WO2022174607A1 - 一种高性能钨合金棒材及其制备方法 - Google Patents

一种高性能钨合金棒材及其制备方法 Download PDF

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WO2022174607A1
WO2022174607A1 PCT/CN2021/125233 CN2021125233W WO2022174607A1 WO 2022174607 A1 WO2022174607 A1 WO 2022174607A1 CN 2021125233 W CN2021125233 W CN 2021125233W WO 2022174607 A1 WO2022174607 A1 WO 2022174607A1
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treatment
sintering
temperature
forging
preparation
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PCT/CN2021/125233
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English (en)
French (fr)
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吴朝圣
苏文国
刘俊海
齐英国
王玲
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安泰科技股份有限公司
安泰天龙(北京)钨钼科技有限公司
安泰天龙钨钼科技有限公司
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Publication of WO2022174607A1 publication Critical patent/WO2022174607A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
    • B21J5/002—Hybrid process, e.g. forging following casting
    • 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
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • 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
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • 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
    • 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
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • 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

Definitions

  • the invention relates to the field of high-performance tungsten alloy bar forging, and more particularly, to a high-performance tungsten alloy bar and a preparation method thereof.
  • High specific gravity alloys have excellent properties such as high density, high strength, good ductility, small thermal expansion coefficient, good electrical and thermal conductivity, strong corrosion resistance and oxidation resistance, good machining and weldability, etc. widely used.
  • it is used as a gyro rotor, inertial rotating element, etc. in the aviation industry; it is used as a kinetic energy armor-piercing bullet core in the weapon industry; it is used as a ray shielding material in the medical and health industry; it is used as an electrothermal upsetting material in the metal processing industry.
  • Deformation strengthening is an effective method to improve the strength of tungsten alloy materials and ensure a certain toughness, and can effectively refine the grains.
  • deformation strengthening methods for high-performance tungsten alloys including various types of deformation methods such as air hammer forging, rotary forging, rapid forging, and rolling.
  • multiple annealing is required, which reduces work efficiency and makes it difficult to achieve the goal of high-efficiency and mass production; because air hammer forging uses up-and-down motion hammering force, the diameter of the tungsten alloy rod produced is reduced.
  • the uniformity of the force in the direction is poor; although the hydraulic force is applied to the fast forging deformation, which is more stable than the air hammer forging, it still has the disadvantage that the uniformity of the radial force of the tungsten alloy bar is poor due to the force applied by the up and down movement of the fast forging machine.
  • the deformation process is often due to the rapid deformation of the surface layer, which makes the performance of the obtained tungsten alloy rods uneven.
  • the present invention provides a high-performance tungsten alloy rod and a preparation method thereof.
  • the preparation method is simple to operate, can realize low-temperature forging, and the obtained tungsten alloy rod has uniform performance and room temperature tensile strength ⁇ 1350MPa , Yield strength ⁇ 1250MPa, elongation after fracture ⁇ 12%.
  • the first aspect of the present invention provides a high-performance tungsten alloy rod, and the rod comprises the following components by mass percentage:
  • nickel, iron and tungsten form a bonding phase to connect the tungsten particles.
  • the tensile strength at room temperature of the rod is greater than or equal to 1350MPa, the yield strength is greater than or equal to 1250MPa, and the elongation after fracture is greater than or equal to 12%; 6-10mm (such as 7mm, 8mm, 9mm), the length of the rod is 300-1000mm (such as 400mm, 500mm, 600mm, 700mm, 800mm, 900mm).
  • a second aspect of the present invention provides a method for preparing a high-performance tungsten alloy rod, the preparation method comprising the following steps:
  • Tungsten powder, nickel powder and iron powder are respectively weighed and mixed according to the composition ratio of the above-mentioned rod to obtain composite powder, and then the binder is added to the composite powder for mixing treatment, and then subjected to extrusion molding treatment, Degumming treatment, sintering treatment, post-sintering heat treatment, precision forging deformation treatment to obtain tungsten alloy rod;
  • the total deformation amount of the finishing forging deformation treatment is 20-60% (for example, 25%, 30%, 35%, 40%, 45%, 50%, 55%).
  • precision forging deformation treatment is selected as the deformation strengthening method for preparing high-performance tungsten alloy bars, mainly because the precision forging deformation treatment has large forging force, can forge large pieces, and makes the deformation of the forged billet more uniform.
  • the precision forging deformation treatment can The realization of low temperature forging, even cold forging, can save energy and reduce consumption, and can also prolong the service life of the equipment.
  • the forged tungsten alloy bar produces less oxide scale and has a smoother surface. Well, it can generally reach Ra3.2, and can be directly applied without subsequent machining.
  • the prepared tungsten alloy rod has a room temperature tensile strength of ⁇ 1350MPa, a yield strength of ⁇ 1250MPa, and an elongation of ⁇ 12%.
  • the total deformation amount of the precision forging deformation treatment is controlled at 20-60%.
  • the prepared tungsten alloy rod can be completely forged from the surface layer to the core, and at the same time, the tungsten alloy rod will not be damaged.
  • the tungsten particles in the bar are broken, resulting in a greatly reduced elongation; if the deformation of the precision forging treatment is too low, the forging of the core of the tungsten alloy rod is incomplete; if the deformation of the precision forging treatment is too high, the tungsten particles will be broken. so as to reduce the plasticity of the tungsten alloy rod.
  • the compact formed by the composite powder after extrusion molding can be more uniform and consistent, so that the final tungsten alloy rod has stable and consistent performance.
  • first heat treatment is performed first, then multiple passes of forging are carried out, and return heating is carried out before the next pass of forging (adjacent pass forging is carried out).
  • the step of returning the billet to the furnace for heating is set between the passes); preferably, the precision forging deformation treatment requires 2-3 passes of forging, and the deformation amount of each pass is 10-20% (such as 12%, 14%, 16%, 18% %); preferably, the forging frequency is 40-50Hz (such as 42Hz, 44Hz, 46Hz, 48Hz), and the advancing speed is 5-12mm/s (such as 7mm/s, 8mm/s, 9mm/s, 10mm/s, 11mm/s); preferably, the heating temperature of the primary heat treatment is 400-1000°C (such as 500°C, 600°C, 700°C, 800°C, 900°C), preferably less than 700°C, more preferably 400-600°C (eg 420°C
  • the deformation amount of each pass is too low, the number of forging passes will be increased to meet the total deformation amount in the process of precision forging deformation, and the increase of forging passes will further increase the processing cost; Work hardening is easy to occur during the beating process. Therefore, excessive deformation in each pass will damage the tungsten particles and reduce the elongation.
  • the purpose of the initial heat treatment in this application is to heat the bar that has undergone heat treatment after sintering.
  • the heating temperature is too low, the risk of fracture of the forged billet will occur, and if the heating temperature is too high, a thick oxide scale will be formed on the surface of the forged billet, which will affect the subsequent processing; in this application, the next pass of forging is carried out.
  • the main purpose of reheating is to cooperate with the subsequent forging, so that the temperature from the core to the outer surface of the bar is uniform, reducing the risk of fracture of the forged bar and the generation of thick oxide scale; the forged bar in this application does not need to be After annealing treatment, the finished product of the required size can be obtained by direct machining.
  • the preparation method in the present application can realize low-temperature forging, and the precision forging deformation can be carried out at a temperature lower than 700°C, preferably 400-600°C, and the operation is simple. Each stand absorbs heat during the rolling process, so continuous rolling deformation below 700°C cannot be achieved.
  • the Fisher particle size of the tungsten powder is 4.0-5.0 ⁇ m (for example, 4.2 ⁇ m, 4.4 ⁇ m, 4.6 ⁇ m, 4.8 ⁇ m), and the particle size of the nickel powder is 3.0-5.0 ⁇ m.
  • the particle size of the iron powder is 2.0-2.8 ⁇ m (such as 2.2 ⁇ m, 2.4 ⁇ m, 2.6 ⁇ m); the tungsten powder, nickel powder and the
  • the mixing of iron powder is carried out in a mixer; preferably, the rotating speed is 50-70r/min (such as 55r/min, 58r/min, 65r/min, 68r/min), and the mixing time is 12-24h (such as 14h, 16h, 18h, 20h, 22h).
  • the binder is added to the composite powder for mixing treatment, and the mixing treatment is performed at 50-80°C (such as 55°C, 60°C, 65°C , 70°C, 75°C), and the mixing time is 3-6h (such as 3.5h, 4h, 4.5h, 5h, 5.5h); preferably, the binder is paraffin;
  • the binder is 3%-5% by weight of the composite powder (eg 3.5%, 4%, 4.5%).
  • the extrusion pressure is 100-150 MPa (for example, 110 MPa, 120 MPa, 130 MPa, 140 MPa).
  • the pressing method of extrusion molding is adopted to overcome the problem of inconsistent bar sizes in the conventional cold isostatic pressing method.
  • the material is automatically discharged after the pressure reaches the set value, without pressure holding, and has no effect on the density of the green compact. Require.
  • the degumming treatment is performed in a degumming furnace under a hydrogen atmosphere
  • the degumming temperature is 400-800°C (such as 500°C, 600°C, 700°C)
  • the degumming time is 10 -15h (eg 11h, 12h, 13h, 14h).
  • the sintering treatment is performed in a hydrogen atmosphere; preferably, the sintering is divided into low-temperature sintering and high-temperature sintering; preferably, the low-temperature sintering temperature is 1100-1250° C. (such as 1120°C, 1150°C, 1180°C, 1220°C), the sintering time is 25-60min (such as 30min, 40min, 50min); the high temperature sintering temperature is 1450-1540°C (such as 1480°C, 1500°C, 1520°C), The sintering time is 25-60min (eg 30min, 40min, 50min).
  • the low-temperature sintering temperature is 1100-1250° C. (such as 1120°C, 1150°C, 1180°C, 1220°C)
  • the sintering time is 25-60min (such as 30min, 40min, 50min)
  • the high temperature sintering temperature is 1450-1540°C (such as 1480°C
  • the low-temperature sintering mainly completes the heat conduction and the volatilization and impurity removal process of low-melting impurities such as carbon, sulfur and oxygen
  • the high-temperature sintering mainly completes the impurity removal and pore closing process of the high-melting impurities, and a sintered bar with excellent mechanical properties is obtained.
  • the post-sintering heat treatment is performed under nitrogen, argon or vacuum conditions; preferably, the post-sintering heat treatment temperature is 800-1300° C. , 1100 °C, 1200 °C), keep warm for 0.5-10h (such as 1h, 3h, 5h, 7h, 9h).
  • the preparation method further includes machining treatment, and the machining treatment is performed after the finish forging deformation treatment.
  • the present invention has the following beneficial effects:
  • the preparation method of the present invention selects the fine forging deformation treatment as the deformation strengthening method, the forging force of the fine forging deformation treatment is large, the forging is uniform, the performance of the forged billet after the fine forging deformation treatment is stable, and the fine forging deformation treatment can realize Low temperature forging (below 700°C, preferably 400-600°C for fine forging deformation), or even cold forging, can save energy and reduce consumption, prolong the service life of the equipment, and the surface finish of the tungsten alloy rod obtained after the fine forging deformation treatment it is good.
  • Low temperature forging below 700°C, preferably 400-600°C for fine forging deformation
  • even cold forging can save energy and reduce consumption, prolong the service life of the equipment, and the surface finish of the tungsten alloy rod obtained after the fine forging deformation treatment it is good.
  • the present invention cooperates with the extrusion molding process by adding a binder, and the green compact after extrusion molding has a good consistency, and then undergoes an inert gas protection heat treatment after sintering to remove the hydrogen in the tungsten alloy bar to ensure the sintered billet. It has excellent deformation ability, and cooperates with precision forging machine for forging deformation, forging evenly, and the obtained tungsten alloy bars have uniform properties.
  • the room temperature tensile strength of the tungsten alloy bar prepared by the invention is greater than or equal to 1350MPa, the yield strength is greater than or equal to 1250MPa, and the elongation after fracture is greater than or equal to 12%, which can meet the use requirements of military applications.
  • FIG. 1 is a metallographic structure diagram of a tungsten alloy rod blank obtained by heat treatment after sintering in Example 1 of the application.
  • FIG. 2 is a metallographic structure diagram of a tungsten alloy forged billet obtained by a precision forging deformation process in Example 1 of the application.
  • FIG. 3 is a metallographic structure diagram of a tungsten alloy rod blank obtained by heat treatment after sintering in Comparative Example 2 of the present application.
  • FIG. 4 is a metallographic structure diagram of a tungsten alloy billet obtained by rolling deformation treatment in Comparative Example 2 of the application.
  • test methods in the following examples are conventional methods, which can be carried out according to the techniques or conditions described in the literature in the field or according to the product specification.
  • the materials used in the following examples are all commercially available.
  • the specific embodiment of the present invention provides a kind of high-performance tungsten alloy rod, and its preparation method comprises:
  • Extrusion molding treatment the above-mentioned composite powder is mixed with a binder that accounts for 3%-5% of the weight of the composite powder, the mixing temperature is 50-80 °C, and the mixing time is 3-6h; then Put it into the barrel of the extruder for extrusion molding, and the extrusion pressure is 100-150MPa to obtain an extrusion billet;
  • Degumming treatment place the extruded billet in a degumming furnace for degumming treatment under a hydrogen atmosphere, the degumming temperature is 400-800°C, and the degumming time is 10-15h;
  • Post-sintering heat treatment the above-mentioned sintered blank is subjected to post-sintering heat treatment under nitrogen, argon or vacuum conditions, and the post-sintering heat treatment temperature is 800-1300°C, and the temperature is kept for 0.5-10h;
  • Performance test refer to GB/T 13239-2006 "Metallic Materials Low Temperature Tensile Test Method" for tensile test.
  • Embodiment 1 a high-performance tungsten alloy rod, its preparation method includes:
  • Degumming treatment place the extruded billet in a degumming furnace for degumming treatment under a hydrogen atmosphere, the degumming temperature is 600°C, and the degumming time is 15h;
  • Post-sintering heat treatment the above-mentioned sintered blanks were subjected to post-sintering heat treatment under nitrogen.
  • the post-sintering heat treatment temperature was 900°C, and the temperature was kept for 6 h; the tensile properties at room temperature were tested, the tensile strength was 920 MPa, the yield strength was 870 MPa, and the elongation at break was 920 MPa.
  • Figure 1 is the metallographic structure diagram of the tungsten alloy billet obtained by heat treatment after sintering;
  • Embodiment 2 a kind of high-performance tungsten alloy rod, its preparation method comprises:
  • Degumming treatment place the extruded billet in a degumming furnace for degumming treatment under a hydrogen atmosphere, the degumming temperature is 700°C, and the degumming time is 12h;
  • Post-sintering heat treatment the above-mentioned sintered blanks were subjected to post-sintering heat treatment under nitrogen.
  • the post-sintering heat treatment temperature was 1000°C, and the temperature was kept for 4 hours; the tensile properties at room temperature were tested, the tensile strength was 970MPa, the yield strength was 905MPa, and the elongation at break was 970MPa. 35%, the metallographic structure of the tungsten alloy billet obtained by heat treatment after sintering is not much different from that in Figure 1;
  • Embodiment 3 a kind of high-performance tungsten alloy rod, its preparation method comprises:
  • Degumming treatment place the above-mentioned extrusion billet in a degumming furnace for degumming treatment under a hydrogen atmosphere, the degumming temperature is 800°C, and the degumming time is 10h;
  • Post-sintering heat treatment the above-mentioned sintered blanks were subjected to post-sintering heat treatment under nitrogen conditions.
  • the post-sintering heat treatment temperature was 1200 °C, and the temperature was kept for 2 h; the tensile properties at room temperature were tested, the tensile strength was 990 MPa, the yield strength was 922 MPa, and the elongation at break was 990 MPa.
  • the metallographic structure of the tungsten alloy billet obtained by heat treatment after sintering is not much different from that in Figure 1;
  • Embodiment 4 a kind of high-performance tungsten alloy rod, its preparation method comprises:
  • Degumming treatment place the extruded billet in a degumming furnace for degumming treatment under a hydrogen atmosphere, the degumming temperature is 700°C, and the degumming time is 12h;
  • Post-sintering heat treatment the above-mentioned sintered blanks were subjected to post-sintering heat treatment under nitrogen.
  • the post-sintering heat treatment temperature was 1000°C, and the temperature was kept for 4 hours; the tensile properties at room temperature were tested, the tensile strength was 970MPa, the yield strength was 905MPa, and the elongation at break was 970MPa. 35%, the metallographic structure of the tungsten alloy billet obtained by heat treatment after sintering is not much different from that in Figure 1;
  • Embodiment 5 a kind of high-performance tungsten alloy rod, its preparation method comprises:
  • a high-performance tungsten alloy rod comprising:
  • Degumming treatment place the extruded billet in a degumming furnace for degumming treatment under a hydrogen atmosphere, the degumming temperature is 700°C, and the degumming time is 12h;
  • Post-sintering heat treatment the above-mentioned sintered blanks were subjected to post-sintering heat treatment under nitrogen.
  • the post-sintering heat treatment temperature was 1000°C, and the temperature was kept for 4 hours; the tensile properties at room temperature were tested, the tensile strength was 970MPa, the yield strength was 905MPa, and the elongation at break was 970MPa. 35%, the metallographic structure of the tungsten alloy billet obtained by heat treatment after sintering is not much different from that in Figure 1;
  • a tungsten alloy rod, its preparation method includes:
  • Post-sintering heat treatment The above-mentioned sintered blanks are subjected to post-sintering heat treatment under nitrogen, argon or vacuum conditions.
  • the post-sintering heat treatment temperature is 1000 ° C, and the temperature is kept for 4 hours; the tensile properties at room temperature are tested, the tensile strength is 952 MPa, and the yield strength is 892MPa, elongation at break 30%;
  • Rotary forging deformation treatment the above-mentioned sintered and heat-treated bar billets are firstly heated in a nitrogen atmosphere, the heating temperature is 700 ° C, and the holding time is 1 h; The tungsten alloy rod and slab are obtained by returning to the furnace before the next pass of forging. The heating temperature is 700°C and the holding time is 15min to obtain a ⁇ 6.9 ⁇ 1080mm tungsten alloy rod slab; the room temperature tensile test is carried out on the tungsten alloy rod slab. , tensile strength 1260MPa, yield strength 1105MPa, elongation at break 8%;
  • Comparative Example 2 A tungsten alloy rod, its preparation method is the same as that of Example 2 except that the fine forging deformation treatment in step (6) is different, and Comparative Example 2 adopts:
  • Rolling deformation treatment heat treatment of the above-mentioned sintered bar billets in a nitrogen atmosphere, the heating temperature is 800 ° C, and the holding time is 1 h; 20%; the rolling speed is 0.5m/s, and the ⁇ 6.9 ⁇ 1080mm tungsten alloy billet is obtained; the room temperature tensile test is carried out on the tungsten alloy billet, the tensile strength is 1310MPa, the yield strength is 1205MPa, and the elongation at break is 8.5%.
  • the metallographic structure of the tungsten alloy billet obtained by rolling deformation treatment is shown in Figure 4.

Abstract

一种高性能钨合金棒材及其制备方法，所述棒材按质量百分比包括以下组分：钨90-95％，镍3.5-7％，铁1.5-3％，其余为不可避免的杂质；所述棒材的制备方法包括：按照上述棒材的组分配比分别称取钨粉、镍粉和铁粉进行混合得到复合粉末，然后将粘结剂加入到复合粉末中进行混料处理，再依次经过挤压成型处理、脱胶处理、烧结处理、烧结后热处理、精锻变形处理，制得钨合金棒材；其中，精锻变形处理的总变形量为20-60％；该制备方法操作简单，能够实现低温锻造，且制得的钨合金棒材性能均一，室温抗拉强度≥1350MPa、屈服强度≥1250MPa、断后延伸率≥12％。

Description

一种高性能钨合金棒材及其制备方法 技术领域
本发明涉及高性能钨合金棒材锻造领域，更具体的说，涉及一种高性能钨合金棒材及其制备方法。
背景技术
高比重合金具有密度高、强度大、延展性好、热膨胀系数小、导电和导热性能好以及抗腐蚀和抗氧化能力强、机加工和可焊性良好等优异性能，在国防和民用工业上得到了广泛应用。如在航空工业中被用作陀螺转子、惯性旋转元件等；在兵器工业中被用作动能穿甲弹弹芯；在医疗卫生行业中被用作射线屏蔽材料；在金属加工行业被用作电热镦粗砧块材料、压铸模材料等。
随着社会的发展和科学技术的进步，对高比重合金的性能要求越来越高。为了提高高比重合金材料的性能，国内外对其制备技术和变形加工等方面进行了大量研究，取得了很大的进展，而不断采用的先进制备技术和加工工艺使得高比重合金材料的使用范围也越来越广。
形变强化是提高钨合金材料强度及保证一定韧性的一种有效方法，且可以有效地细化晶粒。目前，高性能钨合金的形变强化方式有很多，包括空气锤锻造、旋锻、快锻、轧制等各种类型的变形方式，但由于传统的旋锻变形工艺需要通过多道次的锻造，以及为了保证足够的变形能力需要多次退火，这降低了工作效率，难以实现高效率、大批量生产的目标；由于空气锤锻造采用上下运动锤击施力，使得制得的钨合金棒材径向受力均匀性较差；快锻变形虽然采用液压施力，较空气锤锻造稳定，但仍存在由于快锻机上下运动施力，钨合金棒材径向受力均匀性差的缺点；而轧制变形工艺往往由于表层变形较快，使得制得的钨合金棒材性能不均一。
发明内容
为了解决上述技术问题，本发明提供一种高性能钨合金棒材及其制备方 法，该制备方法操作简单，能够实现低温锻造，且制得的钨合金棒材性能均一，室温抗拉强度≥1350MPa、屈服强度≥1250MPa、断后延伸率≥12％。
针对上述发明目的，本发明第一方面提供了一种高性能钨合金棒材，所述棒材按质量百分比包括以下组分：
钨90-95％，镍3.5-7％，铁1.5-3％，其余为不可避免的杂质。
本申请中通过在钨中加入镍、铁元素，经烧结后镍、铁、钨形成粘结相连接钨颗粒，此粘结相具有较好的变形能力，从而使得钨合金具有一定的韧性，克服了纯钨产品由于密度大韧性差的特性；本申请中加入的镍、铁含量过少，钨含量过多将会直接影响制得的钨合金棒材的延伸率，导致韧性变差；本申请中加入的镍、铁含量过多，钨含量过少，则会使得制得的钨合金棒材的抗拉强度无法满足使用要求。
在上述高性能钨合金棒材中，作为一种优选实施方式，所述棒材的室温抗拉强度≥1350MPa，屈服强度≥1250MPa，断后延伸率≥12％；优选地，所述棒材的直径为6-10mm(比如7mm、8mm、9mm)，所述棒材的长度为300-1000mm(比如400mm、500mm、600mm、700mm、800mm、900mm)。
本发明第二方面提供了一种高性能钨合金棒材的制备方法，所述制备方法包含如下步骤：
按照上述棒材的组分配比分别称取钨粉、镍粉和铁粉进行混合得到复合粉末，然后将粘结剂加入到所述复合粉末中进行混料处理，再依次经过挤压成型处理、脱胶处理、烧结处理、烧结后热处理、精锻变形处理，制得钨合金棒材；
其中，所述精锻变形处理的总变形量为20-60％(比如25％、30％、35％、40％、45％、50％、55％)。
本申请选择精锻变形处理作为制备高性能钨合金棒材的形变强化方式，主要因为精锻变形处理的锻造力量大，能够锻大件，使得锻打棒坯变形更加均匀，同时精锻变形处理能够实现低温锻造，甚至冷锻，能够节能降耗，也可延长设备的使用寿命，此外，精锻变形处理相较于轧制变形，锻造出的钨合金棒材产生的氧化皮较少，表面光洁度好，一般能够达到Ra3.2，可不经后续机加工直接应用，制备得到的钨合金棒材室温抗拉强度≥1350MPa，屈服强度≥1250MPa，断后延伸率≥12％。
本申请中通过将精锻变形处理的总变形量控制在20-60％，在此变形量下，能够保证制得的钨合金棒材由表层到心部完全锻透，同时不会使得钨合金棒材中的钨颗粒破粹，从而导致延伸率大大降低；若精锻处理的变形量过低，则钨合金棒心部锻造不完全，若精锻处理的变形量过高，则钨颗粒破粹，从而降低钨合金棒的塑性。本申请中通过加入粘结剂与挤压成型处理相配合，能使复合粉末在挤压成型后形成的压坯均匀一致性较好，从而使得最终制得的钨合金棒材性能稳定一致。
在上述制备方法中，作为一种优选实施方式，在所述精锻变形处理中，先进行初次加热处理，然后进行多道次锻打，在进行下道次锻打前进行回炉加热(相邻道次间设置坯料回炉加热步骤)；优选地，所述精锻变形处理需要进行2-3道次锻打，每道次变形量10-20％(比如12％、14％、16％、18％)；优选地，锻打频率为40-50Hz(比如42Hz、44Hz、46Hz、48Hz)，推进速度为5-12mm/s(比如7mm/s、8mm/s、9mm/s、10mm/s、11mm/s)；优选地，所述初次加热处理的加热温度为400-1000℃(比如500℃、600℃、700℃、800℃、900℃)、优选小于700℃、更优选400-600℃(比如420℃、480℃、520℃、580℃)，保温时间为0.5-2h(比如0.6h、0.8h、1.2h、1.6h、1.8h)；优选地，所述初次加热处理在氮气气氛下进行；优选地，所述回炉加热的加热温度为400-1000℃(比如500℃、600℃、700℃、800℃、900℃)、优选小于700℃、更优选400-600℃(比如420℃、480℃、520℃、580℃)，保温时间为10-40min(比如15min、20min、25min、30min、35min)。
本申请中，每道次变形量过低，将会增加锻打道次，以满足精锻变形处理过程中的总变形量，锻打道次增加，使得加工成本进一步增加；由于钨合金棒材在锻打过程中极易发生加工硬化，因此，每道次变形量过高将会对钨颗粒造成破坏，降低延伸率；本申请中先进行初次加热处理的目的在于将经过烧结后热处理的棒材加热至可塑性变形的温度，加热温度过低会使锻造棒坯出现断裂风险，加热温度过高则会使得锻造棒坯表面产生较厚氧化皮，影响后续加工；本申请中在进行下道次锻打前进行回炉加热的主要目的是为了配合后续锻造，使得棒材的心部到外表面温度均匀一致，降低锻造棒坯出现断裂风险以及较厚氧化皮的产生；本申请中的锻造棒坯不需要经过退火处理，直接机加工即可获得所需尺寸的成品。
本申请中的制备方法能够实现低温锻造，在低于700℃、优选400-600℃ 下即可进行精锻变形，操作简单，而轧制变形虽然效率高，但由多个轧辊机架组成，每个机架在轧制过程中都会吸热，因此无法实现低于700℃进行连续轧制变形。
在上述制备方法中，作为一种优选实施方式，所述钨粉的费氏粒度为4.0-5.0μm(比如4.2μm、4.4μm、4.6μm、4.8μm)，所述镍粉的粒度为3.0-4.0μm(比如3.2μm、3.4μm、3.6μm、3.8μm)，所述铁粉的粒度为2.0-2.8μm(比如2.2μm、2.4μm、2.6μm)；所述钨粉、镍粉和所述铁粉的混合于混料机中进行；优选地，转速为50-70r/min(比如55r/min、58r/min、65r/min、68r/min)，混合时间为12-24h(比如14h、16h、18h、20h、22h)。
在上述制备方法中，作为一种优选实施方式，所述粘结剂加入到所述复合粉末中进行混料处理，所述混料处理在50-80℃(比如55℃、60℃、65℃、70℃、75℃)下进行，混料时间为3-6h(比如3.5h、4h、4.5h、5h、5.5h)；优选地，所述粘结剂为石蜡；优选地，所述粘结剂为所述复合粉末重量的3％-5％(比如3.5％、4％、4.5％)。
在上述制备方法中，作为一种优选实施方式，在所述挤压成型中，挤压压力为100-150MPa(比如110MPa、120MPa、130MPa、140MPa)。
本申请中采用挤压成型的压制方法，克服常规冷等静压成型方式棒料尺寸不一致的问题，本申请中的压力达到设定值后自动出料，不保压，对压坯的密度无要求。
在上述制备方法中，作为一种优选实施方式，所述脱胶处理在脱胶炉内，氢气气氛下进行，脱胶温度为400-800℃(比如500℃、600℃、700℃)，脱胶时间为10-15h(比如11h、12h、13h、14h)。
在上述制备方法中，作为一种优选实施方式，所述烧结处理在氢气气氛下进行；优选地，所述烧结分为低温烧结和高温烧结；优选地，所述低温烧结温度为1100-1250℃(比如1120℃、1150℃、1180℃、1220℃)，烧结时间为25-60min(比如30min、40min、50min)；高温烧结温度为1450-1540℃(比如1480℃、1500℃、1520℃)，烧结时间为25-60min(比如30min、40min、50min)。
本申请中低温烧结主要完成热传导和碳硫氧等低熔点杂质的挥发、排杂过程，高温烧结主要完成高熔点杂质的排杂和气孔闭合过程，得到具有优秀力学性能的烧结棒坯。
在上述制备方法中，作为一种优选实施方式，所述烧结后热处理于氮气、氩气或真空条件下进行；优选地，所述烧结后热处理的温度800-1300℃(比如900℃、1000℃、1100℃、1200℃)，保温0.5-10h(比如1h、3h、5h、7h、9h)。
在上述制备方法中，作为一种优选实施方式，所述制备方法还包括机加工处理，所述机加工处理在精锻变形处理之后进行。
与现有技术相比，本发明具有如下有益效果：
1、本发明的制备方法选择精锻变形处理作为形变强化方式，精锻变形处理的锻造力量大、锻打均匀，经精锻变形处理后的锻造棒坯性能稳定，同时精锻变形处理能够实现低温锻造(低于700℃、优选400-600℃下进行精锻变形)、甚至冷锻，能够节能降耗，延长设备的使用寿命，且经精锻变形处理后得到的钨合金棒材表面光洁度好。
2、本发明通过加入粘结剂与挤压成型处理相配合，经挤压成型后的压坯一致性良好，再经烧结后惰性气体保护热处理，除去钨合金棒料内的氢，保证烧结坯具有优秀的变形能力，配合精锻机锻打变形，锻打均匀，制得的钨合金棒材性能均匀一致。
3、本发明制得的钨合金棒材的室温抗拉强度≥1350MPa，屈服强度≥1250MPa，断后延伸率≥12％，能够满足军事应用的使用要求。
附图说明
图1为本申请实施例1经烧结后热处理得到的钨合金棒坯的金相组织图。
图2为本申请实施例1经精锻变形处理得到的钨合金锻造棒坯的金相组织图。
图3为本申请对比例2经烧结后热处理得到的钨合金棒坯的金相组织图。
图4为本申请对比例2经轧制变形处理得到的钨合金棒坯的金相组织图。
具体实施方式
下面结合具体实施方式对本发明进行进一步的详细描述，给出的实施例仅为了阐明本发明，而不是为了限制本发明的范围。以下提供的实施例可作为本技术领域普通技术人员进行进一步改进或应用的基础，并不以任何方式构成对本发明的具体限制。
下述实施例中的试验方法中，如无特殊说明，均为常规方法，可按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。下述实施例中所用的材料均为市售。
本发明的具体实施方式提供一种高性能钨合金棒材，其制备方法包括：
(1)复合粉末的制备：选择符合要求的原料放入V型混料机混合，转速为50-70r/min，混合时间为12-24h，得到复合粉末；
(2)挤压成型处理：将上述复合粉末与占复合粉末重量的3％-5％的粘结剂进行混料处理，混料温度为50-80℃，混料时间为3-6h；然后将其装入挤压机料桶内进行挤压成型处理，挤压压力为100-150MPa，制得挤压坯；
(3)脱胶处理：将上述挤压坯放置于脱胶炉内进行氢气气氛下的脱胶处理，脱胶温度为400-800℃，脱胶时间为10-15h；
(4)烧结处理：将上述经脱胶处理后的棒坯置于氢气气氛下进行烧结处理，烧结分为低温烧结和高温烧结，低温烧结温度为1100-1250℃，烧结时间为25-60min，高温烧结温度为1450-1540℃，烧结时间为25-60min，得到烧结坯；
(5)烧结后热处理：将上述烧结坯在氮气、氩气或者真空条件下进行烧结后热处理，烧结后热处理的温度800-1300℃，保温0.5-10h；
(6)精锻变形处理：将上述烧结后热处理的棒坯在氮气气氛下先进行初次加热处理，加热温度为400-1000℃，保温时间为0.5-2h；然后进行多道次锻打，每道次变形量为10-20％；在进行下道次锻打前进行回炉加热，加热温度为400-1000℃，保温时间为10-40min；精锻过程中的锻打频率为40-50Hz，推进速度为5-12mm/s，精锻变形处理的总变形量为20-60％，得到钨合金锻造棒坯；
(7)机加工：对上述钨合金锻造棒坯进行机加工处理，得到所需尺寸的钨合金棒成品。
性能测试：参照GB/T 13239-2006《金属材料低温拉伸实试验方法》进行拉伸试验。
实施例1：一种高性能钨合金棒材，其制备方法包括：
(1)复合粉末的制备：称取4.0μm的钨粉18Kg、3.1μm的镍粉1.4Kg、 2.2μm的铁粉0.6Kg，放入V型混料机混合，转速为70r/min，混合时间为12h，得到复合粉末；
(2)挤压成型处理：将上述复合粉末与0.8Kg的石蜡进行混料处理，混料温度为60℃，混料时间为4h；然后将其装入挤压机料桶内进行挤压成型处理，挤压压力为100MPa，制得φ15.4×630mm挤压坯；
(3)脱胶处理：将上述挤压坯放置于脱胶炉内进行氢气气氛下的脱胶处理，脱胶温度为600℃，脱胶时间为15h；
(4)烧结处理：将上述经脱胶处理后的棒坯置于氢气气氛下进行烧结处理，烧结分为低温烧结和高温烧结，低温烧结温度为1100℃，烧结时间为25min，高温烧结温度为1450℃，烧结时间为25min，得到φ12.3×505mm烧结坯；
(5)烧结后热处理：将上述烧结坯在氮气下进行烧结后热处理，烧结后热处理的温度900℃，保温6h；测试室温拉伸性能，抗拉强度920MPa，屈服强度为870MPa，断裂伸长率31％，图1为经烧结后热处理得到的钨合金棒坯的金相组织图；
(6)精锻变形处理：将上述烧结后热处理的棒坯在氮气气氛下先进行初次加热处理，加热温度为400℃，保温时间为2h；然后进行2道次锻打，每道次变形量为15％；在进行下道次锻打前进行回炉加热，加热温度为400℃，保温时间为20min；精锻过程中的锻打频率为40Hz，推进速度为5mm/s，得到φ10.3×720mm钨合金锻造棒坯；对钨合金锻造棒坯进行室温拉伸测试，抗拉强度1365MPa，屈服强度1255MPa，断裂伸长率13％，图2为经精锻变形处理得到的钨合金锻造棒坯的金相组织图；
(7)机加工：对上述钨合金锻造棒坯进行机加工处理，得到所需尺寸的钨合金棒成品。
实施例2：一种高性能钨合金棒材，其制备方法包括：
(1)复合粉末的制备：称取4.2μm的钨粉18.6Kg、3.5μm的镍粉0.98Kg、2.0μm的铁粉0.42Kg，放入V型混料机混合，转速为60r/min，混合时间为18h，得到复合粉末；
(2)挤压成型处理：将上述复合粉末与0.6Kg的石蜡进行混料处理，混 料温度为70℃，混料时间为5h；然后将其装入挤压机料桶内进行挤压成型处理，挤压压力为110MPa，制得φ13.6×540mm挤压坯；
(3)脱胶处理：将上述挤压坯放置于脱胶炉内进行氢气气氛下的脱胶处理，脱胶温度为700℃，脱胶时间为12h；
(4)烧结处理：将上述经脱胶处理后的棒坯置于氢气气氛下进行烧结处理，烧结分为低温烧结和高温烧结，低温烧结温度为1150℃，烧结时间为30min，高温烧结温度为1480℃，烧结时间为30min，得到φ10.9×433mm烧结坯；经挤压成型处理的烧结坯直径尺寸范围为φ10.8-11mm；
(5)烧结后热处理：将上述烧结坯在氮气下进行烧结后热处理，烧结后热处理的温度1000℃，保温4h；测试室温拉伸性能，抗拉强度970MPa，屈服强度为905MPa，断裂伸长率35％，其经烧结后热处理得到的钨合金棒坯的金相组织图与图1差别不大；
(6)精锻变形处理：将上述烧结后热处理的棒坯在氮气气氛下先进行初次加热处理，加热温度为500℃，保温时间为1h；然后进行3道次锻打，每道次变形量为20％；在进行下道次锻打前进行回炉加热，加热温度为500℃，保温时间为15min；精锻过程中的锻打频率为45Hz，推进速度为8mm/s，得到φ6.9×1080mm钨合金锻造棒坯；对钨合金锻造棒坯进行室温拉伸测试，抗拉强度1378MPa，屈服强度1280MPa，断裂伸长率12.2％，其经精锻变形处理得到的钨合金锻造棒坯的金相组织图与图2差别不大；
(7)机加工：对上述钨合金锻造棒坯进行机加工处理，得到所需尺寸的钨合金棒成品。
实施例3：一种高性能钨合金棒材，其制备方法包括：
(1)复合粉末的制备：称取4.5μm的钨粉19Kg、3.0μm的镍粉0.7Kg、2.5μm的铁粉0.3Kg，放入V型混料机混合，转速为50r/min，混合时间为24h，得到复合粉末；
(2)挤压成型处理：将上述复合粉末与1Kg的石蜡进行混料处理，混料温度为80℃，混料时间为6h；然后将其装入挤压机料桶内进行挤压成型处理，挤压压力为120MPa，制得φ12.6×450mm挤压坯；
(3)脱胶处理：将上述挤压坯放置于脱胶炉内进行氢气气氛下的脱胶处 理，脱胶温度为800℃，脱胶时间为10h；
(4)烧结处理：将上述经脱胶处理后的棒坯置于氢气气氛下进行烧结处理，烧结分为低温烧结和高温烧结，低温烧结温度为1200℃，烧结时间为40min，高温烧结温度为1520℃，烧结时间为40min，得到φ10.1×361mm烧结坯；
(5)烧结后热处理：将上述烧结坯在氮气条件下进行烧结后热处理，烧结后热处理的温度1200℃，保温2h；测试室温拉伸性能，抗拉强度990MPa，屈服强度为922MPa，断裂伸长率28％，其经烧结后热处理得到的钨合金棒坯的金相组织图与图1差别不大；
(6)精锻变形处理：将上述烧结后热处理的棒坯在氮气气氛下先进行初次加热处理，加热温度为700℃，保温时间为0.5h；然后进行2道次锻打，每道次变形量为10％；在进行下道次锻打前进行回炉加热，加热温度为700℃，保温时间为10min；精锻过程中的锻打频率为50Hz，推进速度为10mm/s，得到φ9×455mm钨合金锻造棒坯；对钨合金锻造棒坯进行室温拉伸测试，抗拉强度1395MPa，屈服强度1298MPa，断裂伸长率12.8％，其经精锻变形处理得到的钨合金锻造棒坯的金相组织图与图2差别不大；
(7)机加工：对上述钨合金锻造棒坯进行机加工处理，得到所需尺寸的钨合金棒成品。
实施例4：一种高性能钨合金棒材，其制备方法包括：
(1)复合粉末的制备：称取4.2μm的钨粉18.6Kg、3.5μm的镍粉0.98Kg、2.0μm的铁粉0.42Kg，放入V型混料机混合，转速为60r/min，混合时间为18h，得到复合粉末；
(2)挤压成型处理：将上述复合粉末与0.6Kg的石蜡进行混料处理，混料温度为70℃，混料时间为5h；然后将其装入挤压机料桶内进行挤压成型处理，挤压压力为110MPa，制得φ13.6×540mm挤压坯；
(3)脱胶处理：将上述挤压坯放置于脱胶炉内进行氢气气氛下的脱胶处理，脱胶温度为700℃，脱胶时间为12h；
(4)烧结处理：将上述经脱胶处理后的棒坯置于氢气气氛下进行烧结处理，烧结分为低温烧结和高温烧结，低温烧结温度为1150℃，烧结时间为 30min，高温烧结温度为1480℃，烧结时间为30min，得到φ10.9×433mm烧结坯；
(5)烧结后热处理：将上述烧结坯在氮气下进行烧结后热处理，烧结后热处理的温度1000℃，保温4h；测试室温拉伸性能，抗拉强度970MPa，屈服强度为905MPa，断裂伸长率35％，其经烧结后热处理得到的钨合金棒坯的金相组织图与图1差别不大；
(6)精锻变形处理：将上述烧结后热处理的棒坯在氮气气氛下先进行初次加热处理，加热温度为600℃，保温时间为1h；然后进行3道次锻打，每道次变形量为20％；在进行下道次锻打前进行回炉加热，加热温度为600℃，保温时间为15min；精锻过程中的锻打频率为45Hz，推进速度为8mm/s，得到φ6.9×1080mm钨合金锻造棒坯；对钨合金锻造棒坯进行室温拉伸测试，抗拉强度1412MPa，屈服强度1305MPa，断裂伸长率13.2％。
(7)机加工：对上述钨合金锻造棒坯进行机加工处理，得到所需尺寸的钨合金棒成品。
实施例5：一种高性能钨合金棒材，其制备方法包括：
一种高性能钨合金棒材，其制备方法包括：
(1)复合粉末的制备：称取4.2μm的钨粉18.6Kg、3.5μm的镍粉0.98Kg、2.0μm的铁粉0.42Kg，放入V型混料机混合，转速为60r/min，混合时间为18h，得到复合粉末；
(2)挤压成型处理：将上述复合粉末与0.6Kg的石蜡进行混料处理，混料温度为70℃，混料时间为5h；然后将其装入挤压机料桶内进行挤压成型处理，挤压压力为110MPa，制得φ13.6×540mm挤压坯；
(3)脱胶处理：将上述挤压坯放置于脱胶炉内进行氢气气氛下的脱胶处理，脱胶温度为700℃，脱胶时间为12h；
(4)烧结处理：将上述经脱胶处理后的棒坯置于氢气气氛下进行烧结处理，烧结分为低温烧结和高温烧结，低温烧结温度为1150℃，烧结时间为30min，高温烧结温度为1480℃，烧结时间为30min，得到φ10.9×433mm烧结坯；
(5)烧结后热处理：将上述烧结坯在氮气下进行烧结后热处理，烧结后 热处理的温度1000℃，保温4h；测试室温拉伸性能，抗拉强度970MPa，屈服强度为905MPa，断裂伸长率35％，其经烧结后热处理得到的钨合金棒坯的金相组织图与图1差别不大；
(6)精锻变形处理：将上述烧结后热处理的棒坯在氮气气氛下先进行初次加热处理，加热温度为700℃，保温时间为1h；然后进行3道次锻打，每道次变形量为20％；在进行下道次锻打前进行回炉加热，加热温度为700℃，保温时间为15min；精锻过程中的锻打频率为45Hz，推进速度为8mm/s，得到φ6.9×1080mm钨合金锻造棒坯；对钨合金锻造棒坯进行室温拉伸测试，抗拉强度1355MPa，屈服强度1262MPa，断裂伸长率12.1％；
(7)机加工：对上述钨合金锻造棒坯进行机加工处理，得到所需尺寸的钨合金棒成品。
对比例1：一种钨合金棒材，其制备方法包括：
(1)复合粉末的制备：称取4.2μm的钨粉18.6Kg、3.5μm的镍粉0.98Kg、2.0μm的铁粉0.42Kg，放入V型混料机混合，转速为60r/min，混合时间为18h，得到复合粉末；
(2)冷等静压成型处理：将上述复合粉末装入模具中，然后进行压强为220Mpa，时间为15min的冷等静压处理，得到12.8×510mm的压坯；
(4)烧结处理：将上述压坯置于氢气气氛下进行烧结处理，烧结分为低温烧结和高温烧结，低温烧结温度为1150℃，烧结时间为30min，高温烧结温度为1480℃，烧结时间为30min，得到φ10.9×433mm烧结坯；经冷等静压成型处理的烧结坯直径尺寸范围为φ10-11.8mm；
(5)烧结后热处理：将上述烧结坯在氮气、氩气或者真空条件下进行烧结后热处理，烧结后热处理的温度1000℃，保温4h；测试室温拉伸性能，抗拉强度952MPa，屈服强度为892MPa，断裂伸长率30％；
(6)旋锻变形处理：将上述烧结后热处理的棒坯在氮气气氛下先进行初次加热处理，加热温度为700℃，保温时间为1h；然后进行3道次锻打，每道次变形量为20％，在进行下道次锻打前进行回炉加热，加热温度为700℃，保温时间为15min，得到φ6.9×1080mm钨合金棒板坯；对钨合金棒板坯进行室温拉伸测试，抗拉强度1260MPa，屈服强度1105MPa，断裂伸长率8％；
(7)机加工：对上述钨合金棒板坯进行机加工处理，得到所需尺寸的钨 合金棒成品。
对比例2：一种钨合金棒材，其制备方法除了步骤(6)精锻变形处理不同以外，其与均与实施例2相同，对比例2采用：
(6)轧制变形处理：将上述烧结后热处理的棒坯在氮气气氛下进行加热处理，加热温度为800℃，保温时间为1h；然后进行3道次连续轧制，每道次变形量为20％；轧制速度为0.5m/s，得到φ6.9×1080mm钨合金棒坯；对钨合金棒坯进行室温拉伸测试，抗拉强度1310MPa，屈服强度1205MPa，断裂伸长率8.5％，其经轧制变形处理得到的钨合金棒坯的金相组织图如图4所示。
以上对本发明进行了详述。对于本领域技术人员来说，在不脱离本发明的宗旨和范围，以及无需进行不必要的实验情况下，可在等同参数、浓度和条件下，在较宽范围内实施本发明。虽然本发明给出了特殊的实施例，应该理解为，可以对本发明作进一步的改进。总之，按本发明的原理，本申请欲包括任何变更、用途或对本发明的改进，包括脱离了本申请中已公开范围，而用本领域已知的常规技术进行的改变。按以下附带的权利要求的范围，可以进行一些基本特征的应用。

Claims (10)

  1. 一种高性能钨合金棒材，其特征在于，所述棒材按质量百分比包括以下组分：钨90-95％，镍3.5-7％，铁1.5-3％，其余为不可避免的杂质。
  2. 根据权利要求1所述的高性能钨合金棒材，其特征在于，所述棒材的室温抗拉强度≥1350MPa，屈服强度≥1250MPa，断后延伸率≥12％；优选地，所述棒材的直径为6-10mm，所述棒材的长度为300-1000mm。
  3. 一种高性能钨合金棒材的制备方法，其特征在于，按照权利要求1或2所述棒材的组分配比分别称取钨粉、镍粉和铁粉进行混合得到复合粉末，然后将粘结剂加入到所述复合粉末中进行混料处理，再依次经过挤压成型处理、脱胶处理、烧结处理、烧结后热处理、精锻变形处理，制得钨合金棒材；
    其中，所述精锻变形处理的总变形量为20-60％。
  4. 根据权利要求3所述的制备方法，其特征在于，在所述精锻变形处理中，先进行初次加热处理，然后进行多道次锻打，在进行下道次锻打前进行回炉加热；优选地，所述精锻变形处理需要进行2-3道次锻打，每道次变形量10-20％；优选地，锻打频率为40-50Hz，推进速度为5-12mm/s；优选地，所述初次加热处理的加热温度为400-1000℃、优选小于700℃、更优选400-600℃，保温时间为0.5-2h；优选地，所述初次加热处理在氮气气氛下进行；优选地，所述回炉加热的加热温度为400-1000℃、优选小于700℃、更优选400-600℃，保温时间为10-40min。
  5. 根据权利要求3或4所述的制备方法，其特征在于，所述钨粉的费氏粒度为4.0-5.0μm，所述镍粉的粒度为3.0-4.0μm，所述铁粉的粒度为2.0-2.8μm；所述钨粉、镍粉和所述铁粉的混合于混料机中进行；优选地，转速为50-70r/min，混合时间为12-24h。
  6. 根据权利要求3-5任一项所述的制备方法，其特征在于，所述粘结剂加入到所述复合粉末中进行混料处理，所述混料处理在50-80℃下进行，混料时间为3-6h；优选地，所述粘结剂为石蜡；优选地，所述粘结剂为所述复合粉末重量的3％-5％。
  7. 根据权利要求3-6任一项所述的制备方法，其特征在于，在所述挤压成型中，挤压压力为100-150MPa。
  8. 根据权利要求3-7任一项所述的制备方法，其特征在于，所述脱胶处理在脱胶炉内，氢气气氛下进行，脱胶温度为400-800℃，脱胶时间为10-15h。
  9. 根据权利要求3-8任一项所述的制备方法，其特征在于，所述烧结处理在氢气气氛下进行；优选地，所述烧结分为低温烧结和高温烧结；优选地，所述低温烧结温度为1100-1250℃，烧结时间为25-60min；高温烧结温度为1450-1540℃，烧结时间为25-60min。
  10. 根据权利要去3-9任一项所述的制备方法，其特征在于，所述烧结后热处理于氮气、氩气或真空条件下进行；优选地，所述烧结后热处理的温度800-1300℃，保温0.5-10h；优选地，所述制备方法还包括机加工处理，所述机加工处理在精锻变形处理之后进行。
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CN114657431B (zh) * 2022-02-18 2023-01-17 安泰天龙钨钼科技有限公司 一种含能钨合金材料及制备方法
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3979234A (en) * 1975-09-18 1976-09-07 The United States Of America As Represented By The United States Energy Research And Development Administration Process for fabricating articles of tungsten-nickel-iron alloy
CN102787249A (zh) * 2012-09-07 2012-11-21 洛阳高新四丰电子材料有限公司 一种制备高密度钨镍铁合金的烧结工艺
CN103866147A (zh) * 2012-12-17 2014-06-18 中国兵器工业第五二研究所 一种大型高致密钨合金配重的制备方法
US20140308536A1 (en) * 2011-12-07 2014-10-16 A.L.M.T. Corp Sintered tungsten alloy
CN106148745A (zh) * 2015-04-14 2016-11-23 上海六晶科技股份有限公司 采用区域烧结法制备钨镍铁合金的方法
CN108315624A (zh) * 2018-01-09 2018-07-24 安泰天龙钨钼科技有限公司 一种高性能钨合金棒材及其制备方法
CN109306420A (zh) * 2017-11-09 2019-02-05 安泰天龙钨钼科技有限公司 一种高性能钨合金棒材及其制备方法
CN112570710A (zh) * 2020-12-31 2021-03-30 江苏米莫金属股份有限公司 一种钨合金粉末铸件加工方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2633205B1 (fr) * 1988-06-22 1992-04-30 Cime Bocuze Procede de mise en forme directe et d'optimisation des caracteristiques mecaniques de projectiles perforants en alliage de tungstene a haute densite
CN101670434A (zh) * 2009-09-29 2010-03-17 西部金属材料股份有限公司 一种x射线旋转阳极用tzm钼合金棒材的制备方法
CN102717078A (zh) * 2012-05-10 2012-10-10 株洲乐泰金属粉末制品有限公司 一种高密度高性能钨合金旋锻棒工艺
CN104213030B (zh) * 2014-09-25 2016-04-20 湖南英捷高科技有限责任公司 一种注射成形合金粉及其在汽车变速箱滑套中的应用
CN105983698A (zh) * 2016-01-19 2016-10-05 安徽蓝博旺机械集团液压流体机械有限责任公司 一种叉车轮毂轴承的粉末锻造方法
JP6471287B2 (ja) * 2017-01-19 2019-02-20 冨士ダイス株式会社 Ｗ−Ｃｒ基合金またはそれにより作製された金型、電極または押出ダイス
CN108385011A (zh) * 2018-04-10 2018-08-10 抚顺特殊钢股份有限公司 核电用1Cr15Ni36W3Ti合金棒材热处理方法的优化
CN109536758B (zh) * 2018-12-27 2020-10-30 安泰核原新材料科技有限公司 一种钨镍合金及其制备方法
CN110434324A (zh) * 2019-07-10 2019-11-12 西安交通大学 一种高性能粉末锻造合金材料及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3979234A (en) * 1975-09-18 1976-09-07 The United States Of America As Represented By The United States Energy Research And Development Administration Process for fabricating articles of tungsten-nickel-iron alloy
US20140308536A1 (en) * 2011-12-07 2014-10-16 A.L.M.T. Corp Sintered tungsten alloy
CN102787249A (zh) * 2012-09-07 2012-11-21 洛阳高新四丰电子材料有限公司 一种制备高密度钨镍铁合金的烧结工艺
CN103866147A (zh) * 2012-12-17 2014-06-18 中国兵器工业第五二研究所 一种大型高致密钨合金配重的制备方法
CN106148745A (zh) * 2015-04-14 2016-11-23 上海六晶科技股份有限公司 采用区域烧结法制备钨镍铁合金的方法
CN109306420A (zh) * 2017-11-09 2019-02-05 安泰天龙钨钼科技有限公司 一种高性能钨合金棒材及其制备方法
CN108315624A (zh) * 2018-01-09 2018-07-24 安泰天龙钨钼科技有限公司 一种高性能钨合金棒材及其制备方法
CN112570710A (zh) * 2020-12-31 2021-03-30 江苏米莫金属股份有限公司 一种钨合金粉末铸件加工方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHI HONG-GANG, QI ZHI-WANG, SHANG FU-JUN, TIAN KAI-WEN: "Microstructure,mechanical property and recrystallization behavior of swage strengthened tungsten alloy", ORDNANCE MATERIAL SCIENCE AND ENGINEERING, vol. 29, no. 01, 31 January 2006 (2006-01-31), pages 29 - 32, XP055960694, ISSN: 1004-244X *

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