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WO2015032044A1 - 一种无铅易切削高硫含锰铜合金及其制造方法 - Google Patents

一种无铅易切削高硫含锰铜合金及其制造方法 Download PDF

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Publication number
WO2015032044A1
WO2015032044A1 PCT/CN2013/082961 CN2013082961W WO2015032044A1 WO 2015032044 A1 WO2015032044 A1 WO 2015032044A1 CN 2013082961 W CN2013082961 W CN 2013082961W WO 2015032044 A1 WO2015032044 A1 WO 2015032044A1
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Prior art keywords
manganese
sulfur
lead
free
copper alloy
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PCT/CN2013/082961
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English (en)
French (fr)
Inventor
黄劲松
刘彬
李卫
陈志永
彭韬
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HUNAN TERRY NEW MATERIALS Co Ltd
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HUNAN TERRY NEW MATERIALS Co Ltd
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Application filed by HUNAN TERRY NEW MATERIALS Co Ltd filed Critical HUNAN TERRY NEW MATERIALS Co Ltd
Priority to US14/898,602 priority Critical patent/US10519528B2/en
Priority to PCT/CN2013/082961 priority patent/WO2015032044A1/zh
Priority to CN201380079356.2A priority patent/CN105518163B/zh
Priority to JP2016539377A priority patent/JP6239767B2/ja
Priority to EP13892796.7A priority patent/EP3042971B1/en
Publication of WO2015032044A1 publication Critical patent/WO2015032044A1/zh
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • 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
    • C22C9/05—Alloys based on copper with manganese 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • B22F2003/175—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • B22F2003/208—Warm or hot extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0848—Melting process before atomisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a metal material and a method of manufacturing the same, and more particularly to a lead-free free-cutting copper alloy and a method of manufacturing the same.
  • Lead brass has excellent cold and hot workability, excellent cutting performance and self-lubricating characteristics, and can meet the machining requirements of various shapes and components.
  • Lead brass was once widely recognized as an important basic metal material in the world and is widely used in civil water supply systems, electronics, automotive and machinery manufacturing. Since lead brass is widely used, the number of discarded lead brass parts is large. , Only a small amount of it was recycled, and many small pieces were abandoned as garbage. The discarded lead brass is in contact with the soil, and the lead contained in it enters the soil under the long-term action of rain and the atmosphere, thereby contaminating the soil and water. Waste lead brass is used as waste incineration Lead vapor is emitted into the atmosphere. It is extremely harmful to the human body, and its application is increasingly restricted.
  • Lead is not dissolved in copper, nor forms an intermetallic compound with copper, but exists in the form of elemental microparticles at the grain boundaries, sometimes in the crystal.
  • the lead in the lead-containing copper alloy is slowly precipitated in the form of ions under the action of impurities and ions in drinking water, and the existing lead-containing copper alloy is difficult to meet the requirements of the environmental protection law.
  • researchers have systematically studied the corrosion mechanism of drinking water on brass and the corrosive effects of added elements on brass, and adopted various measures, such as adding a small amount of alloys such as tin and nickel.
  • Lead-based brass which uses lead as a major element to improve the cutting performance of brass, has to gradually withdraw from the historical stage under the Environmental Protection Act.
  • phosphorus helps to improve its cutting performance, but at the same time reduces the plasticity of the alloy, and the tendency of the alloy to crack is increased during low pressure casting. This limits the amount of phosphorus added to the brass and limits the use of phosphorous brass. Because of tin, The price of antimony and selenium is high, tin brass and brass containing antimony and selenium are difficult to be widely promoted in the market. The effect of tin on improving the cutting performance of copper alloys is also very limited. There are two kinds of patented silicon brass, one is low zinc silicon brass, such as C69300, due to high copper content, high density, high price, market share is not large. The other is high zinc silicon brass with insufficient cutting performance.
  • Sulfur has a melting point of only 113 ° C and a boiling point of only 445 ° C.
  • the pollution-free production is also a problem, which is also extremely unfavorable for its application.
  • sulfur is usually present at the grain boundary in the copper alloy with a low melting point eutectic, which makes the copper alloy brittle.
  • the difficulty in pressure processing of the sulfur-based free-cutting copper alloy is generally relatively large and the cost is relatively high.
  • the alloy compositions referred to in the application documents refer to the mass fraction content.
  • the composition of the high performance lead-free free-cutting copper alloy of the alloy of the invention is: copper 52.0%-95.0%, phosphorus 0.001%-0.20%, tin 0.01%-20%, manganese 0.55%-7.0%, sulfur 0.191%-1.0%
  • the metal having a affinity for sulfur other than zinc and having a lower affinity for manganese and sulfur is one or more, and the sum of the contents is ⁇ 2.0%; the balance is zinc and unavoidable impurities, wherein lead ⁇ 0.05%.
  • the metal having a affinity for sulfur other than zinc and having a affinity for manganese and sulfur is nickel, iron, tungsten, cobalt, molybdenum, niobium, tantalum or niobium.
  • the composition of the alloy is: copper 54.0% - 68.0%, phosphorus 0.001% - 0.15%, tin 0.01%-1%, manganese 1.5%-4.0%, sulfur 0.2%-0.6%, one or more of nickel, iron, tungsten, cobalt, molybdenum, niobium, tantalum and niobium, the sum of the contents is ⁇ 1.8% The balance is zinc and unavoidable impurities, of which lead ⁇ 0.05%.
  • composition of the alloy is: copper 56.0%-64.0%, phosphorus 0.001%-0.12%, tin 0.01%-0.8%, manganese 2.0%-3.5%, sulfur 0.22%-0.40%, one or more of nickel, iron, tungsten, cobalt, molybdenum, niobium, tantalum and niobium, the sum of the contents is ⁇ 1.5% The balance is zinc and unavoidable impurities, of which lead ⁇ 0.05%.
  • composition of the alloy is: copper 57.0%-62.0%, phosphorus 0.001%-0.12%, tin 0.01%-0.6%, manganese 2.0%-3.5%, sulfur 0.22%-0.40%, nickel 0.1%-1.2%, the balance is zinc and unavoidable impurities, of which lead ⁇ 0.05% .
  • composition of the alloy is: copper 57.0%-62.0%, phosphorus 0.001%-0.08%, tin 0.01%-0.4%, manganese 2.0%-3.5%, sulfur 0.22%-0.30%, nickel 0.1%-0.5%, the balance is zinc and unavoidable impurities, of which lead ⁇ 0.05% .
  • the composition of the alloy is: copper 74%-90%, phosphorus 0.001%-0.12%, tin 5%-20%, manganese 2.5%-3.5%, sulfur 0.2%-1.0%, one or more elements of nickel, iron, tungsten, cobalt, molybdenum, niobium, tantalum and niobium, the sum of the contents is ⁇ 2.0%, the balance is zinc and inevitable Impurity, where lead ⁇ 0.05%.
  • composition of the alloy is: copper 84%-90%, phosphorus 0.001%-0.12%, tin 5%-11%, manganese 2.5%-3.5%, sulfur 0.3%-1.0%, one or more elements of nickel, iron, tungsten, cobalt, molybdenum, niobium, tantalum and niobium, the sum of the contents is ⁇ 1.5%, the balance is zinc and inevitable Impurity, where lead ⁇ 0.05%.
  • composition of the alloy is: copper 84%-90%, phosphorus 0.001%-0.12%, tin 5%-11%, manganese 2.5%-3.5%, sulfur 0.4%-0.8%, nickel 0.1%-1.2%, the balance is zinc and unavoidable impurities, of which lead ⁇ 0.05%.
  • composition of the alloy is: copper 84%-90%, phosphorus 0.001%-0.12%, tin 5%-11%, manganese 2.5%-3.5%, sulfur 0.4%-0.7%, nickel 0.1%-0.5%, the balance is zinc and unavoidable impurities, of which lead ⁇ 0.05%.
  • the process flow of the lead-free free-cutting copper alloy of the present invention is as follows:
  • the manganese alloy-containing copper alloy powder is prepared by water atomization or gas atomization; or copper, tin, phosphorus, and zinc are sequentially melted.
  • the copper alloy powder containing no manganese is prepared by water atomization or gas atomization;
  • One or more kinds of metal sulfides in which nickel powder, manganese-containing copper alloy powder and affinity with sulfur are less than manganese and sulfur, or nickel powder, manganese-free copper alloy powder, manganese powder and heel One or more ingredients in the metal sulfide having an affinity for sulfur that is less than the affinity of manganese and sulfur, and then a forming agent 0.5%-1.5%, all the prepared powders are put into the mixer, mixing time 0.4-5h, so that the various powders are evenly distributed;
  • the uniformly mixed powder is press-formed and then sintered, and the sintering process is: heating from room temperature to sintering temperature 680-780 ° C, heating time 1-5 h, fully removing the forming agent, holding time 30-120min, the sintering atmosphere is a reducing atmosphere or an inert atmosphere; the sintered copper alloy is recompressed with a pressure of
  • the sintering atmosphere is a reducing atmosphere or an inert atmosphere; the copper alloy after recompression and re-baking is subjected to hot working, and the temperature of the hot working is 800 to 870 degrees.
  • the metal sulfide is a solid metal sulfide.
  • the metal sulfides are eleven metal sulfides of iron, cobalt, nickel, tin, tungsten, molybdenum, niobium, copper, zinc, lanthanum and cerium.
  • the metal sulfides are copper sulfide, cuprous sulfide, zinc sulfide, tin sulfide, nickel sulfide, iron sulfide, ferrous sulfide, ferrous sulfide, tungsten sulfide, cobalt sulfide, molybdenum disulfide, molybdenum trisulfide, and four.
  • metal sulfides copper sulfide, zinc sulfide, and iron sulfide are preferable.
  • the hot working is hot swaging or hot extrusion.
  • the lead-free free-cutting copper alloy process is as follows:
  • Copper, tin, manganese, and zinc are sequentially melted, and the manganese alloy-containing copper alloy powder is prepared by water atomization or gas atomization after the alloying elements are homogenized; or copper, tin, and zinc are sequentially melted, and the alloying elements are homogenized.
  • the manganese-free copper alloy powder is prepared; a nickel powder, a manganese-containing copper alloy powder or a nickel powder, a manganese-free copper alloy powder and a manganese powder, and one or more kinds of metal sulfides having an affinity for sulfur to be less than the affinity of manganese and sulfur, and then Adding molding agent 0.5%-1.5%
  • the mixing time is 0.4-5h to make the various powders evenly distributed; the uniformly mixed powder is press-formed and then sintered, and the sintering process is: heating from room temperature to sintering temperature 730-770 ° C, heating time 1-5h, the forming agent is sufficiently removed, the holding time is 30-120 min, and the sintering atmosphere is a reducing atmosphere or an inert atmosphere.
  • the forming agent is paraffin powder or zinc stearate powder.
  • the solubility of lead in copper melt is large, but the solid solubility of lead in room temperature copper is almost zero.
  • the lead brass melt solidifies, the lead is dispersed in the form of fine spherical particles in the grain boundary of the brass, and sometimes distributed in the crystal.
  • Lead is brittle and soft, and the melting point of lead is only 327.5 °C,
  • the frictional heat will further soften the lead particles.
  • these scattered lead particles are equivalent to the voids existing in the brass, and the stress is easily concentrated here. A so-called 'cutting effect' is produced, which leads to easy breakage of the chips.
  • the lead plays a role in changing chip shape, chipping, reducing bonding and soldering, and increasing cutting speed during the cutting process of free-cutting brass materials, which can greatly improve the efficiency of cutting and increase the use of tools.
  • the service life reduces the roughness of the machined surface and makes the machined surface smooth and smooth. The characteristics of lead and its presence in free-cutting lead brass have a decisive effect on its cutting performance. .
  • Lead in lead-containing self-lubricating copper alloys is also due to its soft and brittle nature, which acts as a friction reducer.
  • the mechanism of graphite in graphite self-lubricating copper alloys is similar to that of lead.
  • a method of simultaneously adding manganese and a metal sulfide in a copper alloy is adopted. In the process of sintering, since the activity of manganese is higher than that of the metal sulfide added, the sulfide reacts with manganese to form manganese sulfide or a mixture of manganese sulfide and other sulfides.
  • the in-situ generated sulfide is mainly manganese sulfide, and the combination with the copper alloy structure is a metallurgical bond, the interface is coherent or semi-coherent, and the strength is high.
  • the in-situ reaction product manganese sulfide has a layered structure, its structural characteristics are similar to those of graphite, and it also has soft and slippery properties.
  • the presence of manganese sulfide in copper alloy Corresponding to the presence of holes in the copper alloy, the stress tends to concentrate here, resulting in a so-called 'cutting effect', which causes the chips to break easily.
  • the chip breaking mechanism of manganese sulfide is consistent with the chip breaking mechanism of lead in lead brass.
  • the generated sulfide particles have a lubricating effect on the cutting tool, and can also reduce the wear of the cutting head and greatly improve the cutting efficiency.
  • the generated manganese sulfide particles and The copper alloy grains have good bonding, the interface is clean, and the bonding strength is high.
  • the graphite particles in the graphite self-lubricating copper alloy have no such effect as the manganese sulfide particles, so in addition to good lubrication in the self-lubricating copper alloy, It has higher strength than graphite self-lubricating copper alloy.
  • the role of phosphorus is deoxidation, which can improve the casting properties and weldability of the alloy, reduce the oxidation loss of the beneficial elements silicon, tin and magnesium, and refine the grain of the brass.
  • the phosphorus addition amount is controlled within the range of 0.001% to 0.20%, and the main function is to lower the melting point of the copper alloy powder during the sintering process, thereby functioning to activate sintering.
  • Lead-free free-cutting high-sulfur manganese-containing copper alloy has excellent process properties such as excellent cutting, hot forging and other properties such as high strength, resistance to dezincification, ammonia-resistant, polishing, electroplating and self-lubricating properties.
  • Brass after recompression and reburning has good hot working properties such as hot forging and hot extrusion.
  • Hot extruded brass has good cutting performance and high strength. According to ISO6509: 1981 "Corrosion of metals and alloys - Determination of resistance to dezincification of brass", hot extruded brass has excellent resistance to dezincification.
  • GB/T10567.2-2007 “Test method for residual stress of copper and copper alloy processed materials: ammonia smoke test method", but the ammonia concentration is 14%, and the brass is the longest resistant to ammonia for 16 hours without cracks.
  • Copper-tin alloy-based self-lubricating copper alloys have the highest flexural strength and elongation equivalent to 111% and 116% of graphite self-lubricating copper alloys. .
  • the copper alloy has a simple composition, and the constituent elements do not contain harmful elements such as lead, cadmium, mercury, and arsenic, and the production process is non-polluting.
  • the copper alloy does not contain chrome. It can also be made of alloys without bismuth and antimony. It can fully meet the stringent requirements of the plumbing industry for the leaching of harmful elements.
  • Example 1 The mass fraction of each element in the manganese-containing copper alloy powder was: copper 54.0%, phosphorus 0.11%, tin 0.011%, manganese 0.6%, the balance is zinc and unavoidable impurities.
  • the mass fractions of the various powders are as follows: the sulfide powder is a mixture of copper sulfide powder and zinc sulfide powder, and their contents are respectively 0.8% and 0.30%; the content of the nickel powder is 2.0%; the content of the paraffin powder to be added is 0.5%; the balance is the above-mentioned copper alloy powder containing manganese. Powder mixing time 4.0h After the mixture is finished, it is pressed. After pressing, it is placed in a sintering furnace for sintering.
  • the sintering process is: heating from room temperature to sintering temperature, heating time 5.0h, fully removing the forming agent, sintering temperature 680 °C, holding time At 100 min, the sintering atmosphere was an inert atmosphere, and after cooling, it was cooled to room temperature with water.
  • the sintered brass rod is recompressed with a pressure of 500 MPa, and then re-fired.
  • the re-burning process is: heating from room temperature to sintering temperature 820 ° C, heating time 3.0 h, holding time 120 min, the sintering atmosphere is an inert atmosphere.
  • the re-fired brass was hot extruded at 800 °C and the hot extrusion ratio was 120.
  • Example 2 - Example 33 The chemical composition of the copper alloy powder in all the examples of Examples 2-33 is shown in Table 1. The mass percentage of each powder is shown in Table 2. The process parameters of the copper alloy in the corresponding examples are shown in Table 3. The properties of the copper alloy in Example 2-33 are shown in Table 4.
  • Example 34 The mass fraction of each element in the manganese-containing copper alloy powder was: copper 88%, tin 10.0%, manganese 1.5% The balance is zinc and inevitable impurities.
  • the mass fractions of the various powders are as follows: a mixture of various powders such as copper sulfide, cuprous sulfide, zinc sulfide, tin sulfide, nickel sulfide, etc., each of which has a content of 0.2% by weight.
  • the content of the nickel powder is 0.3%; the content of the paraffin powder to be added is 1.2%; the balance is the above-mentioned copper alloy powder containing manganese.
  • Powder mixing time 2h After the mixture is finished, it is pressed, and after pressing, it is placed in a sintering furnace for sintering.
  • the sintering process is: heating from room temperature to sintering temperature, heating time 2 h, fully removing the forming agent, sintering temperature 750 ° C, holding time At 60 min, the sintering atmosphere was a reducing atmosphere, and after cooling, it was cooled to room temperature with water.
  • the friction and wear samples were immersed in hot oil at 90 °C for 1 hour.
  • the experimental results show that the friction coefficient of lead-free self-lubricating copper alloy is equivalent to 96% of graphite self-lubricating copper alloy, and the wear amount is equivalent to 95% of graphite self-lubricating copper alloy.
  • the mechanical properties of the experimental results show that the tensile strength of the lead-free self-lubricating copper alloy is equivalent to 110% of the graphite self-lubricating copper alloy, and the elongation is equivalent to 116% of the graphite self-lubricating copper alloy.
  • Examples 35-42 The chemical compositions of copper alloy powders are shown in Table 1. The mass fractions of various powders are shown in Table 2. The manufacturing process parameters of the copper alloy in the corresponding examples are shown in Table 3. All the friction and wear samples in Examples 35-42 were immersed in the hot oil at 90 °C for 1 hour. The properties of the copper alloy are shown in Table 5.

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Abstract

一种无铅易切削高硫含锰铜合金及其制造方法。合金组分以质量百分比计为：铜52.0%-95.0%，磷0.01%-0.20%，锡0.01%-20%，锰0.55%-7.0%，硫0.191%-1.0%，除锌外与硫亲和力小于锰与硫亲和力的金属一种或多种，其含量之和≤2.0%，余量为锌及和不可避免的杂质，其中除锌外与硫亲和力小于锰与硫亲和力的金属为镍、铁、钨、钴、钼、锑、铋和铌。该铜合金通过粉末冶金法制造，将合金粉末、硫化物粉和镍粉混合均匀后，进行压制成型、烧结、复压、复烧，得到所述铜合金并进行热加工处理。

Description

一种无铅易切削高硫含锰铜合金及其制造方法
技术领域
本发明涉及一种金属材料及其制造方法，特别是无铅易切削铜合金及其制造方法 。
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要求。铅黄铜一度被世界公认为一种重要的基础金属材料而广泛应用到民用供水系统、电子、汽车及机械制造等领域。由于铅黄铜被广泛使用，废弃的铅黄铜零配件数量很多 , 其中只有少量被回收利用，很多小件被作为垃圾遗弃。废弃的铅黄铜与土壤接触，其所含的铅在雨水及大气的长期作用下，进入土壤，从而污染土壤及水源。废弃铅黄铜被当作垃圾焚烧时 , 铅蒸气散发于大气之中 , 对人体产生极大危害，因而其应用日益受到严格的限制。铅即不固溶于铜，也不与铜形成金属间化合物，而是以单质微颗粒的形式存在于晶界，有时在晶内也有。在饮用水中的杂质及离子等的作用下含铅铜合金中的铅以离子的形式缓慢析出，现有的含铅铜合金很难满足环保法令的要求。为了降低铅的有害作用，科研人员就饮用水对黄铜的腐蚀机理及添加元素对黄铜的腐蚀性影响进行了系统的研究，并采取了多种措施，如添加少量的锡、镍等合金元素来提高铅黄铜的耐蚀性能，或将一定厚度的可溶性铅溶解去除然后在除铅的表面再覆盖铬等耐蚀金属或采取其它的方法抑制铅的浸出等。由于基体黄铜中始终存在着铅，所以这些方法无法从根本上消除铅的有害作用。以铅元素作为一种主要元素改善黄铜切削性能的铅黄铜在环保法令的规定下，不得不逐步退出历史的舞台。
无论从国内外的环保法律法规，还是从技术经济的角度出发，对铅黄铜再进行修修补补的改进已无大的价值，唯有开发无铅的新型铜合金。人们对金属、合金、化合物的研究有一个长期积累的过程，对其特性的认识已相当丰富。铋、锑、镁、磷、硅、硫、钙、 碲、硒 等元素加入到铜合金中对其切削性能的改善已取得共识，国内外都有大量的专利公开。必须指出的是，与易切削铅黄铜相比，目前所有的无铅易切削铜合金的加工性能、使用性能及成本，如：冷热加工性能、切削加工性能等工艺性能或抗脱锌性能、耐氨薰性能等使用性能或多或少地存在一些问题，其综合性能及性价比与铅黄铜相比差距还比较大。以金属铋作为改善切削性能的主要元素时，由于铋的价格贵，市场无法接受高铋含量的铜合金。低铋含量铜合金的切削性能虽然也比较好，但与铅黄铜相比还存在较大差距。另一方面，铋离子对人体健康的影响至今还不是很明确，其副作用的大小尚无定论，在一些国家和地区还不愿意接受铋黄铜。铋资源的有限性，也注定其不能做为易切削含铅铜合金中铅的主要替代元素。铋会使铜合金产生脆性，严重恶化铜合金的压力加工性能，特别是热加工性能，其回收料甚至会危害整个铜加工行业，这会严重降低其回收价值，对含铋易切削铜合金的市场推广不利。锑是对人体有微毒的元素，其在水中的浸出浓度受到非常严格的限制，尽管锑黄铜的切削性能也较好，但其使用亦受到很大的限制。锑黄铜的热加工性能也不太理想；锑的价格也不便宜，对其市场推广也不利。镁能明显改善黄铜的切削性能，但其添加量不能过多，当其质量分数超过 0.2% 时，合金的延伸率开始下降，添加量越多，其延伸性能下降越明显，对黄铜的使用性能不利，这也不利于镁黄铜的应用。镁是非常容易烧损的元素，这对铜合金镁的含量控制带来很大的挑战，对其生产过程中的成分控制也是不利的。磷添加到黄铜中有利于改善其切削性能，但同时降低合金的塑性，低压铸造时合金热裂倾向增大。这使磷在黄铜中的添加量受到很大的限制，也使磷黄铜的使用受到很大限制。由于锡、 碲、硒价格 高昴，锡黄铜以及含 碲、硒黄铜 很难在市场广泛推广。锡对改善铜合金切削性能的作用亦非常有限。已有专利硅黄铜分两种，一种是低锌硅黄铜，如 C69300 ，由于含铜量高，密度偏高，价格贵，市场份额不大。另一种是高锌硅黄铜，切削性能不足。硫的熔点仅为 113 ℃，沸点也仅445℃， 在铜合金的生产过程中很容易进入周围环境而成为污染源，在环保法规越来越严格的今天，其生产的无污染也是个难题，这也对其应用推广极为不利。铜合金中没有锰时，硫在铜合金中通常以低熔点的共晶存在于晶界，使铜合金产生脆性，硫系易切削铜合金进行压力加工的难度一般比较大、成本也比较高。当黄铜熔体中存在锰时，如果加入硫或与硫亲和力小于锰与硫亲和力的硫化物，硫或硫化物就会和锰反应生成硫化锰，在铜合金熔体中以渣的形式浮出，使硫的切削作用明显减弱直至消失。黄铜中锌的含量高，锌是易挥发元素，黄铜熔体中的锰元素与硫元素生成的硫化锰很容易被气态锌带到熔体表面，而且黄铜生产中在出炉之前通常采用喷火工艺以脱气，这会使所生成的硫化锰渣大量被带到熔体表面而以渣的形式去除，这也是铸造黄铜中锰与硫很难共存的重要原因之一。已公开中国发明专利 201110035313.7 在实验室小锭制备中有较好的效果，但是正如其权利要求 3 所述，必须"快速加锌，加锌完成后立即浇铸成铸锭"，在工业化大规模生产中，无法满足上述条件，硫化锰生成物的易切削作用随着铜合金熔体停留时间的延长快速减弱直至消失。而且随着硫含量增加，所生成的硫化锰越多，其变成渣上浮得越快，其切削作用的减弱也越明显。从硫化锰在铜合金中的易切削机理中可知，在不显著恶化铜合金的工艺性能和使用性能的条件下，硫含量越高、硫化锰生成物越多，合金的切削加工性能越好，但是用熔铸法生产时，硫化锰反而更容易浮出熔体，使其提高切削性能的作用减弱得越快，这说明高硫含锰铜合金不宜用熔铸法生产制造。在实际开发中，工程技术人员大多采用合金元素多元化的方法，在铜合金中复合添加多种对切削性能有改进作用的合金元素。但实践证明，添加多种改善切削性能元素的方法也并不理想，一方面，由于元素之间的相互作用，有的会相互降低改善切削性能的效果。另一方面，由于添加多种金属元素后，会产生合金强化的效果，使铜合金的强度、硬度都提高，在一定程度还会降低铜合金的压力加工和机加工性能。而且稀、贵元素的加入量过多也会使铜合金的成本提高，对市场推广应用也不利。利用多种元素的叠加来改善铜合金的工艺性能与使用性能也有很大的局限性。
在含油自润滑轴承中，常采用含铅铜合金，不过铅黄铜面临淘汰的命运。也有采用在铜合金中加入石墨的方法，石墨有优异的润滑性能，是应用非常广泛的润滑剂之一。但是像铅一样，石墨与铜几乎不固溶，其与铜的结合是机械啮合，没有形成冶金结合，界面强度低。这造成石墨含油自润滑轴承的强度有限，不能满足重载高速的使用环境。
当前市场迫切需要一种新的无铅易切削铜合金，该铜合金既有优异的工艺性能如切削加工、热锻、抛光与电镀性能，又有优良的使用性能如高的强度、抗脱锌、耐氨薰与自润滑性能。本发明正是考虑这一需求而开发。
发明内容
本发明的目的是提供一种高性能的无铅易切削铜合金及其制造方法。除特别说明之外，本发明申请文件中所说的合金成分均指质量分数含量。本发明合金高性能的无铅易切削铜合金的成分为：铜 52.0%-95.0% ，磷 0.001%-0.20% ，锡 0.01%-20% ，锰 0.55%-7.0% ，硫 0.191%-1.0% ；除锌外跟硫的亲和力小于锰跟硫的亲和力的金属选取一种或多种，含量之和≤ 2.0% ;余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
除锌外与硫亲和力小于锰与硫亲和力的金属为镍、铁、钨、钴、钼、锑、铋或铌元素。
作为本发明的优选，合金的成分为：铜 54.0%-68.0% ，磷 0.001%-0.15% ，锡 0.01%-1% ，锰 1.5%-4.0% ，硫 0.2%-0.6% ，镍、铁、钨、钴、钼、锑、铋、铌元素选取一种或多种，含量之和≤ 1.8% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
进一步，合金的成分为：铜 56.0%-64.0% ，磷 0.001%-0.12% ，锡 0.01%-0.8% ，锰 2.0%-3.5% ，硫 0.22%-0.40% ，镍、铁、钨、钴、钼、锑、铋、铌元素选取一种或多种，含量之和≤ 1.5% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
进一步，合金的成分为：铜 57.0%-62.0% ，磷 0.001%-0.12% ，锡 0.01%-0.6% ，锰 2.0%-3.5% ，硫 0.22%-0.40% ，镍 0.1%-1.2% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
进一步，合金的成分为：铜 57.0%-62.0% ，磷 0.001%-0.08% ，锡 0.01%-0.4% ，锰 2.0%-3.5% ，硫 0.22%-0.30% ，镍 0.1%-0.5% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
合金的成分为：铜 74%-90% ，磷 0.001%-0.12% ，锡 5%-20% ，锰 2.5%-3.5% ，硫 0.2%-1.0% ，镍、铁、钨、钴、钼、锑、铋、铌元素选取一种或多种，含量之和≤ 2.0% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
进一步，合金的成分为：铜 84%-90% ，磷 0.001%-0.12% ，锡 5%-11% ，锰 2.5%-3.5% ，硫 0.3%-1.0% ，镍、铁、钨、钴、钼、锑、铋、铌元素选取一种或多种，含量之和≤ 1.5% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
进一步，合金的成分为：铜 84%-90% ，磷 0.001%-0.12% ，锡 5%-11% ，锰 2.5%-3.5% ，硫 0.4%-0.8% ，镍 0.1%-1.2% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
进一步，合金的成分为：铜 84%-90% ，磷 0.001%-0.12% ，锡 5%-11% ，锰 2.5%-3.5% ，硫 0.4%-0.7% ，镍 0.1%-0.5% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
当锡的含量小于 5% 时，本发明无铅易切削铜合金工艺流程如下：
按铜、锡、锰、磷、锌依次熔化，待合金元素均匀化后，用水雾化或气雾化的方法制成含锰的铜合金粉末；或按铜、锡、磷、锌依次熔化，待合金元素均匀化后用水雾化或气雾化的方法制成不含锰的铜合金粉末； 将镍粉、含锰的铜合金粉末与跟硫的亲和力小于锰跟硫的亲和力的金属硫化物中的一种或多种配料，或者镍粉、不含锰的铜合金粉末、锰粉与跟硫的亲和力小于锰跟硫的亲和力的金属硫化物中的一种或多种配料，然后外加成形剂 0.5%-1.5% ，将所有配好的粉末装入混料器，混合时间 0.4-5h ，使各种粉末分布均匀； 将混合均匀的粉末压制成型、然后烧结，烧结工艺为：从室温开始加热至烧结温度 680-780 ℃，加热时间 1-5h ，充分去除成形剂，保温时间 30-120min ，烧结气氛为还原性气氛或者惰性气氛； 将烧结后的铜合金用 500-800MPa 的压强冷复压，或者在冲头快速运动的冲床上用 200-400MPa 的压强冷模锻，然后复烧，复烧工艺为：从室温开始加热至烧结温度 820-870 ℃，加热时间 1-3h ，保温时间 30-120min ，烧结气氛为还原性气氛或者惰性气氛； 将复压复烧后的铜合金进行热加工，热加工的温度为 800-870 度。
所述的金属硫化物为固态金属硫化物。
所述的金属硫化物为铁、钴、镍、锡、钨、钼、铌、铜、锌、锑和铋十一种金属硫化物。
所述的金属硫化物为硫化铜、硫化亚铜、硫化锌、硫化锡、硫化镍、硫化铁、二硫化亚铁、硫化亚铁、硫化钨、硫化钴、二硫化钼、三硫化钼、四硫化二锑、五硫化二锑、三硫化二锑、三硫化二铋、二硫化铌和三硫化铌。
所述金属硫化物中，优选为硫化铜、硫化锌和硫化铁。
所述的热加工为热模锻或热挤压。
当锡的含量大于等于 5% 时，无铅易切削铜合金工艺流程如下：
将铜、锡、锰、锌依次熔化，待合金元素均匀化后用水雾化或气雾化的方法制成含锰的铜合金粉末；或将铜、锡、锌依次熔化，待合金元素均匀化后用水雾化或气雾化的方法制成不含锰的铜合金粉末； 将镍粉、含锰的铜合金粉末或者镍粉、不含锰的铜合金粉末与锰粉，与跟硫的亲和力小于锰跟硫的亲和力的金属硫化物中的一种或多种配料，然后外加成形剂 0.5%-1.5% ，混合时间 0.4-5h ，使各种粉末分布均匀； 将混合均匀的粉末压制成型、然后烧结，烧结工艺为：从室温开始加热至烧结温度 730-770 ℃，加热时间 1-5h ，充分去除成形剂，保温时间 30-120min ，烧结气氛为还原性气氛或者惰性气氛。
所述的成形剂是石蜡粉或硬脂酸锌粉。
从热挤压棒上取样制备 抗拉强度试样、切削性能试样、抗脱锌腐蚀试样和氨薰应力腐蚀试样。从烧结后的铜锡合金为基的铜合金样上取样进行抗弯强度和延伸率测试，制备摩擦磨损实验试样并在 90 ℃的热油中浸泡 1 小时，然后将浸油后的试样进行摩擦磨损实验。得到合金的性能。
铅在铜熔体中的溶解度较大，但在室温铜中铅的固溶度几乎为零。铅黄铜熔体凝固时，铅以微细的球形颗粒形式弥散分布在黄铜晶界，有时还会分布在晶内。铅有脆而软的特点，而且铅的熔点只有 327.5 ℃， 当对铅黄铜进行切削加工时产生的摩擦热会使铅颗粒进一步软化，当铅黄铜被切削时，这些弥散的铅颗粒相当于黄铜中存在的一个个空洞，应力容易在此集中，产生所谓的'切口效应'，从而导致切屑易于在此断裂。另外，在刀头与切屑的接触局部因切削加工作功转化为热而使铅瞬间熔化，也有助于改变切屑的形状，并起到润滑刀具的作用，可以使刀头磨损减少到最低。因此，铅在易切削黄铜材料的切削加工过程中起着改变切屑形状、碎裂切屑、减少粘结和焊合以及提高切削速度的作用，可大大提高切削加工的效率，并增加刀具的使用寿命，降低加工表面的粗糙度，使加工表面平整光滑。铅的特性及其在易切削铅黄铜中的存在状态对其切削性能有决定性的作用 。含铅自润滑铜合金中的铅，也是由于其软而脆的特点起到减摩的作用，石墨自润滑铜合金中的石墨作用机理与铅的作用类似。本发明中采用在铜合金中同时添加锰和金属硫化物的方法，在烧结的过程中由于锰的活性高于所添加金属硫化物中的金属，于是硫化物与锰发生反应，生成硫化锰或者硫化锰与其它硫化物的混合物。这种原位生成的硫化物主要为硫化锰，与铜合金组织的结合是一种冶金结合，界面为共格或半共格，强度高。原位反应产物硫化锰具有层状结构，其结构特点与石墨很相似，同时其也具有软而滑的特性。硫化锰在铜合金中的存在 相当于铜合金中存在着孔洞，应力容易在此集中，产生所谓的'切口效应'，从而导致切屑易于在此断裂。硫化锰的断屑机理与铅黄铜中铅的断屑机理是一致的。由于 生成的硫化物 颗粒对切削刀具有润滑的作用，也能减小刀头的磨损作用，大大提高切削加工效率。 所生成的硫化锰颗粒与 铜合金晶粒之间结合良好，界面干净、结合强度高，石墨自润滑铜合金中的石墨颗粒则没有硫化锰颗粒的这种作用，所以在自润滑铜合金中除了有良好的润滑作用，还具有比石墨自润滑铜合金更高的强度。
一般认为磷的作用是脱氧，能改善合金的铸造性能和焊接性能，减少有益元素硅、锡和镁的氧化损失，细化黄铜的晶粒。 在本发明合金中，磷添加量控制在 0.001%-0.20% 范围内，主要作用是在烧结的过程中使铜合金粉末的熔点降低，起到活化烧结的作用。
本发明的优点： 无铅易切削高硫含锰铜合金具有优异的工艺性能如优异的切削加工、热锻等性能和优良的使用性能如高的强度、抗脱锌、耐氨薰、抛光、电镀与自润滑性能。复压复烧后的黄铜有良好的热锻、热挤压等热加工性能 。热挤压黄铜的切削性能好、强度高 。按 ISO6509 ： 1981 《金属及合金的腐蚀 - 黄铜抗脱锌腐蚀性能的测定》，热挤压黄铜的抗脱锌性能优异，按 GB/T10567.2-2007 《铜及铜合金加工材残余应力检验方法 : 氨薰试验法》，但氨水浓度为 14% ，黄铜最长耐氨薰达 16 小时而没有裂纹。 铜锡合金为基的自润滑铜合金的 抗弯强度和延伸率最高相当于石墨自润滑铜合金的 111% 和 116% 。铜合金成分简单，组成元素不含铅、镉、汞、砷等有害元素，生产过程无污染。铜合金不含铬，通过合金设计还能够实现不含铋、锑等元素，完全能满足水暖卫浴行业对有害元素浸出的严格要求。
具体实施方式
实施例 1 ： 含锰的铜合金粉末中各元素的质量分数分别为：铜 54.0% ， 磷 0.11% ，锡 0.011% ， 锰 0.6% ，余量为锌以及不可避免的杂质。各种粉末的质量分数分别如下：硫化物粉末为硫化铜粉末与硫化锌粉末混合物，其含量分别为 0.8% 和 0.30% ；镍粉的含量为 2.0% ；外加成形剂石蜡粉的含量为 0.5% ；余量为上述含锰的铜合金粉末。粉末混料时间 4.0h ，混料结束后即压制，压制完后即放入烧结炉中烧结，烧结工艺为：从室温开始加热至烧结温度，加热时间 5.0h ，充分去除成形剂，烧结温度 680 ℃，保温时间 100min ，烧结气氛为惰性气氛，烧结完后通水冷却到室温。将烧结后的黄铜棒用 500MPa 的压强复压，然后复烧，复烧工艺为：从室温开始加热至烧结温度 820 ℃，加热时间 3.0h ，保温时间 120min ，烧结气氛为惰性气氛。将复烧后的黄铜在 800 ℃热挤压，热挤压比为 120 。从挤压棒上取样制备 抗拉强度试样、切削性能试样、抗脱锌腐蚀试样和氨薰应力腐蚀试样。实验结果发现， 切削能力相当于铅黄铜的 77% 。抗拉强度为 599.0MPa ，屈服强度 329.5MPa ，平均脱锌腐蚀层厚度 192.2μm ，最大脱锌层厚度 329.9μm ，氨薰 16 小时后不开裂。
实施例 2- 实施例 33 : 实施例 2-33 的所有实施例中铜合金粉末的化学成分见表 1 ，各种粉末的质量百分含量见表 2 ，对应实施例中铜合金制造工艺参数见表 3 ，实施例 2-33 中铜合金的性能见表 4 。
实施例 34 ： 含锰的铜合金粉末中各元素的质量分数分别为：铜 88% ，锡 10.0% ， 锰 1.5% ，余量为锌以及不可避免的杂质。各种粉末的质量分数分别如下：硫化铜、硫化亚铜、硫化锌、硫化锡、硫化镍等各种粉末的混合物，每种硫化物的含量分别为 0.2% ；镍粉的含量为 0.3% ；外加成形剂石蜡粉的含量为 1.2% ；余量为上述含锰的铜合金粉末。粉末混料时间 2h ，混料结束后即压制，压制完后即放入烧结炉中烧结，烧结工艺为：从室温开始加热至烧结温度，加热时间 2h ，充分去除成形剂，烧结温度 750 ℃，保温时间 60min ，烧结气氛为还原性气氛，烧结完后通水冷却到室温。摩擦磨损试样在 90 ℃热油中浸泡 1 小时， 实验结果发现，无铅自润滑铜合金的摩擦系数相当于石墨自润滑铜合金的 96% ，磨损量相当于石墨自润滑铜合金的 95% 。力学性能实验结果发现，无铅自润滑铜合金的抗拉强度相当于石墨自润滑铜合金的 110% ，而延伸率相当于石墨自润滑铜合金的 116% 。
实施例 35-42: 铜合金粉末的化学成分见表 1 ，各种粉末的质量分数含量见表 2 ，对应实施例中铜合金制造工艺参数见表 3 ，实施例 35-42 中所有摩擦磨损试样均在 90 ℃热油中浸泡 1 小时， 铜合金的性能见表 5 。
表 1 所有实施例中铜合金粉末的化学成分
实施例 Cu/% Mn/% P/% Sn/% Zn/%
1 54.0 0.6 0.11 0.011 余量
2 54.0 1.5 0.12 0.012 余量
3 54.0 3.5 0.13 0.013 余量
4 54.0 7.0 0.09 0.014 余量
5 59.0 5.0 0.12 0.015 余量
6 59.0 3.0 0.08 0.016 余量
7 59.0 2.5 0.16 0.017 余量
8 59.0 1.5 0.10 0.018 余量
9 64.0 - 0.15 0.019 余量
10 64.0 - 0.12 0.011 余量
11 64.0 - 0.11 0.011 余量
12 64.0 - 0.09 0.011 余量
13 70.0 - 0.15 0.011 余量
14 70.0 - 0.12 0.011 余量
15 70.0 - 0.14 0.011 余量
16 70.0 - 0.12 0.011 余量
17 52.0 0.5 0.05 0.011 余量
18 54.0 1.5 0.05 0.011 余量
19 54.0 3.5 0.05 0.011 余量
20 54.0 7.0 0.05 0.011 余量
21 59.0 5.0 0.05 0.011 余量
22 59.0 3.0 0.05 0.011 余量
23 59.0 2.5 0.05 0.011 余量
24 59.0 1.5 0.05 0.011 余量
25 64.0 - 0.05 0.011 余量
26 64.0 - 0.05 0.011 余量
27 64.0 - 0.05 0.011 余量
28 64.0 - 0.09 0.011 余量
29 70.0 - 0.05 0.011 余量
30 70.0 - 0.05 0.011 余量
31 80.0 - 0.04 0.011 余量
32 88.0 - 0.03 0.011 余量
33 58.0 6.0 0.03 0.011 余量
34 88 1.5 - 10.0 余量
35 88 1.0 - 9.0 余量
36 88 0.6 - 11.0 余量
37 88 1.5 - 10.0 余量
38 77 0.6 - 20.0 余量
39 77 1.0 - 19.0 余量
40 77 1.0 - 21.0 余量
41 77 - - 20.0 余量
42 88 1.0 - 5.5 余量
- 表示未添加，仅有原材料带入
表 2 所有实施例中各种粉末的质量分数含量
实施例 硫化物 /% 镍粉 /% 外加成形剂 /% 锰粉 /% 铜合金粉 /%
1 硫化铜 0.80 ，硫化锌 0.30 2.0 0.5 - 余量
2 硫化锌 0.40 、二硫化亚铁 0.10 、三硫化钼 0.10 1.8 1.5 - 余量
3 硫化铜、四硫化二锑、五硫化二锑、三硫化二锑，三硫化二铋，二硫化铌，三硫化铌混合粉末，含量各 0.10 ，硫化锌 0.30 1.2 0.8 - 余量
4 硫化镍 0.30 ，硫化锌 0.30 0.8 1.0 - 余量
5 硫化锡 0.40 ，硫化锌 0.60 0.3 0.6 - 余量
6 硫化亚铜 1.50 ，硫化锌 0.60 0.3 1.0 - 余量
7 硫化锌 1.20 0.3 1.2 - 余量
8 硫化铜 1.00 ，硫化锌 0.30 0.3 0.9 - 余量
9 硫化铁 0.80 ，硫化锌 0.30 0.3 1.2 3.0 余量
10 硫化亚铁 0.70 硫化锌 0.30 0.3 1.2 2.0 余量
11 硫化钨 1.80 ，硫化锌 0.30 0.3 0.8 1.0 余量
12 硫化钴 2.00 ，硫化锌 0.30 0.3 1.2 3.0 余量
13 二硫化钼 1.80 ，硫化锌 0.30 0.2 1.0 2.0 余量
14 硫化钨、硫化铁、硫化铜混合粉末，含量各 0.30 0.2 1.2 2.0 余量
15 硫化锡、硫化镍、硫化铁、硫化亚铁、硫化钨、硫化钴、二硫化钼、硫化铜混合粉末，含量各 0.10 ，硫化锌 0.30 0.2 1.1 3.5 余量
16 硫化铜、硫化亚铜、硫化锌、硫化锡、硫化镍、硫化铁、硫化亚铁混合粉末，含量各 0.20 0.2 1.2 3.5 余量
17 硫化铜 0.60 ， 硫化锌 0.30 0.3 0.5 - 余量
18 硫化铜 1.07 ， 硫化锌 0.30 0.8 1.5 - 余量
19 硫化铜 1.55 ， 硫化锌 0.30 0.8 0.8 - 余量
20 硫化铜 2.03 ， 硫化锌 0.30 0.3 1.0 - 余量
21 硫化铜 0.60 ， 硫化锌 0.30 0.5 0.6 - 余量
22 硫化铜 1.07 ， 硫化锌 0.30 0.1 1.0 - 余量
23 硫化铜 1.55 ， 硫化锌 0.30 0.1 1.2 - 余量
24 硫化铜 2.03 ， 硫化锌 0.30 0.5 0.9 - 余量
25 硫化铜 0.60 ， 硫化锌 0.30 0.1 1.2 3.0 余量
26 硫化铜 1.07 ， 硫化锌 0.30 0.5 1.2 2.0 余量
27 硫化铜 1.55 ， 硫化锌 0.30 0.5 0.8 1.0 余量
28 硫化铜 2.03 ， 硫化锌 0.30 0.1 1.2 3.0 余量
29 硫化铜 0.60 ， 硫化锌 0.30 0.8 1.0 2.0 余量
30 硫化铜 1.07 ， 硫化锌 0.30 0.3 1.2 2.0 余量
31 硫化铜 1.55 ， 硫化锌 0.30 0.3 1.1 3.5 余量
32 硫化铜 2.03 ， 硫化锌 0.30 0.8 1.2 3.5 余量
33 硫化锌 0.90 0.3 0.5 - 余量
34 硫化铜、硫化亚铜、硫化锌、硫化锡、硫化镍混合粉末，含量各 0.20 0.3 1.2 - 余量
35 硫化锌 1.00 0.3 1.1 - 余量
36 硫化锌 1.40 0.3 1.0 - 余量
37 硫化镍 0.50 ，硫化锌 0.30 0.3 1.2 - 余量
38 硫化铜 1.00 ，硫化锌 0.30 0.3 1.1 - 余量
39 硫化钨 1.80 ，硫化锌 0.30 0.3 1.2 - 余量
40 硫化铁 2.00 ，硫化锌 0.30 0.3 1.0 - 余量
41 二硫化钼 1.00 ，硫化锌 0.30 0.3 0.9 0.6 余量
42 硫化铜 1.55 ， 硫化锌 0.30 0.3 0.6 - 余量
- 表示未添加
表 3 所有实施例中铜合金制造工艺参数
实
施
例		 混料时间 /h 烧结温度 / ℃ 加热时间 /h 保温时间 /min 烧结气氛 复烧温度 / ℃ 加热时间 /h 保温时间 /min 烧结气氛 复压压强 /MPa 冷模锻压强 / MPa 热挤压温度
1 4 680 5 100 惰性 820 3 120 惰性 500 - 800
2 2 680 3 100 惰性 840 2 105 惰性 600 - 810
3 4 680 5 100 还原 860 2 60 还原 800 - 820
4 2 680 5 100 还原 870 1 30 还原 700 - 830
5 4 680 2 100 还原 860 2 90 还原 700 - 840
6 3 680 3 100 还原 860 2 90 还原 700 - 850
7 4 680 2 100 还原 860 2 90 还原 700 - 860
8 2 680 2 100 还原 860 2 90 还原 700 - 870
9 3 730 2 80 还原 860 2 90 还原 700 - 830
10 1 730 2 80 还原 860 2 90 还原 700 - 830
11 2 730 2 80 还原 860 2 90 还原 700 - 830
12 1 730 2 80 还原 860 2 90 还原 700 - 830
13 2 780 1 60 还原 860 2 90 还原 700 - 830
14 2 780 2 60 还原 860 2 90 还原 700 - 830
15 3 780 2 60 还原 860 2 90 还原 700 - 830
16 2 780 2 60 还原 860 2 90 还原 - 200 830
17 4 680 5 100 还原 860 2 90 还原 - 300 830
18 2 680 3 100 还原 860 2 90 还原 - 400 830
19 4 680 5 100 还原 860 2 90 还原 - 300 830
20 2 680 5 100 还原 860 2 90 还原 - 300 830
21 4 680 1 100 还原 860 2 90 还原 - 300 830
22 3 680 3 100 还原 860 2 90 还原 - 300 830
23 4 680 2 100 还原 860 2 90 还原 - 300 830
24 2 680 2 100 还原 860 2 90 还原 - 300 830
25 3 680 2 100 还原 860 2 90 还原 - 300 830
26 1 680 4 100 还原 860 2 90 还原 - 300 830
27 2 680 2 100 还原 860 2 90 还原 - 300 830
28 1 680 4 100 还原 860 2 90 还原 - 300 830
29 2 680 2 100 还原 860 2 90 还原 - 300 830
30 2 680 2 100 还原 860 2 90 还原 - 300 830
31 3 680 2 100 还原 860 2 90 还原 - 300 830
32 2 680 2 100 还原 860 2 90 还原 - 300 830
33 2 780 3 100 还原 870 2 90 还原 - 400 800
34 2 750 2 60 还原 - - - - - - -
35 2 740 2 90 还原 - - - - - - -
36 3 730 2 120 还原 - - - - - - -
37 2 770 2 45 还原 - - - - - - -
38 3 740 2 75 还原 - - - - - - -
39 2 730 2 90 还原 - - - - - - -
40 2 760 2 45 还原 - - - - - - -
41 2 750 2 60 还原 - - - - - - -
42 2 760 2 90 还原 - - - - - - -
- 表示该工序未执行
表 4 实施例 1-33 中铜合金的性能
实施例 热挤压比 相当于铅黄铜切削性能 /% 抗拉强度 /MPa 屈服强度 /MPa 平均脱锌层厚度 /μm 最大脱锌层厚度 /μm 氨薰不开裂时间 /h
1 120 77 599.0 329.5 192.2 329.9 16
2 120 82 624.0 331.7 168.4 296.6 16
3 120 86 574.1 313.8 195.7 338.1 16
4 126 80 554.1 299.5 182.6 321.5 16
5 120 85 614.0 336.4 176.3 310.4 16
6 120 88 604.0 328.9 144.5 257.2 16
7 120 86 439.3 241.2 197.3 341.8 8
8 110 85 429.3 223.1 200.5 343.7 8
9 110 83 579.2 315.3 181.1 318.3 16
10 110 84 603.9 332.1 188.8 329.8 16
11 110 83 588.7 311.2 174.9 307.6 16
12 110 84 579.4 308.2 173.0 304.9 16
13 110 85 574.5 304.9 168.4 299.2 16
14 110 83 539.3 277.1 178.0 307.6 16
15 110 83 479.6 253.7 198.9 341.2 8
16 110 87 449.9 229.5 202.1 349.5 8
17 100 87 664.9 354.2 154.3 476.4 16
18 100 82 458.5 215.7 196.2 457.8 16
19 100 86 583.5 290.8 180.4 258.9 16
20 100 80 426.0 202.3 234.8 398.4 8
21 100 85 516.5 237.2 189.4 301.8 16
22 100 88 609.6 337.7 179.9 293.1 6
23 100 86 454.1 219.1 169.5 341.8 16
24 100 85 391.2 220.7 176.6 230.6 16
25 100 83 613.1 300.9 190.7 386.9 16
26 75 84 579.4 347.0 162.6 205.1 16
27 100 83 657.7 353.2 167.0 296.0 10
28 100 84 355.1 137.7 191.2 371.6 16
29 100 85 375.8 155.2 203.6 317.8 12
30 100 83 403.8 174.8 156.7 250.9 16
31 100 83 363.7 150.7 208.0 337.8 16
32 100 87 377.2 185.9 193.3 321.5 16
33 100 89 676.3 359.8 140.1 199.8 16
表 5 实施例 34-42 中铜合金的性能
实施例 相当于石墨自润滑铜合金摩擦系数 /% 相当于石墨自润滑铜合金磨损量 /% 相当于石墨自润滑铜合金抗弯强度 /% 相当于石墨自润滑铜合金延伸率 /%
34 96 95 110 116
35 97 95 108 114
36 95 94 109 115
37 95 93 111 117
38 94 94 110 114
39 97 96 107 114
40 97 96 107 113
41 97 97 108 113
42 97 96 111 116

Claims (18)

  1. 一种无铅易切削高硫含锰铜合金，其特征在于：铜合金成分的质量分数含量为铜 52.0%-95.0% ，磷 0.001%-0.20%
    ，锡 0.01%-20% ，锰 0.55%-7.0% ，硫 0.191%-1.0% ；除锌外与硫亲和力小于锰与硫亲和力的金属一种或多种，含量之和≤ 2.0% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  2. 根据权利要求 1 所述的无铅易切削高硫含锰铜合金，其特征在于：所述的除锌外与硫亲和力小于锰与硫亲和力的金属为镍、铁、钨、钴、钼、锑、铋和铌元素。
  3. 根据权利要求 2 所述的无铅易切削高硫含锰铜合金，其特征在于：合金的成分为铜 54.0%-68.0% ，磷 0.001%-0.15% ，锡 0.01%-1% ，锰 1.5%-4.0% ，硫 0.2%-0.6% ，镍、铁、钨、钴、钼、锑、铋、铌元素选取一种或多种，含量之和≤ 1.8% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  4. 根据权利要求 3 所述的无铅易切削高硫含锰铜合金，其特征在于：合金的成分为铜 56.0%-64.0% ，磷 0.001%-0.12% ，锡 0.01%-0.8% ，锰 2.0%-3.5% ，硫 0.22%-0.40% ，镍、铁、钨、钴、钼、锑、铋、铌元素选取一种或多种，含量之和≤ 1.5% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  5. 根据权利要求 4 所述的无铅易切削高硫含锰铜合金，其特征在于：合金的成分为铜 57.0%-62.0% ，磷 0.001%-0.12% ，锡 0.01%-0.6% ，锰 2.0%-3.5% ，硫 0.22%-0.40% ，镍 0.1%-1.2% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  6. 根据权利要求 5 所述的无铅易切削高硫含锰铜合金，其特征在于：合金的成分为含铜 57.0%-62.0% ，磷 0.001%-0.08% ，锡 0.01%-0.4% ，锰 2.0%-3.5% ，硫 0.22%-0.30% ，镍 0.1%-0.5% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  7. 根据权利要求 2 所述的无铅易切削高硫含锰铜合金，其特征在于：合金的成分为铜 74%-90% ，磷 0.001%-0.12% ，锡 5%-20% ，锰 2.5%-3.5% ，硫 0.2%-1.0% ，镍、铁、钨、钴、钼、锑、铋、铌元素选取一种或多种，含量之和≤ 2.0% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  8. 根据权利要求 7 所述的无铅易切削高硫含锰铜合金，其特征在于：合金的成分为铜 84%-90% ，磷 0.001%-0.12% ，锡 5%-11% ，锰 2.5%-3.5% ，硫 0.3%-1.0% ，镍、铁、钨、钴、钼、锑、铋、铌元素选取一种或多种，含量之和≤ 1.5% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  9. 根据权利要求 8 所述的无铅易切削高硫含锰铜合金，其特征在于：合金的成分为铜 84%-90% ，磷 0.001%-0.12% ，锡 5%-11% ，锰 2.5%-3.5% ，硫 0.4%-0.8% ，镍 0.1%-1.2% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  10. 根据权利要求 9 所述的无铅易切削高硫含锰铜合金，其特征在于：铜合金的成分为含铜 84%-90% ，磷 0.001%-0.12% ，锡 5%-11% ，锰 2.5%-3.5% ，硫 0.4%-0.7% ，镍 0.1%-0.5% ，余量为锌及不可避免的杂质，其中铅≤ 0.05% 。
  11. 根据权利要求 2 、 3 、 4 、 5 或 6 所述之一的无铅易切削高硫含锰铜合金制造方法，其特征在于：按铜、锡、锰、磷、锌依次熔化，待合金元素均匀化后，用水雾化或气雾化的方法制成含锰的铜合金粉末；或按铜、锡、磷、锌依次熔化，待合金元素均匀化后用水雾化或气雾化的方法制成不含锰的铜合金粉末；将镍粉、含锰的铜合金粉末与跟硫的亲和力小于锰跟硫的亲和力的金属硫化物中的一种或多种配料，或者镍粉、不含锰的铜合金粉末、锰粉与跟硫的亲和力小于锰跟硫的亲和力的金属硫化物中的一种或多种配料，然后外加成形剂 0.5%-1.5% ，混合时间 0.4-5h ，使各种粉末分布均匀； 将混合均匀的粉末压制成型，然后烧结，烧结工艺为：从室温开始加热至烧结温度 680-780 ℃，加热时间 1-5h ，充分去除成形剂，保温时间 30-120min ，烧结气氛为还原性气氛或者惰性气氛； 将烧结后的铜合金用 500-800MPa 的压强冷复压，或者在冲头快速运动的冲床上用 200-400MPa 的压强冷模锻，然后复烧，复烧工艺为：从室温开始加热至烧结温度 820-870 ℃，加热时间 1-3h ，保温时间 30-120min ，烧结气氛为还原性气氛或者惰性气氛；将复压复烧后的铜合金进行热加工，热加工的温度为 800-870 度。
  12. 根据权利要求 7 、 8 、 9 或 10 所述之一的无铅易切削高硫含锰铜合金制造方法，其特征在于：将铜、锡、锰、锌依次熔化，待合金元素均匀化后用水雾化或气雾化的方法制成含锰的铜合金粉末；将铜、锡、锌依次熔化，待合金元素均匀化后用水雾化或气雾化的方法制成不含锰的铜合金粉末； 将镍粉、含锰的铜合金粉末或者镍粉、不含锰的铜合金粉末与锰粉，与跟硫的亲和力小于锰跟硫的亲和力的金属硫化物中的一种或多种配料，然后外加成形剂 0.5%-1.5% ，混合时间 0.4-5h ，使各种粉末分布均匀； 将混合均匀的粉末压制成型、然后烧结，烧结工艺为：从室温开始加热至烧结温度 730-770 ℃，加热时间 1-5h ，充分去除成形剂，保温时间 30-120min ，烧结气氛为还原性气氛或者惰性气氛。
  13. 根据权利要求 11 或 12 所述的无铅易切削高硫含锰铜合金制造方法，其特征在于：所述的金属硫化物为固态金属硫化物。
  14. 根据权利要求 13 所述的无铅易切削高硫含锰铜合金制造方法，其特征在于：所述的金属硫化物为铁、钴、镍、锡、钨、钼、铌、铜、锌、锑和铋十一种金属硫化物。
  15. 根据权利要求 14 所述的无铅易切削高硫含锰铜合金制造方法，其特征在于：所述的金属硫化物为硫化铜、硫化亚铜、硫化锌、硫化锡、硫化镍、硫化铁、二硫化亚铁、硫化亚铁、硫化钨、硫化钴、二硫化钼、三硫化钼、四硫化二锑、五硫化二锑、三硫化二锑、三硫化二铋、二硫化铌和三硫化铌。
  16. 根据权利要求 15 所述的无铅易切削高硫含锰铜合金制造方法，其特征在于：所述的金属硫化物为硫化铜、硫化锌和硫化铁。
  17. 根据权利要求 11 或 12 所述的无铅易切削高硫含锰铜合金制造方法，其特征在于：所述的成形剂为石蜡粉或硬脂酸锌粉 。
  18. 根据权利要求权 11 所述的无铅易切削高硫含锰铜合金制造方法，其特征在于：所述的热加工为热模锻或热挤压。
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