WO2020237945A1 - Multi-element alloy wire for use in spark plug and manufacturing method therefor - Google Patents

Multi-element alloy wire for use in spark plug and manufacturing method therefor Download PDF

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Publication number
WO2020237945A1
WO2020237945A1 PCT/CN2019/108219 CN2019108219W WO2020237945A1 WO 2020237945 A1 WO2020237945 A1 WO 2020237945A1 CN 2019108219 W CN2019108219 W CN 2019108219W WO 2020237945 A1 WO2020237945 A1 WO 2020237945A1
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Prior art keywords
element alloy
alloy wire
wire
alloy
spark plugs
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PCT/CN2019/108219
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French (fr)
Chinese (zh)
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吴宇宁
田开文
徐玉松
马一飞
郭飞
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南京达迈科技实业有限公司
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Publication of WO2020237945A1 publication Critical patent/WO2020237945A1/en

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    • 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
    • B21C37/047—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 of fine wires
    • 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
    • C22C1/023—Alloys based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

Definitions

  • the invention belongs to the field of multi-element alloy filaments, and in particular relates to a multi-element alloy wire for engine spark plugs and a preparation method thereof.
  • the spark plug is a device that ignites the gasoline and air mixture entering the engine. It works under severe conditions of high temperature and high pressure, and also bears high burst pressure and high voltage discharge spark erosion.
  • the side electrode of the spark plug in the combustion chamber of the engine cylinder must have good mechanical strength, thermal conductivity, good oxidation resistance, electrical ablation resistance and chemical corrosion resistance.
  • the electrode material of spark plugs is NiCrMnSi, and its composition is: Cr 1.4 ⁇ 1.8wt.%, Mn 1.3 ⁇ 1.8wt.%, Si 0.4 ⁇ 0.65wt.%, C ⁇ 0.05wt.% and the balance Ni Impurities to avoid.
  • the elongation and tensile strength of the NiCrMnSi alloy spark plug electrode material are not high (the elongation is 28%, the tensile strength is 488MPa), which affects the processing performance of the material, the resistance to deformation during use, and the resistance to high temperature oxidation And poor thermal corrosion performance, its product life is relatively short.
  • the first object of the invention is to provide a multi-element alloy wire for spark plugs with high tensile strength and elongation, and excellent high temperature oxidation resistance;
  • the second object of the present invention is to provide a method for preparing the multi-element alloy wire.
  • the multi-element alloy wire used in the engine spark plug of the present invention is composed of the following components according to mass fraction: Al 0.5 ⁇ 1.5%, Si 0.5 ⁇ 1.5%, B 0.01 ⁇ 0.2%, Y 0.1 ⁇ 0.5%, Nb 0.05 ⁇ 0.7% and the balance Ni and unavoidable impurities.
  • the invention prepares a multi-element alloy wire by compounding Al, Si, B, Y, Nb and Ni, so that the multi-element alloy wire has high melting point, low density, good thermal and electrical conductivity, high temperature resistance, and high temperature oxidation resistance. And high temperature corrosion resistance, and high elongation and tensile strength.
  • the addition of Al can form a nickel-aluminum intermetallic compound with the matrix Ni, which is the main strengthening element of the nickel-based alloy wire and the stabilizer of the high temperature phase;
  • the addition of Y can significantly improve the oxidation resistance of the alloy, and the Al 2 O in the structure alloy 3
  • the continuous formation of protective film, and Y has a greater affinity with O, can form insoluble cermet phase with O, yttrium oxide has a precipitation strengthening effect on the alloy; adding B can prevent or reduce the embrittlement effect of room temperature environment, namely hydrogen Embrittlement, and increase the bonding strength of the grain boundary, increase the ductility of the alloy at room temperature and improve the hot workability.
  • B and the N gas in the alloy can form boron nitride and strengthen the alloy through dispersion and precipitation; the addition of Si can make the alloy have Good fluidity, can reduce porosity and shrinkage, improve alloy compactness and ingot quality.
  • Si combines with oxygen in the alloy liquid to form silicon oxide, which has a solid solution strengthening effect and can further inhibit the oxidation of the alloy; in addition, add Nb can refine the alloy grains and improve the heat resistance of the alloy, and Nb and the remaining N and O gases in the alloy can form nitrides and oxides, and strengthen the alloy through solid solution and dispersion precipitation effects.
  • the diameter of the multi-element alloy wire of the present invention can be ⁇ 0.8 ⁇ 5.0mm.
  • C 0.05wt.%, S ⁇ 0.005wt.%, Cu ⁇ 0.15wt.%, Fe ⁇ 0.2wt.%.
  • the method for preparing the above-mentioned multi-element alloy wire for spark plugs of the present invention includes the following steps:
  • step (1) the casting temperature is 1450-1500°C, and the casting power is 90-100 kW.
  • step (2) the ingot is heated and kept for 2 to 3 hours, and the diameter of the prepared wire rod is 6 to 12 mm.
  • step (3) the drawing passes are 6-8 times, and the average deformation per pass is 7-10%.
  • the multi-element alloy wire not only has superior tensile strength and elongation, but also has good high temperature resistance, high temperature oxidation resistance, and room temperature extensibility;
  • the multi-element alloy wire When preparing the multi-element alloy wire, firstly, it is smelted in a vacuum intermediate frequency induction furnace to further reduce the impurity elements and non-metallic inclusions in the alloy; secondly, it is first heated to 1120 ⁇ 1220°C during rolling to promote the uniform structure of the alloy steel ingot
  • the alloy wire rod defects are significantly reduced; again, after drawing, annealing is carried out at a temperature of 680-780°C for 3-6 hours, which eliminates the cold working stress of the alloy wire, optimizes the alloy grain size, and further improves the comprehensiveness of the alloy wire performance.
  • Table 1 The composition and content of the multi-element alloy wire of Example 1 (wt.%)
  • the preparation method of the multi-element alloy filament includes the following steps:
  • the wire rod prepared above is drawn into a filament with a smooth surface by 6-8 times of drawing process, the average deformation of each pass is 7-10%, and annealed in a vacuum annealing furnace at 730°C for 5h, A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
  • the multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 2 below.
  • the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at 1000°C for 50 hours, and the weight gain of the oxide layer is measured.
  • Table 3 The composition and content of the multi-element alloy wire of Example 2 (wt.%)
  • the preparation method of the multi-element alloy filament includes the following steps:
  • the wire rod prepared above is drawn into a filament with a smooth surface by 6-8 times of drawing process, the average deformation of each pass is 7-10%, and it is annealed in a vacuum annealing furnace at 750°C for 4h, A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
  • the multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 4 below.
  • the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at a temperature of 1000° C. for 50 hours to measure the weight gain of the oxide layer.
  • Table 5 The composition and content of the multi-element alloy wire of Example 3 (wt.%)
  • the preparation method of the multi-element alloy filament includes the following steps:
  • the wire rod prepared above is drawn into a thin wire with a smooth surface by 6-8 times of drawing process, the average deformation of each pass is 7-10%, and annealed in a vacuum annealing furnace at 740°C for 5h, A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
  • the multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 6 below.
  • the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at 1000°C for 50 hours, and the weight gain of the oxide layer is measured.
  • the room temperature tensile strength of the multi-element alloy filament of the present invention reaches 530-600MPa, the elongation rate reaches 40-43%, the surface hardness reaches 130-138HV 10 , and it has been subjected to 1000°C, 50h
  • the weight gain of the oxide layer is 19.1905-21.0865g/m 2 . It can be seen that the use of the multi-element alloy filament as the electrode material has better tensile strength, elongation and high-temperature oxidation resistance than the existing electrode material, and can greatly improve the service life of the spark plug.
  • composition and content of the multi-element alloy wire of this embodiment are shown in Table 7 below.
  • Table 7 The composition and content of the multi-element alloy wire of Example 4 (wt.%)
  • the preparation method of the multi-element alloy filament includes the following steps:
  • the wire rod prepared above is drawn into a thin wire with a smooth surface by 6-8 times of drawing process, with an average deformation of 7-10% per pass, and annealed in a vacuum annealing furnace at 680°C for 6h.
  • a multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
  • the multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 8 below.
  • the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at 1000°C for 50 hours, and the weight gain of the oxide layer is measured.
  • composition and content of the multi-element alloy wire of this embodiment are shown in Table 9 below.
  • Table 9 The composition and content of the multi-element alloy wire of Example 5 (wt.%)
  • the preparation method of the multi-element alloy filament includes the following steps:
  • the wire rod prepared above is drawn into a thin wire with a smooth surface by 6-8 times of drawing process, with an average deformation of 7-10% per pass, and annealed in a vacuum annealing furnace at 780°C for 3h, A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
  • the multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 10 below.
  • the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at 1000°C for 50 hours, and the weight gain of the oxide layer is measured.
  • the room temperature tensile strength of the multi-element alloy filament of the present invention is about 550MPa
  • the elongation is about 40%
  • the surface hardness is about 130HV 10
  • the weight gain of the oxide layer is about 3.83 ⁇ 10 -5 g/m 2 . It can be seen that the use of the multi-element alloy filament as the electrode material has better tensile strength, elongation and high-temperature oxidation resistance than the existing electrode material, and can greatly improve the service life of the spark plug.

Abstract

Disclosed are a multi-element alloy wire for use in a spark plug and a manufacturing method therefor. The multi-element alloy wire consists of Al, Si, B, Y, Nb, balance Ni, and inevitable impurities. The method comprises: first, using a vacuum medium-frequency induction melting furnace to melt a raw material comprising the foregoing components so as to obtain a liquid alloy, and casting the liquid alloy in a metal mold to be an ingot; then heating and rolling the ingot to be wire rods under a reducing atmosphere; finally, drawing the wire rods multiple times to obtain filaments, and performing annealing on the filaments to obtain the multi-element alloy wire. The multi-element alloy wire of the present invention has excellent tensile strength and elongation, and also has good high-temperature resistance, high-temperature oxidation resistance, and room-temperature extensibility; moreover, during manufacturing, impurity elements and non-metallic inclusions in the alloy are reduced, the cold machining stress of the alloy wire is reduced, and the size of an alloy grain is optimized, thereby further improving the comprehensive performance of the alloy wire.

Description

一种用于火花塞的多元合金丝及其制备方法Multi-element alloy wire for spark plug and preparation method thereof 技术领域Technical field
本发明属于多元合金细丝领域，尤其涉及一种用于发动机火花塞的多元合金丝及其制备方法。The invention belongs to the field of multi-element alloy filaments, and in particular relates to a multi-element alloy wire for engine spark plugs and a preparation method thereof.
背景技术Background technique
火花塞是将进入发动机的汽油和空气混合气体加以点燃的装置，工作于高温、高压的恶劣条件下，还要承受高爆发压力和高电压的放电火花侵蚀。火花塞的侧电极发动机气缸的燃烧室中，必须具备良好的机械强度、导热性能，具备良好的抗氧化、耐电烧蚀和耐化学腐蚀能力。The spark plug is a device that ignites the gasoline and air mixture entering the engine. It works under severe conditions of high temperature and high pressure, and also bears high burst pressure and high voltage discharge spark erosion. The side electrode of the spark plug in the combustion chamber of the engine cylinder must have good mechanical strength, thermal conductivity, good oxidation resistance, electrical ablation resistance and chemical corrosion resistance.
传统上火花塞的电极材料是NiCrMnSi材料，其成分为：Cr 1.4～1.8wt.％、Mn 1.3～1.8wt.％、Si 0.4～0.65wt.％、C≤0.05wt.％及余量Ni和不可避免的杂质。但该NiCrMnSi合金火花塞电极材料的延伸率和拉伸强度不高(延伸率为28％、拉伸强度为488MPa)，从而影响了材料的加工性能、使用过程中的抗变形能力，以及抗高温氧化及热腐蚀性能较差，其产品使用寿命相对较短。Traditionally, the electrode material of spark plugs is NiCrMnSi, and its composition is: Cr 1.4～1.8wt.%, Mn 1.3～1.8wt.%, Si 0.4～0.65wt.%, C≤0.05wt.% and the balance Ni Impurities to avoid. However, the elongation and tensile strength of the NiCrMnSi alloy spark plug electrode material are not high (the elongation is 28%, the tensile strength is 488MPa), which affects the processing performance of the material, the resistance to deformation during use, and the resistance to high temperature oxidation And poor thermal corrosion performance, its product life is relatively short.
发明内容Summary of the invention
发明目的：本发明的第一目的是提供一种拉伸强度和延伸率高，且抗高温氧化性优的用于火花塞的多元合金丝；Object of the invention: The first object of the invention is to provide a multi-element alloy wire for spark plugs with high tensile strength and elongation, and excellent high temperature oxidation resistance;
本发明的第二目的是提供该多元合金丝的制备方法。The second object of the present invention is to provide a method for preparing the multi-element alloy wire.
技术方案：本发明用于发动机火花塞的多元合金丝，按质量分数由如下组分组成：Al 0.5～1.5％、Si 0.5～1.5％、B 0.01～0.2％、Y 0.1～0.5％、Nb 0.05～0.7％及余量Ni和不可避免的杂质。Technical solution: The multi-element alloy wire used in the engine spark plug of the present invention is composed of the following components according to mass fraction: Al 0.5~1.5%, Si 0.5~1.5%, B 0.01~0.2%, Y 0.1~0.5%, Nb 0.05~ 0.7% and the balance Ni and unavoidable impurities.
本发明通过将Al、Si、B、Y、Nb及Ni进行复配制备多元合金丝，进而使得该多元合金丝具有熔点高、密度低、导热和导电性能好、耐高温性能、抗高温氧化性及耐高温腐蚀性能等特性，且延伸率和拉伸强度高。其中，Al的加入能够和基体Ni形成镍铝金属间化合物，是镍基合金丝材的主要强化元素和高温相的稳定剂；添加Y能够显著改善合金的抗氧化性能，组织合金中Al 2O 3保护膜的连续生成，且Y与O有较大的亲和力，能与O形成难溶的金属陶瓷相，氧化钇对合金有沉淀强化作用；添加B能够防止或减轻室温环境脆化效应即氢致脆化、 并提高晶界结合强度，提高合金的室温延性并改善热加工性，同时B与合金中的N气能形成氮化硼通过弥散析出对合金有强化作用；添加Si能够使合金具有良好的流动性，能减少疏松、缩孔，提高合金致密性和铸锭质量，同时Si与合金液中的氧结合生成氧化硅，具有固溶强化作用并能进一步抑制合金的氧化；此外，添加Nb能够细化合金晶粒、提高合金的耐热性，且Nb与合金中残留的N、O气体能形成氮化物和氧化物，通过固溶和弥散析出效应对合金进行强化。 The invention prepares a multi-element alloy wire by compounding Al, Si, B, Y, Nb and Ni, so that the multi-element alloy wire has high melting point, low density, good thermal and electrical conductivity, high temperature resistance, and high temperature oxidation resistance. And high temperature corrosion resistance, and high elongation and tensile strength. Among them, the addition of Al can form a nickel-aluminum intermetallic compound with the matrix Ni, which is the main strengthening element of the nickel-based alloy wire and the stabilizer of the high temperature phase; the addition of Y can significantly improve the oxidation resistance of the alloy, and the Al 2 O in the structure alloy 3 The continuous formation of protective film, and Y has a greater affinity with O, can form insoluble cermet phase with O, yttrium oxide has a precipitation strengthening effect on the alloy; adding B can prevent or reduce the embrittlement effect of room temperature environment, namely hydrogen Embrittlement, and increase the bonding strength of the grain boundary, increase the ductility of the alloy at room temperature and improve the hot workability. At the same time, B and the N gas in the alloy can form boron nitride and strengthen the alloy through dispersion and precipitation; the addition of Si can make the alloy have Good fluidity, can reduce porosity and shrinkage, improve alloy compactness and ingot quality. At the same time, Si combines with oxygen in the alloy liquid to form silicon oxide, which has a solid solution strengthening effect and can further inhibit the oxidation of the alloy; in addition, add Nb can refine the alloy grains and improve the heat resistance of the alloy, and Nb and the remaining N and O gases in the alloy can form nitrides and oxides, and strengthen the alloy through solid solution and dispersion precipitation effects.
进一步说，本发明的多元合金丝的直径可为Φ0.8～5.0mm。而杂质中C≤0.05wt.％、S≤0.005wt.％、Cu≤0.15wt.％、Fe≤0.2wt.％。Furthermore, the diameter of the multi-element alloy wire of the present invention can be Φ0.8～5.0mm. In the impurities, C≤0.05wt.%, S≤0.005wt.%, Cu≤0.15wt.%, Fe≤0.2wt.%.
本发明制备上述用于火花塞的多元合金丝的方法，包括如下步骤：The method for preparing the above-mentioned multi-element alloy wire for spark plugs of the present invention includes the following steps:
(1)熔炼、浇铸：采用真空中频感应熔炼炉将含上述组分的原料在120～160KW条件下熔炼制得液态合金，并在金属模中浇铸成铸锭，对该铸锭进行合金组分分析和验证；(1) Melting and casting: Use a vacuum intermediate frequency induction melting furnace to melt the raw materials containing the above components at 120-160KW to obtain a liquid alloy, and cast it into an ingot in a metal mold, and perform alloying on the ingot Analysis and verification;
(2)轧制：在还原性气氛下将上述铸锭加热至1120～1220℃后，进行轧制及盘条；(2) Rolling: After heating the above-mentioned ingot to 1120-1220°C in a reducing atmosphere, rolling and wire rod are carried out;
(3)拉拔：将上述的盘条经多次拉拔后制得细丝，随后将该细丝在680～780℃温度条件下退火3～6h，制得多元合金细丝。(3) Drawing: the wire rod is drawn several times to obtain a filament, and then the filament is annealed at a temperature of 680-780°C for 3-6 hours to obtain a multi-element alloy filament.
进一步说，步骤(1)中，浇铸的温度为1450～1500℃，浇铸的功率为90～100KW。Furthermore, in step (1), the casting temperature is 1450-1500°C, and the casting power is 90-100 kW.
步骤(2)中，铸锭加热保温2～3h，制备的盘条的直径为6～12mm。In step (2), the ingot is heated and kept for 2 to 3 hours, and the diameter of the prepared wire rod is 6 to 12 mm.
步骤(3)中，拉拔道次为6～8次，每道次平均变形量为7～10％。In step (3), the drawing passes are 6-8 times, and the average deformation per pass is 7-10%.
有益效果：与现有技术相比，本发明的显著优点为：该多元合金丝不仅具有优越的拉伸强度和延伸率，且具有良好的抗耐高温性能、抗高温氧化性能、室温延伸性；而制备该多元合金丝时，首先，采用真空中频感应炉熔炼，进一步降低合金中的杂质元素和非金属夹杂物；其次，在轧制时先加热至1120～1220℃，促进了合金钢锭组织均匀化，明显减少了合金盘条缺陷；再次，拉拔后在680～780℃温度条件下退火3～6h，消除了合金丝材冷加工应力，优化了合金晶粒尺寸，进一步提高了合金丝的综合性能。Beneficial effects: Compared with the prior art, the significant advantages of the present invention are: the multi-element alloy wire not only has superior tensile strength and elongation, but also has good high temperature resistance, high temperature oxidation resistance, and room temperature extensibility; When preparing the multi-element alloy wire, firstly, it is smelted in a vacuum intermediate frequency induction furnace to further reduce the impurity elements and non-metallic inclusions in the alloy; secondly, it is first heated to 1120～1220°C during rolling to promote the uniform structure of the alloy steel ingot The alloy wire rod defects are significantly reduced; again, after drawing, annealing is carried out at a temperature of 680-780℃ for 3-6 hours, which eliminates the cold working stress of the alloy wire, optimizes the alloy grain size, and further improves the comprehensiveness of the alloy wire performance.
具体实施方式Detailed ways
下面结合实施例对本发明的技术方案作进一步详细说明。The technical solution of the present invention will be further described in detail below in conjunction with the embodiments.
实施例1Example 1
该实施例的多元合金丝的组分及含量如下表1所示。The components and contents of the multi-element alloy wire of this embodiment are shown in Table 1 below.
表1 实施例1的多元合金丝组分及含量(wt.％)Table 1 The composition and content of the multi-element alloy wire of Example 1 (wt.%)
Figure PCTCN2019108219-appb-000001
Figure PCTCN2019108219-appb-000001
该多元合金细丝的制备方法包括如下步骤：The preparation method of the multi-element alloy filament includes the following steps:
(1)以纯镍板、电解铝、金属硅、金属铌、硼和稀土钇为原料，采用150kg真空中频感应炉熔炼，在熔炼功率为140KW条件下熔炼制得液态合金；(1) Using pure nickel plates, electrolytic aluminum, metallic silicon, metallic niobium, boron and rare earth yttrium as raw materials, smelting in a 150kg vacuum intermediate frequency induction furnace, smelting at a smelting power of 140KW to obtain a liquid alloy;
(2)将上述制备的液态合金在温度1470℃、功率90KW条件下浇注到钢锭模中得到铸锭，并对其进行车光、取样，进行成分分析，验证是否合格；(2) Pour the liquid alloy prepared above into a steel ingot mold at a temperature of 1470°C and a power of 90 kW to obtain an ingot, and conduct polishing, sampling, and composition analysis to verify whether it is qualified;
(3)将上述验证合格的铸锭在还原性气氛加热炉中加热到1160℃、保温2h，在热轧机上进行轧制及制得直径为Φ6～12mm的盘条；(3) Heat the above-mentioned qualified ingots in a reducing atmosphere heating furnace to 1160°C for 2 hours, then roll them on a hot rolling mill to produce wire rods with a diameter of Φ6-12mm;
(4)将上述制备的盘条采用6～8次拉拔工艺拉成表面光滑的细丝，每道次平均变形量为7～10％，并在真空退火炉、730℃条件下退火5h，制得直径为Φ0.8～5.0mm的多元合金细丝。(4) The wire rod prepared above is drawn into a filament with a smooth surface by 6-8 times of drawing process, the average deformation of each pass is 7-10%, and annealed in a vacuum annealing furnace at 730℃ for 5h, A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
性能检测Performance test
将上述制备的多元合金细丝分别进行机械性能、高温氧化性能测试，获得的结果如下表2所示。其中，高温氧化性能测试是将制备的多元合金细丝进行1000℃环境下、50h的高温氧化试验，测得氧化层增重。The multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 2 below. Among them, the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at 1000°C for 50 hours, and the weight gain of the oxide layer is measured.
表2 实施例1制备的多元合金细丝的性能Table 2 Properties of the multi-element alloy filament prepared in Example 1
性能performance 拉伸强度(MPa)Tensile strength (MPa) 延伸率(％)Elongation (%) 表面硬度(HV 10) Surface hardness (HV 10 ) 1000℃、50h氧化增重(g/m 2) Oxidation weight gain at 1000℃, 50h (g/m 2 )
参数parameter 590590 4040 132132 21.086521.0865
实施例2Example 2
该实施例的多元合金丝的组分及含量如下表3所示。The components and contents of the multi-element alloy wire of this embodiment are shown in Table 3 below.
表3 实施例2的多元合金丝组分及含量(wt.％)Table 3 The composition and content of the multi-element alloy wire of Example 2 (wt.%)
Figure PCTCN2019108219-appb-000002
Figure PCTCN2019108219-appb-000002
Figure PCTCN2019108219-appb-000003
Figure PCTCN2019108219-appb-000003
该多元合金细丝的制备方法包括如下步骤：The preparation method of the multi-element alloy filament includes the following steps:
(1)以纯镍板、电解铝、金属硅、金属铌、硼和稀土钇为原料，采用150kg真空中频感应炉熔炼，在熔炼功率为150KW条件下熔炼制得液态合金；(1) Using pure nickel plate, electrolytic aluminum, metallic silicon, metallic niobium, boron and rare earth yttrium as raw materials, smelting in a 150kg vacuum intermediate frequency induction furnace, smelting at a smelting power of 150KW to obtain a liquid alloy;
(2)将上述制备的液态合金在温度1500℃、功率100KW条件下浇注到钢锭模中得到铸锭，并对其进行车光、取样，进行成分分析，验证是否合格；(2) Pouring the above-prepared liquid alloy into a steel ingot mold at a temperature of 1500°C and a power of 100KW to obtain an ingot, and conduct polishing, sampling, and composition analysis to verify whether it is qualified;
(3)将上述验证合格的铸锭在还原性气氛加热炉中加热到1200℃、保温2h，在热轧机上进行轧制及制得直径为Φ6～12mm的盘条；(3) Heat the above-mentioned qualified ingots in a reducing atmosphere heating furnace to 1200°C for 2 hours, and then roll them on a hot rolling mill to produce wire rods with a diameter of Φ6-12mm;
(4)将上述制备的盘条采用6～8次拉拔工艺拉成表面光滑的细丝，每道次平均变形量为7～10％，并在真空退火炉、750℃条件下退火4h，制得直径为Φ0.8～5.0mm的多元合金细丝。(4) The wire rod prepared above is drawn into a filament with a smooth surface by 6-8 times of drawing process, the average deformation of each pass is 7-10%, and it is annealed in a vacuum annealing furnace at 750℃ for 4h, A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
性能检测Performance test
将上述制备的多元合金细丝分别进行机械性能、高温氧化性能测试，获得的结果如下表4所示。其中，高温氧化性能测试是将制备的多元合金细丝进行1000℃环境下、50h的高温氧化试验，测得氧化层增重。The multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 4 below. Among them, the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at a temperature of 1000° C. for 50 hours to measure the weight gain of the oxide layer.
表4 实施例2制备的多元合金细丝的性能Table 4 Properties of the multi-element alloy filament prepared in Example 2
性能performance 拉伸强度(MPa)Tensile strength (MPa) 延伸率(％)Elongation (%) 表面硬度(HV 10) Surface hardness (HV 10 ) 1000℃、50h氧化增重(g/m 2) Oxidation weight gain at 1000℃, 50h (g/m 2 )
参数parameter 580580 4242 138138 3.93×10 -5 3.93×10 -5
实施例3Example 3
该实施例的多元合金丝的组分及含量如下表5所示。The components and contents of the multi-element alloy wire of this embodiment are shown in Table 5 below.
表5 实施例3的多元合金丝组分及含量(wt.％)Table 5 The composition and content of the multi-element alloy wire of Example 3 (wt.%)
Figure PCTCN2019108219-appb-000004
Figure PCTCN2019108219-appb-000004
该多元合金细丝的制备方法包括如下步骤：The preparation method of the multi-element alloy filament includes the following steps:
(1)以纯镍板、电解铝、金属硅、金属铌、硼和稀土钇为原料，采用150kg真空中频感应炉熔炼，在熔炼功率为145KW条件下熔炼制得液态合金；(1) Using pure nickel plate, electrolytic aluminum, metallic silicon, metallic niobium, boron and rare earth yttrium as raw materials, smelting in a 150kg vacuum intermediate frequency induction furnace, smelting at a melting power of 145KW to obtain a liquid alloy;
(2)上述制备的液态合金在温度1500℃、功率95KW条件下浇注到钢锭模中得到铸锭，并对其进行车光、取样，进行成分分析，验证是否合格；(2) The liquid alloy prepared above is poured into a steel ingot mold at a temperature of 1500°C and a power of 95 kW to obtain an ingot, which is polished, sampled, and analyzed to verify whether it is qualified;
(3)将上述验证合格的铸锭在还原性气氛加热炉中加热到1180℃、保温2h，在热轧机上进行轧制及制得直径为Φ6～12mm的盘条；(3) Heat the above-mentioned qualified ingots in a reducing atmosphere heating furnace to 1180°C for 2 hours, and roll them on a hot rolling mill to produce wire rods with a diameter of Φ6-12mm;
(4)将上述制备的盘条采用6～8次拉拔工艺拉成表面光滑的细丝，每道次平均变形量为7～10％，并在真空退火炉、740℃条件下退火5h，制得直径为Φ0.8～5.0mm的多元合金细丝。(4) The wire rod prepared above is drawn into a thin wire with a smooth surface by 6-8 times of drawing process, the average deformation of each pass is 7-10%, and annealed in a vacuum annealing furnace at 740℃ for 5h, A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
性能检测Performance test
将上述制备的多元合金细丝分别进行机械性能、高温氧化性能测试，获得的结果如下表6所示。其中，高温氧化性能测试是将制备的多元合金细丝进行1000℃环境下、50h的高温氧化试验，测得氧化层增重。The multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 6 below. Among them, the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at 1000°C for 50 hours, and the weight gain of the oxide layer is measured.
表6 实施例3制备的多元合金细丝的性能Table 6 Properties of the multi-element alloy filament prepared in Example 3
性能performance 拉伸强度(MPa)Tensile strength (MPa) 延伸率(％)Elongation (%) 表面硬度(HV 10) Surface hardness (HV 10 ) 1000℃、50h氧化增重(g/m 2) Oxidation weight gain at 1000℃, 50h (g/m 2 )
参数parameter 530530 4343 130130 4.12×10 -5 4.12×10 -5
通过上述实施例1-3可知，本发明的多元合金细丝丝的室温拉伸强度达530～600MPa，延伸率达40～43％，表面硬度达130～138HV 10，且经过1000℃、50h的高温氧化试验，氧化层增重为19.1905～21.0865g/m 2。由此可知，采用该多元合金细丝作电极材料，相对于现有的电极材料，具有更好抗拉强度、延伸率和高温抗氧化性能，能够极大地提高火花塞使用寿命。 From the above examples 1-3, it can be seen that the room temperature tensile strength of the multi-element alloy filament of the present invention reaches 530-600MPa, the elongation rate reaches 40-43%, the surface hardness reaches 130-138HV 10 , and it has been subjected to 1000℃, 50h In the high temperature oxidation test, the weight gain of the oxide layer is 19.1905-21.0865g/m 2 . It can be seen that the use of the multi-element alloy filament as the electrode material has better tensile strength, elongation and high-temperature oxidation resistance than the existing electrode material, and can greatly improve the service life of the spark plug.
实施例4Example 4
该实施例的多元合金丝的组分及含量如下表7所示。The composition and content of the multi-element alloy wire of this embodiment are shown in Table 7 below.
表7 实施例4的多元合金丝组分及含量(wt.％)Table 7 The composition and content of the multi-element alloy wire of Example 4 (wt.%)
Figure PCTCN2019108219-appb-000005
Figure PCTCN2019108219-appb-000005
该多元合金细丝的制备方法包括如下步骤：The preparation method of the multi-element alloy filament includes the following steps:
(1)以纯镍板、电解铝、金属硅、金属铌、硼和稀土钇为原料，采用150kg 真空中频感应炉熔炼，在熔炼功率为120KW条件下熔炼制得液态合金；(1) Using pure nickel plate, electrolytic aluminum, metallic silicon, metallic niobium, boron and rare earth yttrium as raw materials, smelting in a 150kg vacuum intermediate frequency induction furnace, smelting at a smelting power of 120KW to obtain a liquid alloy;
(2)上述制备的液态合金在温度1450℃、功率95KW条件下浇注到钢锭模中得到铸锭，并对其进行车光、取样，进行成分分析，验证是否合格；(2) The liquid alloy prepared above is poured into a steel ingot mold at a temperature of 1450°C and a power of 95 kW to obtain an ingot, which is then polished, sampled, and analyzed to verify whether it is qualified;
(3)将上述验证合格的铸锭在还原性气氛加热炉中加热到1120℃、保温3h，在热轧机上进行轧制及制得直径为Φ6～12mm的盘条；(3) Heat the above-mentioned qualified ingots in a reducing atmosphere heating furnace to 1120°C and hold for 3 hours, then roll them on a hot rolling mill and produce wire rods with a diameter of Φ6-12mm;
(4)将上述制备的盘条采用6～8次拉拔工艺拉成表面光滑的细丝，每道次平均变形量为7～10％，并在真空退火炉、680℃条件下退火6h，制得直径为Φ0.8～5.0mm的多元合金细丝。(4) The wire rod prepared above is drawn into a thin wire with a smooth surface by 6-8 times of drawing process, with an average deformation of 7-10% per pass, and annealed in a vacuum annealing furnace at 680℃ for 6h. A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
性能检测Performance test
将上述制备的多元合金细丝分别进行机械性能、高温氧化性能测试，获得的结果如下表8所示。其中，高温氧化性能测试是将制备的多元合金细丝进行1000℃环境下、50h的高温氧化试验，测得氧化层增重。The multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 8 below. Among them, the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at 1000°C for 50 hours, and the weight gain of the oxide layer is measured.
表8 实施例4制备的多元合金细丝的性能Table 8 Properties of the multi-element alloy filament prepared in Example 4
性能performance 拉伸强度(MPa)Tensile strength (MPa) 延伸率(％)Elongation (%) 表面硬度(HV 10) Surface hardness (HV 10 ) 1000℃、50h氧化增重(g/mm 2) Oxidation weight gain at 1000℃, 50h (g/mm 2 )
参数parameter 550550 3939 135135 3.98×10 -5 3.98×10 -5
实施例5Example 5
该实施例的多元合金丝的组分及含量如下表9所示。The composition and content of the multi-element alloy wire of this embodiment are shown in Table 9 below.
表9 实施例5的多元合金丝组分及含量(wt.％)Table 9 The composition and content of the multi-element alloy wire of Example 5 (wt.%)
Figure PCTCN2019108219-appb-000006
Figure PCTCN2019108219-appb-000006
该多元合金细丝的制备方法包括如下步骤：The preparation method of the multi-element alloy filament includes the following steps:
(1)以纯镍板、电解铝、金属硅、金属铌、硼和稀土钇为原料，采用150kg真空中频感应炉熔炼，在熔炼功率为160KW条件下熔炼制得液态合金；(1) Using pure nickel plate, electrolytic aluminum, metallic silicon, metallic niobium, boron and rare earth yttrium as raw materials, smelting in a 150kg vacuum intermediate frequency induction furnace, smelting at a smelting power of 160KW to obtain a liquid alloy;
(2)上述制备的液态合金在温度1480℃、功率90KW条件下浇注到钢锭模中得到铸锭，并对其进行车光、取样，进行成分分析，验证是否合格；(2) The liquid alloy prepared above is poured into a steel ingot mold at a temperature of 1480°C and a power of 90 kW to obtain an ingot, which is then polished, sampled, and analyzed to verify whether it is qualified;
(3)将上述验证合格的铸锭在还原性气氛加热炉中加热到1220℃、保温2h， 在热轧机上进行轧制及制得直径为Φ6～12mm的盘条；(3) Heat the above-mentioned qualified ingots in a reducing atmosphere heating furnace to 1220°C for 2 hours, and roll them on a hot rolling mill to produce wire rods with a diameter of Φ6-12mm;
(4)将上述制备的盘条采用6～8次拉拔工艺拉成表面光滑的细丝，每道次平均变形量为7～10％，并在真空退火炉、780℃条件下退火3h，制得直径为Φ0.8～5.0mm的多元合金细丝。(4) The wire rod prepared above is drawn into a thin wire with a smooth surface by 6-8 times of drawing process, with an average deformation of 7-10% per pass, and annealed in a vacuum annealing furnace at 780℃ for 3h, A multi-element alloy filament with a diameter of 0.8 to 5.0 mm is prepared.
性能检测Performance test
将上述制备的多元合金细丝分别进行机械性能、高温氧化性能测试，获得的结果如下表10所示。其中，高温氧化性能测试是将制备的多元合金细丝进行1000℃环境下、50h的高温氧化试验，测得氧化层增重。The multi-element alloy filaments prepared above were tested for mechanical properties and high-temperature oxidation properties, and the results obtained are shown in Table 10 below. Among them, the high-temperature oxidation performance test is to subject the prepared multi-element alloy filaments to a high-temperature oxidation test at 1000°C for 50 hours, and the weight gain of the oxide layer is measured.
表10 实施例5制备的多元合金细丝的性能Table 10 Properties of the multi-element alloy filament prepared in Example 5
性能performance 拉伸强度(MPa)Tensile strength (MPa) 延伸率(％)Elongation (%) 表面硬度(HV 10) Surface hardness (HV 10 ) 1000℃、50h氧化增重(g/m 2) Oxidation weight gain at 1000℃, 50h (g/m 2 )
参数parameter 545545 4141 132132 3.83×10 -5 3.83×10 -5
通过上述实施例4和5可知，本发明的多元合金细丝丝的室温拉伸强度达550MPa左右，延伸率达40％左右，表面硬度达130HV 10左右，且经过1000℃、50h的高温氧化试验，氧化层增重为3.83×10 -5g/m 2左右。由此可知，采用该多元合金细丝作电极材料，相对于现有的电极材料，具有更好抗拉强度、延伸率和高温抗氧化性能，能够极大地提高火花塞使用寿命。 From the above examples 4 and 5, it can be seen that the room temperature tensile strength of the multi-element alloy filament of the present invention is about 550MPa, the elongation is about 40%, the surface hardness is about 130HV 10 , and it has passed the high temperature oxidation test at 1000°C for 50h. , The weight gain of the oxide layer is about 3.83×10 -5 g/m 2 . It can be seen that the use of the multi-element alloy filament as the electrode material has better tensile strength, elongation and high-temperature oxidation resistance than the existing electrode material, and can greatly improve the service life of the spark plug.

Claims (8)

  1. 一种用于火花塞的多元合金丝，其特征在于按质量分数由如下组分组成：Al 0.5～1.5％、Si 0.5～1.5％、B 0.01～0.2％、Y 0.1～0.5％、Nb 0.05～0.7％及余量Ni和不可避免的杂质。A multi-element alloy wire for spark plugs, characterized in that it is composed of the following components according to mass fraction: Al 0.5~1.5%, Si 0.5~1.5%, B 0.01~0.2%, Y 0.1~0.5%, Nb 0.05~0.7 % And the balance Ni and unavoidable impurities.
  2. 根据权利要求1所述用于火花塞的多元合金丝，其特征在于：所述杂质中C≤0.05wt.％、S≤0.005wt.％、Cu≤0.15wt.％、Fe≤0.2wt.％。The multi-element alloy wire for spark plugs according to claim 1, characterized in that C≤0.05wt.%, S≤0.005wt.%, Cu≤0.15wt.%, Fe≤0.2wt.% in the impurities.
  3. 根据权利要求1所述用于火花塞的多元合金丝，其特征在于：所述多元合金丝的直径为Φ0.8～5.0mm。The multi-element alloy wire for spark plugs according to claim 1, wherein the diameter of the multi-element alloy wire is 0.8-5.0 mm.
  4. 一种制备权利要求1所述用于火花塞的多元合金丝的方法，其特征在于包括如下步骤：A method for preparing a multi-element alloy wire for spark plugs according to claim 1, characterized in that it comprises the following steps:
    (1)熔炼、浇铸：采用真空中频感应熔炼炉将含上述组分的原料在120～160KW条件下熔炼制得液态合金，并在金属模中浇铸成铸锭，对该铸锭进行合金组分分析和验证；(1) Melting and casting: use a vacuum intermediate frequency induction melting furnace to melt the raw materials containing the above components under the condition of 120-160KW to obtain a liquid alloy, and cast it into an ingot in a metal mold, and perform the alloy composition on the ingot Analysis and verification;
    (2)轧制：在还原性气氛下将上述铸锭加热至1120～1220℃后，进行轧制及盘条；(2) Rolling: After heating the above-mentioned ingot to 1120-1220°C in a reducing atmosphere, rolling and wire rod are carried out;
    (3)拉拔：将上述的盘条经多次拉拔后制得细丝，随后将该细丝在680～780℃温度条件下退火3～6h，制得多元合金细丝。(3) Drawing: the wire rod is drawn several times to obtain a filament, and then the filament is annealed at a temperature of 680-780°C for 3-6 hours to obtain a multi-element alloy filament.
  5. 根据权利要求4所述制备用于火花塞的多元合金丝的方法，其特征在于：步骤(1)中，所述浇铸的温度为1450～1500℃，浇铸的功率为90～100KW。The method for preparing a multi-element alloy wire for spark plugs according to claim 4, characterized in that: in step (1), the casting temperature is 1450-1500°C, and the casting power is 90-100 kW.
  6. 根据权利要求4所述制备用于火花塞的多元合金丝的方法，其特征在于：步骤(2)中，所述铸锭加热后保温2～3h。The method for preparing a multi-element alloy wire for spark plugs according to claim 4, characterized in that: in step (2), the ingot is heated and kept for 2 to 3 hours.
  7. 根据权利要求4所述制备用于火花塞的多元合金丝的方法，其特征在于：步骤(2)中，盘条的直径为6～12mm。The method for preparing a multi-element alloy wire for spark plugs according to claim 4, characterized in that: in step (2), the diameter of the wire rod is 6-12 mm.
  8. 根据权利要求4所述制备用于火花塞的多元合金丝的方法，其特征在于：步骤(3)中，所述拉拔道次为6～8次，每道次平均变形量为7～10％。The method for preparing a multi-element alloy wire for spark plugs according to claim 4, characterized in that: in step (3), the drawing passes are 6-8 times, and the average deformation per pass is 7-10% .
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