WO2016177018A1 - 一种可切削加工黄铜合金及制备方法 - Google Patents

一种可切削加工黄铜合金及制备方法 Download PDF

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WO2016177018A1
WO2016177018A1 PCT/CN2016/000230 CN2016000230W WO2016177018A1 WO 2016177018 A1 WO2016177018 A1 WO 2016177018A1 CN 2016000230 W CN2016000230 W CN 2016000230W WO 2016177018 A1 WO2016177018 A1 WO 2016177018A1
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weight
content
brass alloy
solid solution
stress relief
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PCT/CN2016/000230
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English (en)
French (fr)
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梅景
任世影
陈湖
赵红彬
杨朝勇
毛建锋
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宁波博威合金材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • 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

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  • the invention relates to the technical field of alloys, in particular to a machinable brass alloy and a preparation method thereof.
  • Brass has good process properties, mechanical properties and corrosion resistance and is one of the most widely used alloy materials for non-ferrous metals. Some functional elements are added to the copper-zinc alloy to form a multi-component brass alloy, which can meet the application of specific working conditions.
  • the most widely used lead brass is lead alloy added to copper-zinc alloy.
  • Lead brass has the mechanical properties, corrosion resistance, hot and cold processing properties of ordinary brass, and because lead is present in the alloy as a free lead point, the cuttings are shredded during the cutting process, after high speed cutting. Lead-baked surfaces are widely used in aerospace, automotive, fasteners, hardware and other industries. At present, the copper content in the lead brass alloy is generally between 57 and 75%, and the copper content is relatively high.
  • a copper alloy wear resistant material and a preparation method thereof are disclosed, for example, in Chinese patent application CN101532100A (Application No. 200910058578.1), the alloy composition is as follows: Cu: 54% - 57%; Al: 3% - 5.0%; Mn: 3.5 %-5.5%; Si: 0.5%-1.3%; Fe: 0.7%-1.5%; Zn: balance.
  • the copper content of the alloy is reduced by more than 2% compared with HPb59-1, which can better reduce the cost of raw materials.
  • the tensile strength of the alloy material is ⁇ 700 MPa
  • the hardness is ⁇ 90 HRB
  • the elongation is 3-5%.
  • the performance is very different from that of lead brass. Due to the high strength and hardness of the material, the cutting performance of the material is poor, and the wear of the tool is extremely large, which cannot meet the requirements of high-speed cutting.
  • a lead-free free-cutting deformable tin-bismuth-zinc aluminum alloy is disclosed, the composition of which is 8-12% of aluminum; 0.8-1.5% of copper; ⁇ 0.05-0.2%; tin 0.05-0.15%; the balance is zinc and unavoidable impurities; impurity content ⁇ 0.05%.
  • the alloy uses a lot of cheap zinc, aluminum and other elements, and has good cutting performance, but because of the strength, hardness, creep resistance, fatigue strength and other properties of zinc-aluminum alloy, it is much lower than lead brass, and can not be completely Meet the needs of the application.
  • the first technical problem to be solved by the present invention is to provide a machinable brass alloy which can greatly reduce the alloy cost and has better cutting performance in view of the state of the art.
  • a second technical problem to be solved by the present invention is to provide a method for preparing a machinable brass alloy which can greatly reduce the alloy cost and has better cutting performance.
  • the machinable brass alloy characterized by comprising the following weight composition
  • the sum of copper, manganese and zinc is ⁇ 95wt%, and the unavoidable impurity content is ⁇ 0.1wt%;
  • the alloy contains a body-centered cubic Cu-Zn solid solution and a face-centered cubic Cu-Mn solid solution.
  • the ratio of the Cu-Zn solid solution is ⁇ 80%, the ratio of Cu-Mn solid solution is ⁇ 20%; and the ratio of the body-centered cubic structure in the Cu-Zn solid solution is ⁇ 85%.
  • the ratio of the body-centered cubic structure in the Cu-Zn solid solution is 95-100%.
  • the Cu-Zn solid solution has a particle diameter of 10 to 30 nm, and the Cu-Mn solid solution has a particle diameter of 15 to 40 nm.
  • the alloy has a grain size of 0.03 - 0.2 mm.
  • the alloy may further comprise 0.001% by weight to 4% by weight of component X selected from 0.1% by weight to 4% by weight of Pb, 0.1% by weight to 4% by weight of Bi, 0.1% by weight to 4% by weight of Sb, 0.1wt %-4 wt% of Se, at least one of 0.001 wt% to 2.0 wt% of B, 0.001 wt% to 2.0 wt% of P, and 0.001 wt% to 1 wt% of As.
  • component X selected from 0.1% by weight to 4% by weight of Pb, 0.1% by weight to 4% by weight of Bi, 0.1% by weight to 4% by weight of Sb, 0.1wt %-4 wt% of Se, at least one of 0.001 wt% to 2.0 wt% of B, 0.001 wt% to 2.0 wt% of P, and 0.001 wt% to 1 wt% of As.
  • the content of the Pb is from 0.5% by weight to 3.0% by weight
  • the content of the Bi is from 0.1% by weight to 3.0% by weight
  • the content of the Sb is from 0.1% by weight to 2.5% by weight
  • the content of the Se is 0.1% by weight to 2.0% by weight
  • the content of B is 0.01% by weight to 1.0% by weight
  • the content of P is 0.001% by weight to 1.0% by weight
  • the content of As is 0.002% by weight to 0.6% by weight.
  • the Pb content is from 0.8 wt% to 2.5 wt%
  • the Bi content is from 0.5 wt% to 2.5 wt%
  • the Sb content is from 0.2 wt% to 1.5 wt%
  • the Se The content is from 0.2 wt% to 1.0 wt%
  • the content of B is from 0.05 wt% to 0.5 wt%
  • the content of P is from 0.01 wt% to 0.8 wt%
  • the content of As is from 0.003 to 0.3 wt%.
  • the alloy further contains 0.01% by weight to 5% by weight of the component Y selected from at least one of Al, Fe, Si, Sn, Ni, and Co.
  • the content of the Al is from 0.1% by weight to 3.5% by weight
  • the content of the Fe is from 0.1% by weight to 3.0% by weight
  • the content of the Si is from 0.05% by weight to 1.2% by weight
  • the Sn is The content is from 0.05% by weight to 3% by weight
  • the content of Ni is from 0.5% by weight to 2.5% by weight
  • the content of the Co is from 0.1% by weight to 2% by weight.
  • the content of Al is 0.5 wt% to 3 wt%
  • the content of Fe is 0.1 wt% to 2.5 wt%
  • the content of Si is 0.08 wt% to 1.0 wt%
  • the content of Sn 0.1% by weight to 1.5% by weight
  • the content of Ni is 0.6% by weight to 1.5% by weight
  • the content of Co is from 0.5% by weight to 1% by weight.
  • the content of the Cu is preferably 47.8 wt% to 53.5 wt%, and the content of the Mn is 0.8 wt% to 6.0 wt%.
  • the content of Cu is from 48.9 wt% to 52.7 wt%, and the content of Mn is from 1.0 wt% to 3.9 wt%.
  • the vertical semi-continuous casting temperature is 980 ° C - 1080 ° C
  • the heating extrusion temperature is 550 ° C - 750 ° C
  • the stress relief annealing temperature is 200 ° C - 400 ° C
  • the stress relief annealing heating rate The cooling rate of the stress relief annealing is 5 to 50 ° C / min at 2 to 50 ° C / min.
  • Another technical solution adopted by the present invention to solve the above second technical problem is: a method for preparing the machinable brass alloy, which comprises the following steps in sequence:
  • the temperature of the horizontal continuous casting is 950 ° C - 1080 ° C
  • the heating extrusion temperature is 550 ° C - 750 ° C
  • the stress relief annealing temperature is 200 ° C - 400 ° C
  • the heating rate of the stress relief annealing The cooling rate of the stress relief annealing is 5 to 50 ° C / min at 2 to 50 ° C / min.
  • Another technical solution adopted by the present invention to solve the above second technical problem is: a method for preparing the machinable brass alloy, which comprises the following steps in sequence:
  • the temperature of the horizontal continuous casting is 950 ° C - 1080 ° C
  • the stress relief annealing temperature is 200 ° C - 400 ° C
  • the heating rate of the stress relief annealing is 2-50 ° C / min
  • the stress relief annealing The cooling rate is 5-50 ° C / min.
  • the present application controls the copper content to 45 wt% to 54 wt%, which can balance the cutting performance and mechanical properties of the alloy, and can greatly reduce the alloy cost.
  • the copper content is preferably from 47.8 wt% to 53.5 wt%, more preferably from 48.9 wt% to 52.7 wt%.
  • Manganese and copper can form a Cu-Mn solid solution with a face-centered cubic structure, which can improve the mechanical properties and make the performance of the brass alloy of the present invention more in line with the application of the traditional lead brass.
  • the manganese content is less than 0.5wt%, it cannot form a sufficient amount of Cu-Mn solid solution with face-centered cubic structure, and the material plasticity is not good; as the manganese content increases, the comprehensive performance of the product increases; when the manganese content is greater than 9.0 When wt%, it will lead to excessive sedimentation during casting, affecting the casting performance and due to the solid solution strengthening effect of manganese, the strength and plasticity of the material will be drastically reduced, the hardness will be too high, and the cutting difficulty will increase.
  • the content of manganese is preferably 0.8wt%-6.0wt%, It is preferably from 1.0% by weight to 3.9% by weight.
  • the lead element is distributed in the form of free particles on the substrate because it is not dissolved in copper, forming an effective chip breaking point.
  • the lead element is very soft and has a lubricating effect, which can significantly reduce the cutting resistance and significantly improve the cutting performance of the brass alloy.
  • the lead element content is controlled to be 0.1 wt% to 4 wt%, preferably 0.5 wt% to 3.0 wt%, It is preferably from 0.8% by weight to 2.5% by weight.
  • the lanthanum element is distributed in the form of a sheet on the matrix in the brass alloy, which can significantly improve the chip breaking performance of the brass alloy and reduce the cutting resistance.
  • the addition of lanthanum element to the lead element improves the cutting performance of the brass alloy. obvious.
  • the cerium element content is controlled to be from 0.1% by weight to 4% by weight, preferably from 0.1% by weight to 3.0% by weight, more preferably from 0.5% by weight to 2.5% by weight.
  • the lanthanum element can be dissolved in the brass alloy in a small amount to improve the mechanical properties of the brass alloy, and the lanthanum element can change the distribution of the ruthenium element in the brass alloy, and the yttrium element can be added on the basis of adding yttrium.
  • the niobium element content is less than 0.1 wt%, the improvement effect is not significant, and more than 4 wt% significantly reduces the plasticity of the brass alloy. Therefore, the content of cerium in the brass alloy is controlled to be from 0.1% by weight to 4% by weight, preferably from 0.1% by weight to 2.5% by weight, more preferably from 0.2% by weight to 1.5% by weight.
  • the selenium element is present in the form of a CuSe compound in the brass alloy of the present invention, and the CuSe compound is relatively hard, so that the turning debris can be smoothly broken, thereby improving the cutting performance of the brass alloy, and in the brass alloy containing bismuth element,
  • the addition of selenium can significantly improve the cutting performance.
  • the selenium content is less than 0.1% by weight, a sufficient amount of compound cannot be formed to improve the cutting performance of the brass alloy, but the selenium content is more than 4% by weight, which leads to a decrease in the elongation of the brass alloy, so the selenium content is controlled at 0.1 wt. %-4wt%, preferably from 0.1% by weight to 2.0% by weight, more preferably from 0.2% by weight to 1.0% by weight.
  • Boron and phosphorus can refine grains and improve the strength, hardness and plasticity of brass alloys. Boron is present in the form of oxides on the matrix to improve the structure and properties of the materials, and boron can improve the distribution of lead.
  • the lead is distributed on the substrate in a fine and uniform spherical shape to improve the cutting stability of the brass alloy; if the boron content is less than 0.001% by weight, the cutting performance of the brass alloy cannot be significantly improved.
  • the phosphorus element forms a Cu 3 P compound with copper, which forms a “hole effect” on the brass alloy matrix, increases the chip breaking ability of the brass alloy during the cutting process, improves the cutting performance of the material, and the phosphorus content is less than 0.001% by weight.
  • the boron element content is controlled to be 0.001% by weight to 2% by weight, preferably 0.01% by weight to 1.0% by weight, more preferably 0.05% by weight to 0.5% by weight.
  • the phosphorus element content is controlled to be 0.001% by weight to 2% by weight, preferably 0.001% by weight to 1.0% by weight, more preferably 0.01% by weight to 0.8% by weight.
  • Iron as a nucleating agent in brass alloys, increasing the number of nucleation, hindering the growth of crystal grains, and refining
  • the effect of the grain improves the overall performance of the material, and the undissolved part of the iron element is distributed on the brass matrix in a star-like shape, which can promote the fracture of the chip and improve the cutting performance of the brass alloy.
  • excessive iron content particularly when the content exceeds 5 wt%, causes iron segregation and aggregation, resulting in deterioration of the overall properties of the material. Therefore, the iron element content is controlled to be 0.01 wt% to 5 wt%, preferably 0.1 wt% to 3.0 wt%, more preferably 0.1 wt% to 2.5 wt%.
  • the aluminum element acts to stabilize and strengthen the body-centered cubic Cu-Zn solid solution, so that the matrix of the brass alloy has higher strength and stability.
  • the addition of aluminum element can form an FeAl compound, further improving the mechanical properties of the material.
  • the addition of aluminum can form a dense aluminum oxide protective film on the surface of the brass alloy, increasing the corrosion resistance of the brass alloy.
  • the content of aluminum is less than 0.01% by weight, and the improvement effect is not obvious, but the effect of solid solution strengthening of aluminum is very obvious. Excessive aluminum, especially more than 5% by weight, causes the strength and hardness of the brass alloy to rise sharply and extend sharply. Dropping will limit the range of applications of brass alloys. Therefore, the aluminum element content is controlled to be 0.01 wt% to 5 wt%, preferably 0.1 wt% to 3.5 wt%, more preferably 0.5 wt% to 3 wt%.
  • the addition of silicon forms a SiMn compound with manganese in the brass alloy, and the hardness of the SiMn compound is extremely high, which increases the strength and hardness of the brass alloy, and improves the wear resistance of the brass alloy, so it is required in the field of wear resistance.
  • the brass alloy can be selectively added with silicon.
  • the content of silicon is less than 0.01wt%, which can not significantly improve the properties of the material and cannot form a sufficient amount of SiMn compound, but the highest zinc equivalent of silicon is the highest, such as silicon.
  • the silicon element content is controlled to be 0.01 wt% to 1.5 wt%, preferably 0.05 wt% to 1.2 wt%, more preferably 0.08 wt% to 1.0 wt%.
  • Tin element can be dissolved in copper in a small amount, improve the mechanical properties of brass alloy, and form a layer of tin oxide on the surface of brass alloy, which can significantly increase the corrosion resistance of brass alloy, which is beneficial to the high humidity of brass alloy.
  • the tin element content is controlled to be 0.01 wt% to 5 wt%, preferably 0.05 wt% to 3 wt%, more preferably 0.1 wt% to 1.5 wt%.
  • Nickel and cobalt have good solid solution strengthening effect, can enhance the stability of body-centered cubic Cu-Zn solid solution, and improve the stress distribution, which is beneficial to reduce the gold-containing cutting resistance of brass and improve the cutting of brass alloy. Processing performance. Nickel or cobalt and silicon can be added simultaneously to form stable NiSi, CoSi compounds, forming stress concentration points, improving the chip breaking performance of brass alloys, and increasing the wear resistance of materials, making brass alloys suitable for use. The field of wear resistance requirements.
  • the nickel element content is controlled to be 0.01 wt% to 5 wt%, preferably 0.5 wt% to 2.5 wt%, more preferably 0.6 wt% to 1.5 wt%; and the cobalt element content is controlled to be 0.01 wt% to 5 wt%, preferably 0.1 wt%. %-2 wt%, more preferably 0.5 wt%-1 wt%.
  • Arsenic forms a Cu-As-Zn protective layer on the grain boundary of the brass alloy, which prevents the dissolution of zinc and greatly improves the corrosion resistance of the brass alloy. Therefore, when the brass alloy has corrosion resistance requirements, A small amount of As can be added, the content is less than 0.001% by weight, the corrosion resistance is not obvious, and excessive As (more than 1.5wt%) will increase the stress corrosion of brass.
  • the sensitivity of the crack, so the As content needs to be controlled from 0.001 wt% to 1.0 wt%, preferably from 0.002 wt% to 0.6 wt%, more preferably from 0.003 to 0.3 wt%.
  • the As-B atom pair formed by arsenic and boron can be quickly filled in the vacancy after dezincification corrosion, preventing further dissolution of zinc, and further improving the corrosion resistance of the brass alloy.
  • the Cu-Zn solid solution of the body-centered cubic structure forms a stress concentration point during the cutting process, which is beneficial to the cutting of the cutting chips during the cutting process and improves the cutting performance of the material.
  • the ratio of the solid solution of Cu-Zn is less than 80%, the above effect is not remarkable.
  • the Cu-Mn solid solution of the face-centered cubic structure cannot form stress concentration points during the cutting process, which is not conducive to the fracture of turning chips.
  • the Cu-Mn solid solution content of the face-centered cubic structure is more than 20%, it will cause the cutting process. The difficulty is increased.
  • the Cu-Zn solid solution ratio is controlled to be ⁇ 80%, and the Cu-Mn solid solution ratio is controlled to be ⁇ 20%.
  • the sum of the elements of Cu, Mn and Zn needs to be ⁇ 95% by weight. Due to its special atomic force and stress direction characteristics, the body-centered cubic structure of Cu-Zn solid solution is more obvious than the face-centered cubic structure, which ensures the smooth disconnection of turning chips and avoids the winding process of turning. Knife, poor chip removal, etc., improve the cutting performance of machinable brass alloys.
  • the body-centered cubic structure ratio is ⁇ 85%.
  • the brass alloy has very small chips and no tangles. The problem is that when the body-centered cubic structure ratio reaches 95-100%, the cutting performance is further improved.
  • the particle size of Cu-Zn solid solution determines the difficulty of stress concentration in cutting.
  • the Cu-Zn solid solution has a particle size of more than 30 nm, and the processing stress distribution is relatively dispersed. It cannot form a stress concentration point that meets the requirements of cutting chip breaking, but the solid solution particle size. When it is less than 10 nm, the processing stress concentration effect is very obvious, and it is easy to cause stress cracking during processing. Therefore, the Cu-Zn solid solution particle size of the machinable brass alloy is controlled to be 10-30 nm.
  • the particle size of the Cu-Mn solid solution determines the mechanical properties of the machinable brass alloy.
  • the particle size of the Cu-Mn solid solution is controlled to be 15-40 nm.
  • the grain size of the alloy is less than 0.03mm.
  • the strength and hardness of the brass alloy are too high, which is not conducive to subsequent riveting, hot forging, bending and other processing; while the grain size is greater than 0.2mm, the mechanical properties of the brass alloy are deteriorated.
  • the requirements of the application cannot be fully satisfied; therefore, the present invention controls the grain size of the brass alloy to be 0.03-0.2 mm.
  • the tensile strength of the machinable brass alloy provided by the invention is greater than 450 MPa, which can fully meet the structural strength requirements of the application; the elongation is greater than 15%, and meets the requirements of cold heading, riveting, bending, etc.; HB hardness is 110-180 Between the process, no deformation occurs during the machining process, and the wear of the tool is small. Compared with the lead-bronze alloys of the prior art such as HPb59-1 and C36000, the cutting performance and mechanical properties are superior, and the alloy is greatly reduced. The cost can replace the existing machinable brass alloy in the field of valve copper parts, coaxial connector copper parts, pump heads, lock copper parts, etc., which can alleviate the shortage of copper resources and excess zinc resources in China.
  • Figure 1 is the relationship between the Mn content and the tensile strength of the alloy
  • Figure 2 is the relationship between Mn content and elongation
  • Figure 3 is a relationship between the Mn content and the hardness of the alloy
  • Figure 4 is the relationship between Mn content and cutting force
  • Figure 5 is a photograph of the surface color of the product with different manganese contents, and the reference numerals in the figure are the embodiment numbers;
  • FIG. 6 and FIG. 7 are structural diagrams of the XRD solid solution test of Example 16;
  • Figure 8 is a photograph of the broken pieces after cutting from Example 30 to Example 35, and the reference numerals in the figures are the embodiment numbers;
  • Figure 9 is a photomicrograph of Example 54.
  • Figure 10 is a scanning electron micrograph of the hardness test of CuSe compound on the micro Vickers hardness tester of Example 54;
  • Figure 11 is a photograph of the product obtained by cutting in Example 86;
  • Figure 12 is a photograph of a product obtained by cutting in Example 87.
  • Example 1 and Example 2 are HPb59-1 and C36000 lead brass alloys which are produced according to conventional steps of casting, extrusion, drawing, straightening and annealing.
  • Each component is smelted in a low-frequency melting furnace, and the semi-continuous casting ingot is vertical.
  • the casting temperature is 990 ° C - 1030 ° C, and is heated and extruded into a ⁇ 20 mm bar blank, and the extrusion temperature is 630 ° C - 670 ° C. , drawn into a ⁇ 19mm rod blank, and then subjected to stress annealing at 250 ° C - 280 ° C, the stress relief annealing heating rate is 40-45 ° C / min below 200 ° C, 5-8 ° C / min above 200 ° C.
  • the de-stressing annealing cooling rate is 5-7 ° C / min at 300 ° C or higher, and 45-48 ° C / min at 300 ° C or lower. Finally, the finished bar blank is straightened.
  • the obtained bar stock was sampled, and the contents of the respective elements in each of the samples of Examples 1 to 15 were tested in accordance with GB/T 5121-2008. The results are shown in Table 1.
  • the obtained bar blank was sampled to prepare a tensile specimen of ⁇ 8 mm.
  • the samples were subjected to a tensile test on a 10 ton hydraulic stretching machine.
  • the tensile strength and elongation results obtained are shown in Table 1.
  • the obtained bar blank was sampled to prepare a hardness sample of ⁇ 19 mm and a thickness of 30 mm.
  • the hardness samples were tested on a Brinell hardness tester.
  • the diameter of the ball used was 2.5 mm and the pressure was 62.5 kg.
  • the results of the HB hardness obtained in the test are shown in Table 1.
  • the obtained blank was sampled and prepared into a cutting force sample of ⁇ 19mm and length of 300mm for cutting force test.
  • the test equipment was Chongqing Dijia cutting force test system.
  • the test conditions were: feed rate 0.078, cutting speed 31.5674, back knife volume 0.5.
  • the cutting force calculated by the force calculation formula is shown in Table 2.
  • Examples 1, 2, 3, 14, and 15 are comparative examples, and Example 2 is a standard formulation of the existing grade C36000 lead brass alloy.
  • the relationship between the Mn content and the tensile strength of the alloy is shown in Fig. 1.
  • the relationship between the Mn content and the elongation is shown in Fig. 2, and the relationship between the Mn content and the hardness of the alloy is shown in Fig. 3.
  • the elongation of the machinable brass alloy having a Mn content of between 0.5% by weight and 10.03% by weight is higher than that of the HPb59-1 lead brass.
  • the Mn content is higher than 9.0% by weight, the hardness of the machinable brass alloy begins to rise sharply, much higher than HPb59-1 lead brass.
  • the Mn content is less than 0.5% by weight, or higher than 9.0% by weight, and the tensile strength of the machinable brass alloy is much higher than that of HPb59-1 lead brass, and between 0.5% and 6% by weight, machinable
  • the tensile strength of brass alloys is slightly higher than that of HPb59-1 lead brass. Therefore, a suitable addition range of Mn is from 0.5% by weight to 9.0% by weight.
  • the Mn content is less than 0.5 wt% or higher than 9.0 wt%, and the cutting force of the machinable brass alloy is sharply increased compared with C36000, and the Mn content is 0.5 wt% - 9.0 wt%, and the machinable yellow
  • the cutting force of copper alloys is slightly increased compared to C36000.
  • the cutting performance of C36000 in the field of non-ferrous metal processing is the most recognized copper alloy in the prior art, and the cutting force of the alloy formulation of the present invention is 1.04-1.15 times that of C36000, which can meet the requirements of high-speed cutting.
  • the surface color of the cutting force samples of Example 4, Example 5, Example 7, Example 11, Example 12, and Example 13 after turning was as shown in FIG. It can be seen from Fig. 5 that when the Mn content is less than 6.0 wt%, the surface of the machinable brass alloy is bright yellow, the Mn content is above 6 wt%, and the surface color of the machinable brass alloy is white and the Mn content is reached. 9.0 wt%, the surface color of the brass alloy is white.
  • the Mn element content is from 0.5% by weight to 9.0% by weight, and the Mn content is more preferably from 1.0% by weight to 6.0% by weight, and the desirable Mn content is from 1.3% by weight to 4.9% by weight.
  • Samples were prepared to obtain a tensile specimen of ⁇ 8 mm.
  • the samples were subjected to a tensile test on a 10 ton hydraulic stretching machine.
  • the tensile strength and elongation results obtained are shown in Table 3.
  • the obtained bar blank was sampled to prepare a hardness sample of ⁇ 19 mm and a thickness of 30 mm.
  • the hardness samples were tested on a Brinell hardness tester.
  • the diameter of the ball used was 2.5 mm and the pressure was 62.5 kg.
  • the results of the HB hardness obtained in the test are shown in Table 3.
  • Examples 20, 21, 22, 23, 24, and 25 are comparative examples.
  • the Cu content is more than 45wt%, and the tensile strength, elongation and HB hardness of the machinable brass alloy are closer to that of lead brass.
  • the Cu content is more than 54wt%, the brass alloy can be cut.
  • the tensile strength is lower than that of lead brass, and the elongation is slightly higher than that of lead brass. Therefore, it is suitable that the Cu content of the machinable brass alloy ranges from 45 wt% to 54 wt%.
  • the brass bar blanks prepared in Examples 16 to 25 were made into XRD samples with a diameter of 19 mm and a thickness of 1 mm, and the XRD samples were tested on a solid solution structure and ratio on a Brooke X-ray diffractometer in Germany. The test results are shown in Table 4. Shown.
  • the brass blanks prepared in Examples 16 to 25 were made into a cutting force sample of ⁇ 19 mm and a length of 300 mm, and subjected to a cutting force test on a Chongqing Dijia cutting force test system.
  • the test conditions are: feed rate 0.078, cutting speed 31.5674, and back knife volume 0.5.
  • the tangential force, axial force and radial force were tested.
  • the test results and the cutting forces calculated according to the cutting force calculation formula are shown in Table 4.
  • 6 and 7 are views showing the structure of a solid solution of XRD analysis of Example 16.
  • the ratio of Cu-Zn solid solution is ⁇ 80%, and the ratio of body-centered cubic structure in Cu-Zn solid solution is ⁇ 85%; the ratio of Cu-Mn solid solution is ⁇ 20%, and the cutting force of machinable brass alloy is lower. s level. Therefore, the ratio of Cu-Zn solid solution of the brass alloy can be ⁇ 80%, and the ratio of Cu-Mn solid solution ⁇ 20% is suitable.
  • the copper content when the copper content is above 54 wt%, the Cu-Zn solid solution is above 80%, and the body-centered cubic structure ratio in the Cu-Zn solid solution is ⁇ 85%, the cutting force of the product is at a higher level, The Cu-Zn solid solution of the body-centered cubic structure is improved in terms of cutting performance, and the copper content needs to be less than 54% by weight.
  • Each component is batch-cast ingot after smelting in a low-frequency melting furnace.
  • the casting temperature of horizontal continuous casting is 970°C-1020°C; then it is heated and extruded into ⁇ 20mm bar blank, and the heating extrusion temperature is 620°C-660°C.
  • the stress relief annealing temperature is 260 ° C -300 ° C
  • the de-stress annealing heating rate is below 40-43 ° C / min below 200 ° C, and 8-10 ° C above 200 ° C /min
  • the stress relief annealing cooling rate is 5-6 ° C / min, 200 ° C below 32-34 ° C / min; finally straightened to the finished bar blank.
  • Each component is batch-cast ingot after smelting in a low-frequency melting furnace.
  • the casting temperature of horizontal continuous casting is 970°C-1020°C; then it is heated and extruded into ⁇ 20mm bar blank, and the heating extrusion temperature is 620°C-660°C.
  • the obtained bar blank was sampled and prepared into a hardness sample of ⁇ 19 mm and thickness of 30 mm, and tested on a Brinell hardness tester.
  • the diameter of the ball used was 2.5 mm and the pressure was 62.5 kg.
  • the hardness of the test was as follows. 5 is shown.
  • the prepared rod blank was prepared into XRD samples of ⁇ 19 mm and thickness of 1 mm, and the particle size test of body-centered cubic Cu-Zn solid solution and face-centered cubic Cu-Mn solid solution was carried out on a German Brook X-ray diffractometer. As shown in Table 6.
  • the prepared bar blank was prepared into a cutting force sample of ⁇ 19 mm and a length of 300 mm, and the cutting force test was performed on the Chongqing Dijia cutting force test system.
  • the test conditions are: feed rate 0.078, cutting speed 31.5674, and back knife volume 0.5.
  • the tangential force, axial force, radial force during the cutting of the test material, the test results and the cutting force calculated according to the cutting force calculation formula are shown in Table 6.
  • Examples 27, 30, 31, and 32 are comparative examples.
  • the cutting force of the machinable brass alloy is generally high, when the Cu-Mn solid solution particle size ⁇ 15 nm Or Cu-Mn solid solution When the volume of the body is ⁇ 40 nm, the cutting force of the machinable brass alloy is as high as the whole. Therefore, the Cu-Zn solid solution particle size of the machinable brass alloy is 10-30 nm, and the Cu-Mn solid solution particle size of 15-40 nm is a suitable range.
  • the obtained bar blank was prepared into a tensile specimen of ⁇ 8 mm, and a tensile test was performed on a 10 ton hydraulic stretching machine. The tensile strength and elongation results obtained by the test are shown in Table 7.
  • the obtained bar blank was made into a hardness sample of ⁇ 19 mm and a thickness of 30 mm, and was tested on a Brinell hardness tester.
  • the diameter of the ball used was 2.5 mm and the pressure was 62.5 kg.
  • the results of the HB hardness obtained by the test are shown in Table 7.
  • the obtained bar blank was made into a cutting force sample with a diameter of 19 mm and a length of 300 mm, and the cutting force test was performed in the Chongqing Dijia cutting force test system.
  • the test conditions are: feed rate 0.078, cutting speed 31.5674, and back knife volume 0.5.
  • the tangential force, axial force, radial force during the cutting process, the test results and the cutting force calculated according to the cutting force calculation formula are shown in Table 8.
  • Photographs of the broken pieces after cutting from Examples 30 to 35 are shown in Fig. 8.
  • Example 38 is a comparative example.
  • the cutting foam becomes smaller as the Pb element increases, which is more favorable for the discharge of cutting debris during the cutting process, and the surface roughness of the slit is improved;
  • the content of the Pb element should be controlled to be from 0.1% by weight to 4% by weight, preferably from 0.5% by weight to 3.0% by weight, more preferably from 0.8% by weight to 2.5% by weight.
  • Example 39 to 51 were the same as those of Example 33 to Example 38.
  • the samples were prepared to determine the content of each component and the tensile strength, elongation and hardness of each alloy are shown in Table 9; the results of the cutting force test are shown in Table 10.
  • Example 44 is a comparative example.
  • Example 47 is a comparative example.
  • the Bi, Sb element addition range is from 0.1 wt% to 4 wt%; and, according to the analysis results of Example 43 and Example 48, the Pb or Sb element is simultaneously added in the presence of the Bi element, which can more effectively reduce the cutting force. .
  • Example 52 to 56 were the same as those of Examples 33 to 38.
  • the test results of the sample component contents and the tensile strength, elongation and hardness of the respective examples are shown in Table 11; the cutting force test results are shown in Table 12.
  • the rod obtained by the preparation of Example 54 was subjected to a metallographic sample having a diameter of 19 mm and a thickness of 30 mm, which was polished by a metallographic polishing machine and then observed in a ferric chloride hydrochloric acid alcohol solution to observe the microstructure and microstructure under a Leica microscope. As shown in Figure 9 (magnification is 100X). After the metallographic test was completed, the hardness of the compound was measured under a Vickers microhardness tester. The test results are shown in Table 13.
  • Figure 10 is a photograph of a hardness test of a CuSe compound on a micro Vickers hardness tester.
  • KN Example Tangential force
  • KN Axial force
  • KN Radial force
  • KN Cutting force
  • 52 55.137 68.109 69.216 111.668
  • 54.228 68.92 64.209 108.690 55.001 64.292 65.201 105.800
  • the addition of Se element can form a CuSe compound.
  • the compound has a high microhardness and can form a stress concentration point during the cutting process, which is beneficial to the brass alloy during the cutting process. Chip breaking, improve the cutting performance of brass alloys.
  • Bi is added in the presence of Se
  • the cutting force of the alloy is at a lower level, which can significantly improve the cutting performance of the brass alloy.
  • the Se content exceeds 4% by weight, the elongation of the alloy is largely decreased, so the content of Se is controlled to be 0.1 wt% to 4 wt%, preferably 0.1 wt% to 2.0 wt%, more preferably 0.2 wt% to 1.0. Wt%.
  • Example 57 to 67 were the same as those of Examples 33 to 38.
  • Table 14 The test results of the contents of each component and the tensile strength, elongation and hardness in the samples of the examples are shown in Table 14, and the results of the cutting force test are shown in Table 15.
  • Examples 61 and 67 are comparative examples.
  • the Fe content is controlled at 0.01 wt% to 5 wt%
  • the Al content is controlled at 0.01 wt% to 5 wt%
  • the Si content is controlled at 0.01 wt% to 5 wt%
  • the Sn content is controlled at 0.01 wt% to 5 wt%
  • the Ni content is controlled at 0.01 wt%. %-5 wt%
  • the Co content is controlled to be 0.01 wt% to 5 wt%.
  • the mechanical properties of the brass alloy are improved overall, and the cutting force is increased slightly.
  • Ni, Co and Si elements are simultaneously added to the machinable brass alloy, and the mechanical properties of the brass alloy are improved overall.
  • the cutting force has a small increase, and the addition of Fe, Si and Pb elements in the machinable brass alloy, the cutting force of the brass alloy is not significantly increased, and the mechanical properties are generally improved.
  • Example 86 is a comparative C3604 lead brass alloy which is produced in accordance with conventional melt casting, extrusion, drawing, straightening, annealing process steps to produce a ⁇ 40 mm bar stock.
  • the preparation method of Example 87 is as follows:
  • Example 86 is a comparative example.
  • Example 86 and Example 87 were prepared as high frequency connector copper parts on a Mazak CNC lathe using a tungsten steel cutter. The processed product is shown in Figures 11 and 12.
  • the surface finish of Example 86 (C3604) was 1.38 and the surface finish of Example 87 was 0.65 by surface finish test. It can be seen that the alloy of the present invention has a superior surface finish than conventional lead brass.
  • Example 86 and Example 87 Five test pieces of 50 mm length were taken from each of Example 86 and Example 87, and after heating at 680 ° C for 30 minutes, they were taken out, compressed to a specified height on a 315 ton vertical hydraulic press, and surface cracks were observed. The test results are shown in Table 20.
  • the alloy of the present invention has superior forging properties than conventional lead brass.

Abstract

一种可切削加工黄铜合金及制备方法，其中，黄铜合金包括下述重量组成：铜45wt％-54wt％、锰0.5wt％-9.0wt％、锌37wt％-53wt％，铜、锰、锌三者之和≥95wt％，不可避免杂质含量≤0.1wt％；并且该合金中含有体心立方结构的Cu-Zn固溶体和面心立方的Cu-Mn固溶体。制备方法主要步骤包括配料→熔炼→连铸→刨皮→拉拔→去应力退火→校直→定尺→包装等。该黄铜合金切削性能和机械性能更优异，可替代现有的可切削黄铜合金，缓解铜资源短缺以及锌资源过剩的问题。

Description

一种可切削加工黄铜合金及制备方法 技术领域
本发明涉及到合金的技术领域，具体指一种可切削加工黄铜合金及制备方法。
背景技术
黄铜有良好的工艺性能、机械性能和耐蚀性能，是有色金属中应用最广泛的合金材料之一。在铜锌合金中加入一些功能元素，构成多元黄铜合金，使其能满足特定工况的应用，最广泛使用的是在铜锌合金中加入铅元素形成的铅黄铜。铅黄铜具有普通黄铜的机械性能、耐蚀性能、冷热加工性能，并且由于铅在合金中以游离的铅质点存在，在切削加工过程中使切削屑呈碎沫状，在高速切削后可获得光洁度很高的表面，因此铅黄铜在航空航天、汽车、紧固件、五金件等各行各业都有广泛的应用。目前铅黄铜合金中铜含量一般在57～75％之间，铜含量较高。
我国是铜资源紧缺的国家，2014年我国精铜消费量872万吨，其中359万吨为进口，进口比例达到41％，并且由于铜价持续保持高位，铜原材料价格占铜合金售价的70％以上，因此对铜合金加工企业而言，铜价对其资金流动和市场供求关系的影响非常严重。而在锌资源储备方面，2010年起，中国矿山产量增加幅度较大，国产锌矿供应能力增强，自2011年起国内锌精矿市场处于过剩状态，市场积压了大量锌精矿库存。并且锌原材料的价格仅为铜价的三分之一左右。因此降低铜合金的成本已经成为迫在眉睫的问题。
如中国专利申请CN101532100A(申请号为200910058578.1)公开了一种铜合金耐磨材料及其制备方法，该合金组分如下：Cu：54％-57％；Al：3％-5.0％；Mn：3.5％-5.5％；Si：0.5％-1.3％；Fe：0.7％-1.5％；Zn：余量。该合金的铜含量较HPb59-1降低了2％以上，能较好的降低原材料的成本，但根据说明书记载，该合金材料的抗拉强度≥700MPa，硬度≥90HRB，延伸率3-5％，性能与铅黄铜差异极大，由于该材料具有很高的强度和硬度，使得材料的切削加工性能较差，对刀具的磨损极大，不能满足高速切削的要求。
又如中国专利申请CN101906556A(申请号为201010232763.0)公开了一种无铅易切削变形锡铋锌铝合金，该合金组成为铝8-12％；铜0.8-1.5％；铋0.05-0.2％；锡0.05-0.15％；其余为锌和不可避免的杂质；杂质含量≤0.05％。该合金大量使用廉价的锌、铝等元素，并且具有较好的切削加工性能，但由于锌铝合金的强度、硬度、抗蠕变性能、疲劳强度等性能较铅黄铜要低很多，不能完全满足应用的需求。
发明内容
本发明所要解决的第一个技术问题是针对现有技术的现状提供一种能大大降低合金成本且切削性能更好的可切削加工黄铜合金。
本发明所要解决的第二个技术问题是提供一种能大大降低合金成本且切削性能更好的可切削加工黄铜合金的制备方法。
本发明解决上述第一个技术问题所采用的技术方案为：该可切削加工黄铜合金，其特征在于包括下述重量组成；
铜                    45wt％-54wt％
锰                    0.5wt％-9.0wt％
锌                    37wt％-53wt％
铜、锰、锌三者之和≥95wt％，不可避免杂质含量≤0.1wt％；
并且该合金中含有体心立方结构的Cu-Zn固溶体和面心立方的Cu-Mn固溶体。
较好的，所述Cu-Zn固溶体的比例≥80％，Cu-Mn固溶体比例≤20％；并且Cu-Zn固溶体中体心立方结构的比例≥85％。
更好的，所述Cu-Zn固溶体中体心立方结构的比例为95-100％。
优选所述Cu-Zn固溶体粒径为10-30nm，Cu-Mn固溶体的粒径为15-40nm。
所述合金的晶粒度为0.03-0.2mm。
该合金还可以包含0.001wt％-4wt％的组分X，所述X选自0.1wt％-4wt％的Pb、0.1wt％-4wt％的Bi、0.1wt％-4wt％的Sb、0.1wt％-4wt％的Se、0.001wt％-2.0wt％的B、0.001wt％-2.0wt％的P和0.001wt％-1wt％的As中的至少一种。
优选，所述Pb的含量为0.5wt％-3.0wt％，所述Bi的含量为0.1wt％-3.0wt％，所述Sb的含量为0.1wt％-2.5wt％，所述Se的含量为0.1wt％-2.0wt％，所述B的含量为0.01wt％-1.0wt％，所述P的含量为0.001wt％-1.0wt％，所述As的含量为0.002wt％-0.6wt％。
更有选，所述Pb的含量为0.8wt％-2.5wt％，所述Bi的含量为0.5wt％-2.5wt％，所述Sb的含量为0.2wt％-1.5wt％，所述Se的含量为0.2wt％-1.0wt％，所述B的含量为0.05wt％-0.5wt％，所述P的含量为0.01wt％-0.8wt％，所述As的含量为0.003-0.3wt％。
进一步地，该合金还包含0.01wt％-5wt％的组分Y，所述Y选自Al、Fe、Si、Sn、Ni和Co中的至少一种。
优选，所述Al的含量为0.1wt％-3.5wt％，所述Fe的含量为0.1wt％-3.0wt％，，所述Si的含量为0.05wt％-1.2wt％，，所述Sn的含量为0.05wt％-3wt％，所述Ni的含量为0.5wt％-2.5wt％，所述Co的含量为0.1wt％-2wt％。
更有选，所述Al的含量为0.5wt％-3wt％，所述Fe的含量为0.1wt％-2.5wt％，所述Si的含量为0.08wt％-1.0wt％，所述Sn的含量为0.1wt％-1.5wt％，所述Ni的含量为 0.6wt％-1.5wt％，所述Co的含量为0.5wt％-1wt％。
上述各方案中，，优选所述Cu的含量为47.8wt％-53.5wt％，所述Mn的含量为0.8wt％-6.0wt％。
更优选，所述Cu的含量为48.9wt％至52.7wt％，所述Mn的含量为1.0wt％-3.9wt％。
本发明为解决上述第二个技术问题所采用的一种技术方案为：该可切削加工黄铜合金的制备方法，其特征在于依次包括下述步骤：
配料→熔炼→垂直半连铸铸锭→加热挤压→拉拔→去应力退火→校直→定尺→包装；
其中，所述垂直半连铸的温度为980℃-1080℃，所述加热挤压温度为550℃-750℃，所述去应力退火温度为200℃-400℃，所述去应力退火加热速率为2-50℃/分钟，所述去应力退火的冷却速度为5-50℃/分钟。
本发明为解决上述第二个技术问题所采用的又一种技术方案为：该可切削加工黄铜合金的制备方法，其特征在于依次包括下述步骤：
配料→熔炼→水平连铸铸锭→加热挤压→拉拔→去应力退火→校直→定尺→包装；
其中，所述水平连铸的温度为950℃-1080℃，所述加热挤压温度为550℃-750℃，所述去应力退火温度为200℃-400℃，所述去应力退火的加热速率为2-50℃/分钟，所述去应力退火的冷却速度为5-50℃/分钟。
本发明为解决上述第二个技术问题所采用的再一种技术方案为：该可切削加工黄铜合金的制备方法，其特征在于依次包括下述步骤：
配料→熔炼→水平连铸棒坯→刨皮→拉拔→去应力退火→校直→定尺→包装；
其中，所述水平连铸的温度为950℃-1080℃，所述去应力退火温度为200℃-400℃，所述去应力退火的加热速率为2-50℃/分钟，所述去应力退火的冷却速度为5-50℃/分钟。
经大量实验发现，铜与锌形成固溶体，而且根据不同的铜锌比例，形成不同结构类型的固溶体，如面心立方结构、体心立方结构。当铜含量在54wt％以下时，体心立方结构的Cu-Zn固溶体具有特殊的原子力方向和应力分布，使得材料在切削过程中切削屑能更容易断裂，从而提高材料切削性能；而铜含量低于45wt％会导致材料变脆，合金的综合性能急剧下降，硬度急剧上升。使得黄铜合金的切削阻力变大，切削加工性能变差。本申请将铜含量控制在45wt％～54wt％，能够兼顾合金的切削性能和机械性能，且能大大降低合金成本。铜含量优选为47.8wt％至53.5wt％，更优选为48.9wt％至52.7wt％。
锰与铜能够形成面心立方结构的Cu-Mn固溶体，可改善机械性能，使本发明的黄铜合金的性能更加符合传统铅黄铜的应用。当锰含量小于0.5wt％时，其不能与铜形成足够量的面心立方结构的Cu-Mn固溶体，材料塑性不好；随着锰含量的增加，产品的综合性能提高；当锰含量大于9.0wt％时，会导致铸造时沉渣量过多，影响铸造性能并且由于锰的固溶强化效果，会导致材料的强度和塑性急剧降低、硬度过高，切削难度增 加，使其不能达到HPb59-1等铅黄铜的综合性能水平；当锰含量超过6wt％时，会使黄铜合金的黄色偏白，因此锰的含量优选0.8wt％-6.0wt％，更优选为1.0wt％-3.9wt％。
优选方案中，铅元素由于其不固溶于铜，以游离态质点形式分布于基体上，形成有效的切削屑断点。同时铅元素很软，具有润滑作用，能显著地减少切削阻力，明显提升黄铜合金的切削性能。当铅元素的低于0.1wt％，改善效果不明显，超过4wt％则断屑效果不再增加，因此铅元素含量控制在0.1wt％-4wt％，优选为0.5wt％-3.0wt％，更优选为0.8wt％-2.5wt％。
铋元素在黄铜合金中以片状分布在基体上，能显著改善黄铜合金的断屑性能并减少切削阻力，在加入铅元素的基础上加入铋元素，对黄铜合金的切削性能改善更加明显。当铋元素含量低于0.1wt％，改善效果不明显，超过4wt％，则铋元素在晶界上大量分布，降低黄铜合金的晶界强度，使得黄铜合金的机械性能降低。因此铋元素含量控制在0.1wt％-4wt％，优选为0.1wt％-3.0wt％，更优选为0.5wt％-2.5wt％。
锑元素能少量固溶于黄铜合金中，提高黄铜合金的力学性能，并且锑元素能改普铋元素在黄铜合金中的分布形貌，在加入铋的基础上加入锑元素，能更好的改善黄铜合金的切削性能。当锑元素含量低于0.1wt％，改善效果不明显，超过4wt％则显著降低黄铜合金的塑性。因此黄铜合金中锑元素含量控制在0.1wt％-4wt％，优选为0.1wt％-2.5wt％，更优选为0.2wt％-1.5wt％。
硒元素在本发明黄铜合金中以CuSe化合物的形式存在，而CuSe化合物较硬，可使得车削屑能顺利断裂，从而提高黄铜合金的切削性能，而在含有铋元素的黄铜合金中，加入硒元素能更明显的改善切削性能。硒元素含量低于0.1wt％时，不能形成足够量的化合物以改善黄铜合金的切削性能，但是硒含量大于4wt％，会导致黄铜合金的延伸率降低，因此硒元素含量控制在0.1wt％-4wt％，优选为0.1wt％-2.0wt％，更优选为0.2wt％-1.0wt％。
硼元素、磷元素能够细化晶粒，提高黄铜合金的强度、硬度及塑性；其中硼元素以氧化物形式存在基体上，改善材料的组织和性能，并且硼元素能改善铅的分布，使铅以细小均匀的球状分布在基体上，提高黄铜合金的切削稳定性；硼元素含量若低于0.001wt％，则不能明显的改善黄铜合金的切削性能。而磷元素与铜形成Cu3P化合物，在黄铜合金基体上形成“空穴效应”，增加黄铜合金在切削过程的断屑能力，提高材料的切削性能，磷元素含量低于0.001wt％，不能形成足够量的化合物，不能明显的改善黄铜合金的切削加工性能。但硼或磷元素超过2wt％则使材料的机械性能急剧下降，因此硼元素含量控制在0.001wt％-2wt％，优选为0.01wt％-1.0wt％，更优选为0.05wt％-0.5wt％；磷元素含量控制在0.001wt％-2wt％，优选为0.001wt％-1.0wt％，更优选为0.01wt％-0.8wt％。
铁元素在黄铜合金中作为形核剂，增加形核的数量，阻碍了晶粒的长大，起到细化 晶粒的效果，提高材料的综合性能，并且铁元素未固溶部分以星花状分布在黄铜基体上，能促进切削屑的断裂，改善黄铜合金的切削性能。但是过量的铁元素，特别是含量超过5wt％时，会出现铁偏析聚集的问题，导致材料的综合性能变差。因此铁元素含量控制在0.01wt％-5wt％，优选为0.1wt％-3.0wt％，更优选为0.1wt％-2.5wt％。
铝元素起到稳定并强化体心立方结构Cu-Zn固溶体的效果，使得黄铜合金的基体具有更高的强度及稳定性。在添加铁的情况下，加入铝元素，可形成FeAl化合物，进一步提高材料的机械性能。另外，铝元素的加入可在黄铜合金表面形成致密的氧化铝保护膜，增加黄铜合金的耐蚀性能。铝元素含量低于0.01wt％，改善效果不明显，但由于铝元素的固溶强化效果非常明显，过量的铝，特别是超过5wt％，会使黄铜合金的强度和硬度急剧上升，延伸急剧下降，会限制黄铜合金的应用范围。因此铝元素含量控制在0.01wt％-5wt％，优选为0.1wt％-3.5wt％，更优选为0.5wt％-3wt％。
硅元素的加入与黄铜合金中的锰形成SiMn化合物，并且SiMn化合物的硬度极高，可增加黄铜合金的强度和硬度，并且提高黄铜合金的耐磨性能，因此在需要耐磨领域应用的黄铜合金可选择性添加硅元素，硅元素含量低于0.01wt％，不能明显的改善材料的性能并无法形成足够量的SiMn化合物，但由于硅元素的虚拟锌当量是最高的，如硅元素含量超过1.5wt％，材料的脆性急剧增加，塑性急剧下降。因此硅元素含量控制在0.01wt％-1.5wt％，优选为0.05wt％-1.2wt％，更优选为0.08wt％-1.0wt％。
锡元素能少量固溶于铜中，提高黄铜合金的机械性能，同时在黄铜合金表面形成一层氧化锡，可显著地增加黄铜合金的耐蚀性能，有利于黄铜合金在湿度高的环境中应用。锡元素含量小于0.01wt％，则以上改善效果不明显，含量大于5wt％，容易出现锡的反偏析问题，影响黄铜合金性能的稳定性，并且影响黄铜合金的经济效果。因此锡元素含量控制在0.01wt％-5wt％，优选为0.05wt％-3wt％，更优选为0.1wt％-1.5wt％。
镍元素、钴元素有较好的固溶强化效果，能增强体心立方结构Cu-Zn固溶体的稳定性，并改善其应力分布，有利于降低黄铜含金切削阻力，改善黄铜合金的切削加工性能。镍元素或钴元素与硅元素同时加入可形成稳定的NiSi、CoSi化合物，形成应力集中点，改善黄铜合金的切削断屑性能，并增加材料的耐磨性能，使得黄铜合金能适用于有耐磨要求的领域。含量若低于0.01wt％，则以上改善效果不明显，由于镍、钴价格高昂，若含量高于5wt％，影响黄铜合金的经济效果，并且过高的镍、钴含量使得黄铜合金的硬度升高明显，增加黄铜合金的切削阻力，降低黄铜合金的切削性能。因此镍元素含量控制在0.01wt％-5wt％，优选为0.5wt％-2.5wt％，更优选为0.6wt％-1.5wt％；钴元素含量控制在0.01wt％-5wt％，优选为0.1wt％-2wt％，更优选为0.5wt％-1wt％。
砷元素在黄铜合金的晶界上形成Cu-As-Zn保护层，阻止了锌的溶解，能极大的提高黄铜合金的耐蚀性能，因此黄铜合金在有耐腐蚀性能要求时，可添加少量的As元素，含量低于0.001wt％，耐蚀性能不明显，过量的As(超过1.5wt％)会增加黄铜应力腐蚀破 裂的敏感性，因此As含量需控制在0.001wt％-1.0wt％以下，优选为0.002wt％-0.6wt％，更优选为0.003-0.3wt％。并且砷与硼形成的As-B原子对可快速填充脱锌腐蚀后的空位处，阻止了锌的进一步溶解，可进一步提高黄铜合金的耐蚀性能。
本发明中合金在加工时，在切削加工过程中体心立方结构的Cu-Zn固溶体会形成应力集中点，有利于切削加工过程切削屑的断裂，提高材料的切削加工性能。当Cu-Zn固溶体比例低于80％，则以上的效果不明显。而面心立方结构的Cu-Mn固溶体在切削加工过程中无法形成应力集中点，不利于车削屑的断裂；当面心立方结构的Cu-Mn固溶体含量大于20％时，会导致切削加工过程的切削难度增大。因此本发明优选方案中，将Cu-Zn固溶体比例控制在≥80％，Cu-Mn固溶体比例控制在≤20％。为了保证两者固溶体的比例，Cu，Mn，Zn元素的总和需≥95wt％。Cu-Zn固溶体中体心立方结构由于其特殊的原子力和应力方向特点使得其加工应力集中的特点较面心立方结构更加明显，更加充分的保证车削屑顺利断开，避免了车削加工过程的缠刀，排屑不畅等问题，改善了可切削加工黄铜合金的切削性能，在Cu-Zn固溶体中体心立方结构比例≥85％，黄铜合金的切削屑很小，不会出现缠刀的问题，当体心立方结构比例达到95-100％时，切削性能进一步得到改善。
Cu-Zn固溶体的粒径决定其切削加工应力集中的难易程度，Cu-Zn固溶体粒径大于30nm，其加工应力分布较分散，不能形成满足切削断屑要求的应力集中点，但固溶体粒径小于10nm时，其加工应力集中效果非常明显，在加工过程中容易导致其应力开裂。因此可切削加工黄铜合金的Cu-Zn固溶体粒径控制在10-30nm。Cu-Mn固溶体的粒径决定可切削加工黄铜合金的机械性能，当Cu-Mn固溶体粒径小于15nm时，可切削加工黄铜合金的塑性降低明显，机械性能无法满足应用要求，而Cu-Zn固溶体粒径大于40nm时，则黄铜合金的强度、硬度过低，同样无法满足应用要求。因此优选方案中Cu-Mn固溶体粒径控制在15-40nm。
合金的晶粒度小于0.03mm，黄铜合金的强度、硬度过高，不利于后续的铆接、热锻、折弯等加工；而晶粒度大于0.2mm，黄铜合金的机械性能变差，不能完全满足应用的要求；因此本发明将黄铜合金晶粒度控制在0.03-0.2mm。
本发明提供的可切削加工黄铜合金抗拉强度大于450MPa以上，完全能够满足应用的结构强度要求；延伸率大于15％，满足冷镦、铆接、折弯等应用要求；HB硬度在110-180之间，加工过程中不会产生变形，对刀具的磨损小；与现有技术中HPb59-1、C36000等牌号的铅黄铜合金相比较，切削性能和机械性能更优异，并且大大降低了合金的成本，可替代现有的可切削黄铜合金应用于阀门铜部件、同轴连接器铜部件、泵头、锁具铜部件等领域，可缓解我国铜资源短缺以及锌资源过剩的问题。
附图说明
图1为Mn含量与合金抗拉强度的关系；
图2为Mn含量与延伸率的关系；
图3为Mn含量与合金硬度的关系；
图4为Mn含量与切削力的关系；
图5为不同锰含量的产品表面颜色照片，图中的标号为实施例编号；
图6和图7为实施例16的XRD固溶体测试结构图；
图8为实施例30至实施例35切削后的碎沫照片，图中的标号为实施例编号；
图9为实施例54的显微组织照片；
图10为实施例54显微维氏硬度计上对CuSe化合物硬度测试电镜扫描照片；
图11实施例86切削得到的产品照片；
图12为实施例87切削得到的产品照片。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
实施例1至实施例15
实施例1至实施例15的配方如表1所示。
其中实施例1和实施例2为HPb59-1和C36000铅黄铜合金，其按照常规的熔铸、挤压、拉拔、校直、退火工艺步骤进行生产。
实施例3至实施例15的制备方法如下：
各组分配料，在低频熔炼炉熔炼，垂直半连铸铸锭，所述的铸造温度为990℃-1030℃，加热挤压成Φ20mm棒坯，所述的挤压温度为630℃-670℃，拉拔成Φ19mm棒坯，之后在250℃-280℃下去应力退火，去应力退火加热速率在200℃以下时为40-45℃/分钟，在200℃以上时为5-8℃/分钟。所述的去应力退火冷却速率300℃以上时为5-7℃/分钟，300℃以下时为45-48℃/分钟。最后校直定尺出成品棒坯。对所得的棒坯取样，按照GB/T5121-2008测试实施例1至实施例15各样品中各元素的含量，结果如表1所示。
所得棒坯取样制备成Φ8mm的抗拉样品。在10吨液压拉伸机上对样品进行拉力测试，测试得到的抗拉强度和延伸率结果如表1所示。
所获得的棒坯取样制备成Φ19mm，厚度为30mm的硬度样品。所述的硬度样品在布氏硬度计上进行测试，测试采用的圆球直径2.5mm，压力为62.5公斤力，测试得到的HB硬度结果如表1所示。
所获得的棒坯取样制备成Φ19mm，长度300mm的切削力样品，进行切削力测试，测试设备为重庆迪佳切削力测试系统，测试条件为：进给量0.078，切削速度31.5674，背吃刀量0.5。测试样品切削过程中的切向力、轴向力、径向力，测试结果以及按照切 削力计算公式计算得到的切削力如表2所示。
表1
Figure PCTCN2016000230-appb-000001
实施例1、2、3、14、15为对比例，其中实施例2为现有的牌号为C36000铅黄铜合金的标准配方。
Mn含量与合金抗拉强度的关系如图1所示，Mn含量与延伸率的关系如图2所示，Mn含量与合金硬度的关系如图3所示。
由图1至图3可知，Mn含量在0.5wt％-10.03wt％之间可切削加工黄铜合金的延伸率较HPb59-1铅黄铜要高。Mn含量高于9.0wt％，可切削加工黄铜合金的硬度开始急剧升高，远远高出HPb59-1铅黄铜。Mn含量低于0.5wt％，或高于9.0wt％，可切削加工黄铜合金的抗拉强度远远高于HPb59-1铅黄铜，而在0.5wt％-6wt％之间，可切削加工黄铜合金的抗拉强度较HPb59-1铅黄铜有少量的升高。因此Mn的适宜添加范围在0.5wt％-9.0wt％。
表2
Figure PCTCN2016000230-appb-000002
Figure PCTCN2016000230-appb-000003
Mn含量与切削力的关系如图4所示。
根据图4可知，Mn含量低于0.5wt％或高于9.0wt％，可切削加工黄铜合金的切削力较C36000要急剧升高，Mn含量在0.5wt％-9.0wt％，可切削加工黄铜合金的切削力较C36000有少量的升高。在有色金属加工领域C36000的切削性能是现有技术中公认最优秀的铜合金，而本发明合金配方的切削力是C36000的1.04-1.15倍，能满足高速切削的要求。
实施例4、实施例5、实施例7、实施例11、实施例12、实施例13切削力样品车削后的表面颜色如图5所示。由图5可以看出，当Mn含量在6.0wt％以下，可切削加工黄铜合金的表面呈亮黄色，Mn含量在6wt％以上，可切削加工黄铜合金的表面颜色发白，Mn含量达到9.0wt％，黄铜合金的表面颜色为白色。
综上所述可知，Mn元素含量为0.5wt％-9.0wt％是合适的，Mn含量在1.0wt％-6.0wt％时效果更优，理想的Mn含量为1.3wt％-4.9wt％。
实施例16至实施例25
实施例16至实施例25的制备方法与实施例1至实施例16相同。
对制备得到的棒坯取样，按照GB/T5121-2008测试各实施例样品中铜和各元素的含量，测试结果如表3所示。
取样制备成Φ8mm的抗拉样。样品在10吨液压拉伸机上进行拉力测试，测试得到的抗拉强度和延伸率结果如表3所示。所获得的棒坯取样制备成Φ19mm，厚度为30mm的硬度样品。所述的硬度样品在布氏硬度计上进行测试，测试采用的圆球直径2.5mm，压力为62.5公斤力，测试得到的HB硬度结果如表3所示。
表3
Figure PCTCN2016000230-appb-000004
实施例20、21、22、23、24、25为对比例。
由表3可以看出，Cu含量大于45wt％，可切削加工黄铜合金的抗拉强度、延伸率和HB硬度是比较接近铅黄铜的，当Cu含量大于54wt％，可切削加工黄铜合金的抗拉强度较铅黄铜要偏低，延伸率较铅黄铜要稍高。因此可切削加工黄铜合金的Cu含量范围在45wt％-54wt％是合适的。
将实施例16至实施例25制备得到的黄铜棒坯制成Φ19mm、厚度为1mm的XRD样品，将XRD样品在德国布鲁克X射线衍射仪上进行固溶体结构和比例的测试，测试结果如表4所示。
将实施例16至实施例25制备得到的黄铜棒坯制成Φ19mm、长度为300mm的切削力样品，在重庆迪佳切削力测试系统上进行切削力测试。测试条件为：进给量0.078，切削速度31.5674，背吃刀量0.5。测试切向力、轴向力和径向力，测试结果以及按照切削力计算公式计算得到的切削力如表4所示。
图6和图7为实施例16的XRD分析固溶体结构图。
表4
Figure PCTCN2016000230-appb-000005
由表4可知，Cu-Zn固溶体比例≥80％，并且Cu-Zn固溶体中体心立方结构比例≥85％；Cu-Mn固溶体比例≤20％，可切削加工黄铜合金的切削力处于较低的水平。因此可切削加工黄铜合金的Cu-Zn固溶体比例≥80％，Cu-Mn固溶体比例≤20％是比较合适的。根据实施例23-25，当铜含量在54wt％以上，Cu-Zn固溶体在80％以上，并且Cu-Zn固溶体中体心立方结构比例≥85％，产品的切削力处于较高的水平，说明了体心立方结构的Cu-Zn固溶体改善切削性能的前提是铜含量需低于54wt％。
实施例26至实施例32
实施例26至实施例29的制备方法如下；
各组分配料，在低频熔炼炉熔炼后进行水平连铸铸锭，水平连铸的铸造温度为970℃-1020℃；然后加热挤压成Φ20mm棒坯，加热挤压温度为620℃-660℃；拉拔成Φ19mm棒坯；之后去应力退火，去应力退火温度为260℃-300℃，200℃以下时去应力退火加热速率为40-43℃/分钟，200℃以上时为8-10℃/分钟；200℃以上时去应力退火冷却速度为5-6℃/分钟，200℃以下为32-34℃/分钟；最后校直定尺出成品棒坯。
实施例30至实施例32的制备方法如下：
各组分配料，在低频熔炼炉熔炼后进行水平连铸铸锭，水平连铸的铸造温度为970℃-1020℃；然后加热挤压成Φ20mm棒坯，加热挤压温度为620℃-660℃；拉拔成Φ19mm棒坯；之后去应力退火，所述的去应力退火温度为180℃-200℃，所述的去应力退火加热速度为51-55℃/分钟，所述的去应力退火冷却速度为51-55℃/分钟；最后校直定尺出成品棒坯。
对所得的棒坯取样按照GB/T5121-2008测试各实施例样品中铜和各元素的含量， 测试结果如表5所示，并取样制备成Φ8mm的抗拉样。将得到的样品在10吨液压拉伸机上进行拉力测试，测试得到的抗拉强度和延伸率结果如表5所示。
将所获得的棒坯取样制备成Φ19mm、厚度为30mm的硬度样品，在布氏硬度计上进行测试，测试采用的圆球直径2.5mm，压力为62.5公斤力，测试得到的HB硬度结果如表5所示。
将制备得到的棒坯制备成Φ19mm、厚度为1mm的XRD样品，在德国布鲁克X射线衍射仪上进行体心立方结构Cu-Zn固溶体和面心立方结构Cu-Mn固溶体的粒径测试，测试结果如表6所示。
将制备得到的棒坯制备成Φ19mm、长度为300mm的切削力样品，在重庆迪佳切削力测试系统上进行切削力测试。测试条件为：进给量0.078，切削速度31.5674，背吃刀量0.5。测试材料切削过程中的切向力、轴向力、径向力，测试结果以及按照切削力计算公式计算得到的切削力如表6所示。
表5
Figure PCTCN2016000230-appb-000006
其中，实施例27、30、31、32是对比例。
表6
Figure PCTCN2016000230-appb-000007
由表5和表6可知，当Cu-Zn固溶体粒径≤10nm或Cu-Zn固溶体粒径≥30nm时，可切削加工黄铜合金的切削力整体偏高，当Cu-Mn固溶体粒径≤15nm或Cu-Mn固溶 体粒径≥40nm时，可切削加工黄铜合金的切削力整体偏高。因此可切削加工黄铜合金的Cu-Zn固溶体粒径为10-30nm，Cu-Mn固溶体的粒径为15-40nm是合适的范围。
实施例33至实施例38
实施例33至实施例38的制备方法如下：
配料，在中频熔炼炉熔炼；水平连铸棒坯；水平连铸的铸造温度为970℃-1020℃；刨皮；拉拔成Φ19mm棒坯；之后去应力退火，去应力退火温度为250℃-280℃，去应力退火加热速率为2-5℃/分钟，去应力退火冷却速度为5-8℃/分钟；最后校直定尺出成品棒坯。
所得棒坯取样按照OD/T5121-2008测试各实施例样品中铜和各元素的含量，测试结果如表7所示。
所得棒坯制备成Φ8mm的抗拉样，在10吨液压拉伸机上进行拉力测试，测试得到的抗拉强度和延伸率结果如表7所示。
所得棒坯制成Φ19mm、厚度30mm的硬度样品，在布氏硬度计上进行测试，测试采用的圆球直径2.5mm，压力为62.5公斤力，测试得到的HB硬度结果如表7所示。
所得棒坯制成Φ19mm、长度为300mm的切削力样品，在重庆迪佳切削力测试系统进行切削力测试。测试条件为：进给量0.078，切削速度31.5674，背吃刀量0.5。测试切削过程中的切向力、轴向力、径向力，测试结果以及按照切削力计算公式计算得到的切削力如表8所示。
实施例30至实施例35切削后的碎沫照片如图8所示。
表7
Figure PCTCN2016000230-appb-000008
其中实施例38是对比例。
表8
Figure PCTCN2016000230-appb-000009
由表7、表8和图8可知，添加一定量的Pb元素，切削碎沫随着Pb元素的增加变小，更有利于切削加工过程中切削碎沫的排出，并且切口表面光洁度提高；但随着Pb元素的增加，延伸率呈降低的趋势；当Pb元素含量超过4wt％时，其延伸率会有较大幅度的下降。因此Pb元素的含量应控制在0.1wt％-4wt％，优选为0.5wt％-3.0wt％，更优选为0.8wt％-2.5wt％。
实施例39至实施例51
实施例39至实施例51的制备方法与实施例33至实施例38相同。制备样品测定各组分含量以及各合金的抗拉强度、延伸率和硬度结果如表9所示；切削力测试结果如表10所示。
表9
Figure PCTCN2016000230-appb-000010
Figure PCTCN2016000230-appb-000011
实施例44是对比例。
表10
Figure PCTCN2016000230-appb-000012
实施例47是对比例。
由表9和表10可知，添加一定量的Bi，Sb元素，可减少切削加工过程的切削力，有利于提高可切削加工黄铜合金的切削加工性能。但Sb，Bi元素添加超过4wt％，合金的延伸率出现了较大幅度的下降，因此Bi，Sb的含量需控制在4wt％以下；而Bi，Sb元素添加量小于0.1wt％时，改善效果不明显。因此Bi，Sb元素添加范围为0.1wt％-4wt％；并且，根据实施例43和实施例48的分析结果，在Bi元素存在的情况下同时添加Pb或Sb元素，可更有效的降低切削力。
实施例52至实施例56
实施例52至实施例56的制备方法与实施例33至实施例38相同。各实施例样品组分含量以及抗拉强度、延伸率和硬度的测试结果如表11所示；切削力测试结果如表12所示。
将实施例54制备得到的棒坯取Φ19mm，厚度为30mm的金相样品，经金相抛光机抛光后使用三氯化铁盐酸酒精溶液中腐蚀后在莱卡显微镜下观察组织形貌，显微组织如图9(放大倍率为100X)所示。金相测试完成后取该样品在维氏显微硬度仪下测试化合物的硬度，测试结果如表13所示。图10为在显微维氏硬度计上对CuSe化合物进行硬度测试的照片。
表11
Figure PCTCN2016000230-appb-000013
表12
实施例 切向力(KN) 轴向力(KN) 径向力(KN) 切削力(KN)
52 55.137 68.109 69.216 111.668
53 54.189 69.012 66.218 109.927
54 54.228 68.92 64.209 108.690
55 53.001 64.292 65.201 105.800
56 53.192 63.299 64.829 105.066
表13
Figure PCTCN2016000230-appb-000014
由表11、表12、表13和图10可知，加入Se元素可形成CuSe化合物，化合物显微硬度较高，在切削过程中能够形成应力集中点，有利于黄铜合金在切削加工过程中的断屑，提高黄铜合金的切削加工性能。而Se存在下再加入Bi元素，合金的切削力处于较低的水平，可显著改善黄铜合金的切削性能。但当Se含量超过4wt％，合金的延伸率有较大幅度的下降，因此Se的含量控制在0.1wt％-4wt％，优选为0.1wt％-2.0wt％，更优选为0.2wt％-1.0wt％。
实施例57至实施例67
实施例57至实施例67的制备方法和测试方法与实施例33至实施例38的相同。各 实施例样品中各组分含量及抗拉强度、延伸率和硬度的测试结果如表14所示，切削力测试结果如表15所示。
Figure PCTCN2016000230-appb-000015
实施例61、67是对比例。
表15
实施例 切向力(KN) 轴向力(KN) 径向力(KN) 切削力(KN)
57 55.731 67.189 66.916 109.991
58 56.468 71.432 74.192 117.455
59 60.287 66.567 71.841 115.008
60 64.774 70.061 66.939 116.555
61 75.251 76.239 78.089 132.563
62 53.798 65.295 63.713 105.910
63 61.582 58.767 69.089 109.632
64 56.695 61.842 69.415 108.891
65 58.387 59.29 69.498 108.417
66 61.208 62.911 74.125 114.886
67 75.499 76.383 72.957 129.835
由表14和表15可知，加入B和/或P元素，可改善合金的机械性能，可切削力未明显增加。但B元素≥2wt％或P元素≥2wt％，可切削加工黄铜合金的延伸率急剧降低， 而低于0.001wt％则效果不明显。因此B元素含量0.001wt％-2wt％，P元素含量控制在0.001wt％-2wt％。
实施例68至实施例85
实施例57至实施例67的制备方法和测试方法与实施例33至实施例38的相同。各组分含量、抗拉强度、延伸率和硬度结果如表16所示，切削力测试结果如表17所示。
表16
Figure PCTCN2016000230-appb-000016
表17
实施例 切向力(KN) 轴向力(KN) 径向力(KN) 切削力(KN)
68 63.991 62.226 62.621 109.034
69 62.021 64.461 70.004 113.589
70 63.925 68.464 78.139 121.981
71 59.755 63.273 63.16 107.533
72 63.318 69.339 74.176 119.663
73 68.134 72.007 71.831 122.421
74 60.891 68.631 65.905 112.966
75 60.181 65.755 66.078 110.958
76 62.228 70.211 72.28 118.433
77 64.983 73.21 77.063 124.584
78 65.673 64.802 65.73 113.281
79 62.09 61.718 60.094 106.186
80 76.375 74.792 66.607 125.950
81 60.201 63.815 60.15 106.370
82 66.06 68.761 71.832 119.381
83 53.13 63.228 65.363 105.323
84 70.95 73.291 70.075 123.758
85 65.512 61.205 64.095 110.209
由表16和表17可知，在可切削加工黄铜合金中加入Fe，Al，Si，Sn，Ni，Co元素的一种或多种可提高产品的机械性能，改善了可切削加工黄铜合金的综合性能。但Fe，Al，Si，Sn，Ni或Co元素含量超过5wt％时，可切削加工黄铜合金的延伸率急剧降低，含量低于0.01wt％时改善效果不明显，因此可切削加工黄铜的Fe含量控制在0.01wt％-5wt％，Al含量控制在0.01wt％-5wt％，Si含量控制在0.01wt％-5wt％，Sn含量控制在0.01wt％-5wt％，Ni含量控制在0.01wt％-5wt％，Co含量控制在0.01wt％-5wt％。同时加入Al和Fe元素，黄铜合金的机械性能整体提高，切削力有小幅度的升高，在可切削加工黄铜合金中同时加入Ni、Co和Si元素，黄铜合金的机械性能整体提高，切削力有小幅度的升高，而在可切削加工黄铜合金中同时加入Fe、Si和Pb元素，黄铜合金的切削力未明显增加，机械性能整体提高。
实施例86和实施例87
实施例86是作为对比的C3604铅黄铜合金，其按照常规的熔铸、挤压、拉拔、校直、退火工艺步骤进行生产出Φ40mm棒坯。实施例87的制备方法如下：
配料，在低频熔炼炉熔炼，垂直半连铸铸锭，所述的铸造温度为1000℃-1040℃，加热挤压成Φ42mm棒坯，所述的挤压温度为620℃-690℃，拉拔成Φ40mm棒坯，之后去应力退火，所述的去应力退火温度为250℃-350℃，，去应力退火加热速率为2-5℃/分钟，去应力退火冷却速度为5-8℃/分钟；最后校直定尺出成品棒坯。实施例86与实施例87的抗拉强度、延伸率、HB硬度及切削力的测试结果如表18所示，切削力测试结果见表19。
表18
Figure PCTCN2016000230-appb-000017
实施例86是对比例。
表19
实施例 切向力(KN) 轴向力(KN) 径向力(KN) 切削力(KN)
86 46.315 62.089 65.918 101.712
87 47.214 63.186 68.428 104.422
将实施例86和实施例87采用钨钢刀具，在马扎克数控车床上制备成高频连接器铜部件。加工后的产品如图11和图12所示。经表面光洁度测试，实施例86(C3604)的表面光洁度为1.38，实施例87的表面光洁度为0.65。由此可知，本发明合金较传统铅黄铜具有更优秀的表面光洁度。
从实施例86和实施例87上各取50mm长的试验料5个，经680℃加热30分钟后取出，在315吨立式油压机上压缩至指定高度，并观察表面裂纹情况。测试结果如表20所示。
表20
Figure PCTCN2016000230-appb-000018
计算压缩比(压缩比＝50/压缩后的高度)，表20中的优表示压缩后的样品表面光洁且无裂纹；良为表面粗糙且无明显裂纹；表面存在裂纹为差。
由表20可知，本发明合金较传统铅黄铜具有更优秀的锻造性能。

Claims (16)

  1. 一种可切削加工黄铜合金，其特征在于包括下述重量组成：
    铜  45wt％-54wt％
    锰  0.5wt％-9.0wt％
    锌  37wt％-53wt％
    铜、锰、锌三者之和≥95wt％，不可避免杂质含量≤0.1wt％：
    并且该合金中含有体心立方结构的Cu-Zn固溶体和面心立方的Cu-Mn固溶体。
  2. 根据权利要求1所述的可切削加工黄铜合金，其特征在于所述Cu-Zn固溶体的比例≥80％，Cu-Mn固溶体比例≤20％；并且Cu-Zn固溶体中体心立方结构的比例≥85％。
  3. 根据权利要求2所述的可切削加工黄铜合金，其特征在于所述Cu-Zn固溶体中体心立方结构的比例为95-100％。
  4. 根据权利要求1、2或3所述的可切削加工黄铜合金，其特征在于所述Cu-Zn固溶体粒径为10-30nm，Cu-Mn固溶体的粒径为15-40nm。
  5. 根据权利要求4所述的可切削加工黄铜合金，其特征在于所述合金的晶粒度为0.03-0.2mm。
  6. 根据权利要求5所述的可切削加工黄铜合金，其特征在于该合金还包含0.001wt％-4wt％的组分X，所述X选自0.1wt％-4wt％的Pb、0.1wt％-4wt％的Bi、0.1wt％-4wt％的Sb、0.1wt％-4wt％的Se、0.001wt％-2.0wt％的B、0.001wt％-2.0wt％的P和0.001wt％-1wt％的As中的至少一种。
  7. 根据权利要求6所述的可切削加工黄铜合金，其特征在于所述Pb的含量为0.5wt％-3.0wt％，所述Bi的含量为0.1wt％-3.0wt％，所述Sb的含量为0.1wt％-2.5wt％，所述Se的含量为0.1wt％-2.0wt％，所述B的含量为0.01wt％-1.0wt％，所述P的含量为0.001wt％-1.0wt％，所述As的含量为0.002wt％-0.6wt％。
  8. 根据权利要求7所述的可切削加工黄铜合金，其特征在于所述Pb的含量为0.8wt％-2.5wt％，所述Bi的含量为0.5wt％-2.5wt％，所述Sb的含量为0.2wt％-1.5wt％，所述Se的含量为0.2wt％-1.0wt％，所述B的含量为0.05wt％-0.5wt％，所述P的含量为0.01wt％-0.8wt％，所述As的含量为0.003-0.3wt％。
  9. 根据权利要求6所述的所述的可切削加工黄铜合金，其特征在于该合金还包含0.01wt％-5wt％的组分Y，所述Y选自Al、Fe、Si、Sn、Ni和Co中的至少一种。
  10. 根据权利要求9所述的可切削加工黄铜合金，其特征在于所述Al的含量为0.1wt％-3.5wt％，所述Fe的含量为0.1wt％-3.0wt％，，所述Si的含量为0.05wt％-1.2wt％，，所述Sn的含量为0.05wt％-3wt％，所述Ni的含量为0.5wt％-2.5wt％，所述Co的含量为0.1wt％-2wt％。
  11. 根据权利要求10所述的可切削加工黄铜合金，其特征在于所述Al的含量为0.5wt％-3wt％，所述Fe的含量为0.1wt％-2.5wt％，所述Si的含量为0.08wt％-1.0wt％，所述Sn的含量为0.1wt％-1.5wt％，所述Ni的含量为0.6wt％-1.5wt％，所述Co的含量为0.5wt％-1wt％。
  12. 根据权利要求6所述的可切削加工黄铜合金，其特征在于所述Cu的含量为47.8wt％-53.5wt％，所述Mn的含量为0.8wt％-6.0wt％。
  13. 根据权利要求12所述的可切削加工黄铜合金，其特征在于所述Cu的含量为48.9wt％至52.7wt％，所述Mn的含量为1.0wt％-3.9wt％。
  14. 一种如权利要求1所述的可切削加工黄铜合金的制备方法，其特征在于依次包括下述步骤：
    配料→熔炼→垂直半连铸铸锭→加热挤压→拉拔→去应力退火→校直→定尺→包装；
    其中，所述垂直半连铸的温度为980℃-1080℃，所述加热挤压温度为550℃-750℃，所述去应力退火温度为200℃-400℃，所述去应力退火加热速率为2-50℃/分钟，所述去应力退火的冷却速度为5-50℃/分钟。
  15. 一种如权利要求1所述的可切削加工黄铜合金的制备方法，其特征在于依次包括下述步骤：
    配料→熔炼→水平连铸铸锭→加热挤压→拉拔→去应力退火→校直→定尺→包装；
    其中，所述水平连铸的温度为950℃-1080℃，所述加热挤压温度为550℃-750℃，所述去应力退火温度为200℃-400℃，所述去应力退火的加热速率为2-50℃/分钟，所述去应力退火的冷却速度为5-50℃/分钟。
  16. 一种如权利要求1所述的可切削加工黄铜合金的制备方法，其特征在于依次包括下述步骤：
    配料→熔炼→水平连铸棒坯→刨皮→拉拔→去应力退火→校直→定尺→包装；
    其中，所述水平连铸的温度为950℃-1080℃，所述去应力退火温度为200℃-400℃，所述去应力退火的加热速率为2-50℃/分钟，所述去应力退火的冷却速度为5-50℃/分钟。
PCT/CN2016/000230 2015-05-05 2016-04-29 一种可切削加工黄铜合金及制备方法 WO2016177018A1 (zh)

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