 所述的合金的组成为: 铜: 55〜65wt %、 鉍: 0.3〜1.5wt%、 锑: 0.05〜1.0.wt%、 硼: 0.0002〜0.05 wt%、 其它元素: 0.2〜 1.2 wt%,余量为锌和不可避免的杂质; 不可避免的杂质中铅的含量小于 0.1 wt%; 所述 的合金组成中铜加锌加铋加锑加硼大于 97 wt%, 且其中锌大于 35.5 wt%; 所述的其它 元素是选自以下元素中的至少两种元素: 钛、 镍、 铁、 锡、 磷、 稀土金属。
2.根据权利要求 1所述的无铅易切削低锑铋黄铜合金,其特征在于:所述的合金的 组成为:铜: 58〜63wt%、铋: 0.4〜1.4wt%、锑: 0.06〜0.8wt%、硼: 0.0006〜0.03 wt %、 其它元素: 0.2〜1.0wt%、 余量为锌和不可避免的杂质; 不可避免的杂质中铅的含 量小于 0.1 wt%;所述的合金组成中铜加锌加铋加锑加硼大于 97.5 ^%且不大于 99.8 wt %,其中锌大于 35.5 wt%;所述的其它元素是选自以下元素中的至少两种元素:钛、镍、 铁、 锡、 磷、 稀土金属。
3. 一种生态环保新型无铅易切削低锑铋黄铜合金, 其特征在于合金的组成为: 铜:
55〜63wt%、铋: 0.3〜1.5wt%、锑: 0.05〜1.0wt%、镍: 0.1〜0.6wt%、硼: 0.0002〜 0.05 wt%、 其它元素: 0.2〜1.5wt%、 余量为锌和不可避免的杂质; 不可避免的杂质中 铅的含量小于 0.1 wt%;所述的合金组成中铜加锌加铋加锑加硼大于 97 wt%,且其中锌 大于 36.5wt%; 所述的其它元素是选自以下元素中的至少两种元素: 钛、 铁、 硅、 锡、 磷、 稀土金属。
4.根据权利要求 3所述的无铅易切削低锑铋黄铜合金, 其特征在于: 所述的合金的 组成为:铜: 57〜62wt%、 铋: 0.4〜1.4wt%、 锑: 0.06〜0.8wt%、 镍: 0.1〜0.5wt%、 硼: 0.0006〜0.03 wt%、其它元素: 0.2〜1.2wt%、 余量为锌和不可避免的杂质; 不可避 免的杂质中铅的含量小于 0.1 wt%; 所述的合金组成中铜加锌加铋加锑加硼大于 97.5 wt %且不大于 99.8 wt%,其中锌大于 36.5 wt%;所述的其它元素是选自以下元素中的至少 两种元素: 钛、 铁、 硅、 锡、 磷、 稀土金属。
.5.一种生态环保新型无铅易切削低锑铋黄铜合金, 其特征在于合金的组成为: 铜:
55〜64wt%、 铋: 0.3〜1.5wt%、 锑: 0.05〜1.0wt%、 硼: 0崖2〜0.05 wt%、 其它元 素: 0.2〜1.6 wt%、余量为锌和不可避免的杂质;不可避免的杂质中铅的含量小于 0.03 wt %; 所述的合金组成中铜加锌加铋加锑加硼大于 97 wt%, 且其中锌大于 35.5 wt% ; 所 述的其它元素是选自以下元素中的至少两种元素: 钛、 镍、 铁、 锡、 磷、 稀土金属。
6.根据权利要求 5所述的无铅易切削低锑铋黄铜合金,其特征在于:所述的合金的 组成为:铜: 58〜63 wt%、铋: 0.4〜1.4 wt%、锑: 0.06〜0.8 wt%、硼: 0扁6〜0.03 wt %、 其它元素: 0.2〜1.3 wt%、 余量为锌和不可避免的杂质; 不可避免的杂质中铅的含 量小于 0.03 wt% ; 所述的合金组成中铜加锌加铋加锑加硼大于 97.5 \¥1%且不大于 99.8 wt% , 其中锌大于 35.5 wt% ; 所述的其它元素是选自以下元素中的至少两种元素: 钛、 镍、 铁、 锡、 磷、 稀土金属。
7.根据权利要求 1至 6中任一权利要求所述的无铅易切削低锑铋黄铜合金,其特征 在于: 所述铁的含量为 0.1~0.3wt%。
8.根据权利要求 1至 6中任一权利要求所述的无铅易切削低锑铋黄铜合金,其特征 在于: 所述锡的含量为 0.1~0.4wt%。
9.根据权利要求 3或 4所述的无铅易切削低锑铋黄铜合金,其特征在于:所述硅的 含量为 0.1~0.7wt%。
10.—种制造如权利要求 1或 3或 5所述的无铅易切削低锑铋黄铜合金的方法, 其 特征在于:其制造过程是:采用合金化处理和覆盖保护方法熔炼低锑铋黄铜合金,使硼、 锑在黄铜熔液中快速固溶为金属间化合物, 并使金属铋均匀分布于晶内和晶界, 并在 1040°C下连续铸造成黄铜铸锭,在 680〜760°C温度下进行大挤压比挤压,中间热处理按 冷加工的条件在 500〜700°C温度下进行,在低于 400°C的温度下可进行消除应力的退火。
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 Ceased WO2006136065A1 (fr)

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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
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DE112021004805T5 (de) 2020-11-13 2023-07-27 T.C. Marmara Üni̇versi̇tesi̇ Herstellung einer bleifreien messinglegierung mit verbesserter bearbeitbarkeit
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