CN103394822B - Nickel-base alloy submerged arc welding sintered flux - Google Patents
Nickel-base alloy submerged arc welding sintered flux Download PDFInfo
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- 230000004907 flux Effects 0.000 title claims abstract description 36
- 238000003466 welding Methods 0.000 title claims abstract description 30
- 239000000956 alloy Substances 0.000 title claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 14
- 229910004261 CaF 2 Inorganic materials 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
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- 239000002184 metal Substances 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 20
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- 230000008018 melting Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
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- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
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- 239000011148 porous material Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- Nonmetallic Welding Materials (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种镍基合金埋弧焊接用烧结焊剂，属于焊接材料技术领域。所述焊剂适用于石油化工，冶金，原子能，海洋开发，航空，航天等行业镍基合金结构件的埋弧焊接。 The invention relates to a sintered flux for nickel-based alloy submerged arc welding, which belongs to the technical field of welding materials. The flux is suitable for submerged arc welding of nickel-based alloy structural parts in petrochemical, metallurgy, atomic energy, ocean development, aviation, aerospace and other industries.
背景技术 Background technique
镍基合金（Ni≥55%）是重要的结构材料，对有害成分特别敏感并能溶解气体，焊接比较困难：一方面，液态镍能够大量溶解O2、H2、和CO气体，而在冷凝期溶解度急剧下降，造成气孔和氢脆，并且由于焊接时镍的氧化会形成Ni-NiO低熔点共晶体，这些低熔点共晶体于结晶时分布在晶界上，易发生脆性；另一方面，Ni与S和P有很强的化学亲和力，很易在粗大的晶界上形成低熔点共晶化合物，降低焊缝强度并导致结晶裂纹。 Nickel-based alloys (Ni≥55%) are important structural materials, which are particularly sensitive to harmful components and can dissolve gases, so welding is difficult: on the one hand, liquid nickel can dissolve a large amount of O 2 , H 2 , and CO gases, while condensing The solubility drops sharply in the early stage, causing pores and hydrogen embrittlement, and due to the oxidation of nickel during welding, Ni-NiO low-melting eutectics will be formed. These low-melting eutectics are distributed on the grain boundaries during crystallization and are prone to brittleness; on the other hand, Ni has a strong chemical affinity with S and P, and it is easy to form a low-melting eutectic compound on the coarse grain boundary, which reduces the strength of the weld and causes crystallization cracks.
一般广泛采用埋弧自动焊接镍基合金中，埋弧自动焊热源集中，通过金属与熔渣的冶金反应可以使熔池金属达到精炼、脱氧和变性处理，使焊缝金属化学成分均一。由于焊剂层的静压力作用使焊缝成形改善，形成的渣壳能保护熔池免于受到空气中的氧和其他气体的侵害。采用一般常用的“150”、“431”、“430”、“433”等熔炼焊剂进行埋弧焊接镍基合金完全不适用。尽管焊缝成形良好，脱渣容易，但所得焊缝易出现气孔，裂纹等缺陷。并且采用这些焊剂所得的焊缝金属具有粗大的铸态组织，晶粒方向性很强，在晶界有较厚的低熔点共晶薄膜，导致焊缝强度、塑性下降。 Generally, submerged arc automatic welding is widely used in nickel-based alloys. The heat source of submerged arc automatic welding is concentrated. Through the metallurgical reaction between metal and slag, the molten pool metal can be refined, deoxidized and denatured, so that the chemical composition of the weld metal is uniform. Due to the static pressure of the flux layer, the weld shape is improved, and the formed slag shell can protect the molten pool from oxygen and other gases in the air. It is not suitable for submerged arc welding of nickel-based alloys with commonly used melting fluxes such as "150", "431", "430", and "433". Although the weld is well formed and slag is easy to remove, the resulting weld is prone to defects such as pores and cracks. Moreover, the weld metal obtained by using these fluxes has a coarse as-cast structure, strong grain orientation, and a thick eutectic film with a low melting point at the grain boundary, resulting in a decrease in weld strength and plasticity.
烧结焊剂与熔炼焊剂相比，具有制造容易，能量消耗低，对环境污染小，焊缝化学成分易于调整等特点。与此同时，应用烧结焊剂埋弧焊方法所得到的焊缝金属合金化的效果好，其综合性能能够得到有效的保证。为此，研究开发出一种适用于镍基合金埋弧焊接用烧结焊剂，以保证焊缝金属得到精炼，具有除S、P作用，防止裂纹等缺陷的发生，便成为业内的期待。 Compared with smelting flux, sintered flux has the characteristics of easy manufacture, low energy consumption, less environmental pollution, and easy adjustment of weld chemical composition. At the same time, the alloying effect of the weld metal obtained by the sintered flux submerged arc welding method is good, and its comprehensive performance can be effectively guaranteed. Therefore, research and development of a sintered flux suitable for submerged arc welding of nickel-based alloys has become the expectation of the industry to ensure that the weld metal is refined, has the effect of removing S and P, and prevents cracks and other defects.
发明内容 Contents of the invention
本发明解决的技术问题是，研制一种具有焊接过程稳定、脱氧性强、抗焊接裂纹性能强以及焊缝成形良好等优点的镍基合金埋弧焊接渣系为CaF2- CaO- Al2O3的烧结焊剂，以满足制造业日益发展的需要。 The technical problem solved by the present invention is to develop a nickel-based alloy submerged arc welding slag system with the advantages of stable welding process, strong deoxidation, strong resistance to welding cracks and good weld formation, which is CaF 2 - CaO- Al 2 O 3 sintered fluxes to meet the growing needs of the manufacturing industry.
本发明实现其目的的策略是：根据镍基合金焊丝的焊接特点，在保证焊接工艺性良好的条件下，尽量提高焊剂的碱度，使其具备强的脱氧能力，并有效脱除S、P，充分保证焊缝金属的机械性能。 The strategy of the present invention to achieve its purpose is: according to the welding characteristics of nickel-based alloy welding wire, under the condition of ensuring good welding processability, try to increase the alkalinity of the flux so that it has a strong deoxidation ability and effectively removes S, P , fully guarantee the mechanical properties of the weld metal.
本发明的技术方案是，以CaF2、MgO、Al2O3、CaCO3为焊剂的主要组分，通过调整熔渣的碱度、粘度、表面张力等来改善焊剂的工艺性能和焊缝金属的抗裂能力。同时增加少量的Ti和Mn，以充分排除焊缝中的氧，脱去S、P杂质元素，增加焊缝金属的机械性能。 The technical solution of the present invention is to use CaF 2 , MgO, Al 2 O 3 , and CaCO 3 as the main components of the flux, and improve the technological performance of the flux and the weld metal by adjusting the basicity, viscosity, and surface tension of the slag. crack resistance. At the same time, a small amount of Ti and Mn is added to fully eliminate oxygen in the weld, remove S and P impurity elements, and increase the mechanical properties of the weld metal.
本发明所述烧结焊剂的组分及各组分的重量百分含量是， The components of the sintered flux of the present invention and the weight percentage of each component are,
CaF2 ：25～35%，MgO：10～20%，Al2O3 ：30～40%，CaCO3 ：5～10%，Ti ： 3～8%，Mn：3～8%。 CaF 2 : 25-35%, MgO: 10-20%, Al 2 O 3 : 30-40%, CaCO 3 : 5-10%, Ti: 3-8%, Mn: 3-8%.
对本发明各种组分的限定理由如下： The reasons for limiting the various components of the present invention are as follows:
CaF2：主要用于作造渣剂、脱硫和去氢成分。CaF2溶点较低，在高温作用下比较活泼，能与SiO2反应生成SiF4气体，这些气体能排除电弧区的氢气，防止氢溶解于金属中，减少产生气孔的机会。由于熔点低，对熔渣起稀释作用，会降低熔渣熔点。当焊剂中CaF2过高时，电离所得的F-离子极易夺取电弧中的电子，使焊接电弧的稳定性降低，从而导致堆焊层金属成形变差。为此本发明将CaF2的含量限定在30～40%之间。 CaF 2 : mainly used as slagging agent, desulfurization and dehydrogenation components. CaF 2 has a low melting point and is relatively active under high temperature. It can react with SiO 2 to generate SiF 4 gas. These gases can eliminate hydrogen in the arc area, prevent hydrogen from dissolving in the metal, and reduce the chance of pores. Due to the low melting point, it will dilute the slag and reduce the melting point of the slag. When the CaF 2 in the flux is too high , the F- ions obtained by ionization can easily capture the electrons in the arc, which will reduce the stability of the welding arc, resulting in poor metal forming of the surfacing layer. For this reason the present invention limits the content of CaF2 between 30～40%.
MgO：作为造渣剂。它能提高熔渣的碱度和改善熔渣覆盖和堆焊层金属成形。MgO的熔点很高，提高了溶渣的粘度，抑制了熔渣的流动性。MgO具有增大熔渣表面张力的作用。为了保证烧结焊剂有较高的熔点和碱度，为此本发明将MgO的含量限定在10～20%之间。 MgO: as a slagging agent. It increases the basicity of the slag and improves slag coverage and overlay metal formation. MgO has a high melting point, which increases the viscosity of the slag and inhibits the fluidity of the slag. MgO has the effect of increasing the surface tension of slag. In order to ensure that the sintered flux has a higher melting point and basicity, the present invention limits the content of MgO to 10-20%.
Al2O3 ：作为造渣剂。它具有良好的化学稳定性，溶点较高，当其和CaF2、CaO共存时，能提高焊剂的脱硫能力，在焊剂中随着Al2O3含量的提高，脱渣愈容易，Al2O3 的加入可以代替部分SiO2，降低焊剂的氧化性，过多的Al2O3将会增加熔渣的溶点和粘度。为此本发明将Al2O3 的含量限定在 30～50%。 Al 2 O 3 : as a slagging agent. It has good chemical stability and high melting point. When it coexists with CaF 2 and CaO, it can improve the desulfurization ability of the flux. With the increase of Al 2 O 3 content in the flux, the slag removal is easier, and Al 2 The addition of O 3 can replace part of SiO 2 and reduce the oxidation of the flux. Excessive Al 2 O 3 will increase the melting point and viscosity of slag. For this reason, the present invention limits the content of Al2O3 to 30-50 %.
CaCO3：作为造气剂、造渣剂。CaCO3在焊接高温作用下分解成CaO和CO2 。CaO是较强的碱性氧化物，对S、P的结合能力较强，可以降低焊缝金属中的S、P含量。分解的CO2气体，起到排除空气保护熔池作用。CaCO3含量过高时，分解的CO2增多，破坏电弧稳定性，影响焊缝成形。CaCO3含量过低时，达不到保护效果，易降低熔敷金属纯净度。为此本发明将CaCO3的含量限定在5～10%。 CaCO 3 : as a gas-forming agent and a slag-forming agent. CaCO 3 decomposes into CaO and CO 2 under the action of welding high temperature. CaO is a strong basic oxide with strong binding ability to S and P, which can reduce the content of S and P in the weld metal. The decomposed CO 2 gas plays the role of removing air and protecting the molten pool. When the content of CaCO 3 is too high, the decomposed CO 2 will increase, which will damage the arc stability and affect the weld formation. When the CaCO 3 content is too low, the protective effect cannot be achieved, and the purity of the deposited metal is easily reduced. For this reason, the present invention limits the content of CaCO to 5-10%.
Ti：强脱氧剂，Ti 的氧化物很容易从金属向溶渣过渡，并能强烈细化晶粒，提高焊缝金属的抗结晶裂纹能力。在本发明中将Ti 的含量限定在3～8%。 Ti: Strong deoxidizer, Ti oxides can easily transition from metal to slag, and can strongly refine grains, improving the resistance to crystallization cracks of weld metal. In the present invention, the content of Ti is limited to 3-8%.
Mn：脱氧剂，有脱S、P作用，在镍中会形成连续的固溶体，在保持较高的塑性条件下还能够强化金属。在本发明中将Mn 的含量限定在3～8%。 Mn: Deoxidizer, has the effect of removing S and P, and will form a continuous solid solution in nickel, which can also strengthen the metal while maintaining high plasticity. In the present invention, the content of Mn is limited to 3-8%.
碱度计算采用国际焊接学会推荐的BⅡW公式（式中用物质的分子式表示其质量分数）： Alkalinity calculation adopts the B Ⅱ W formula recommended by the International Welding Society (in which the molecular formula of the substance is used to represent its mass fraction):
BⅡW＝[CaO+MgO+K2O+Na2O+ CaF2+BaO+0.5（MnO+FeO）]/[ SiO2+0.5（TiO2+ZrO2+ Al2O3 ）] B ⅡW ＝[CaO+MgO+K 2 O+Na 2 O+ CaF 2 +BaO+0.5(MnO+FeO)]/[SiO 2 +0.5(TiO 2 +ZrO 2 +Al 2 O 3 )]
本发明此配方的碱度为2.0～3.0，为碱性烧结焊剂。 The basicity of the formula of the present invention is 2.0-3.0, which is an alkaline sintered flux.
具体实施方式 detailed description
根据本发明的设计组分含量，配制焊剂粉料，该焊剂采用普通的烧结焊剂制作方法，即：对所述组分组成的粉料进行干混、湿混、成粒、低温烘干、高温烧结、过筛等制取所述烧结焊剂，其制成品的粒径在φ0.5～5mm范围内。考虑碳酸盐的分解特性，烧结温度控制在600～800℃范围内，其组成成分见表1。 According to the design component content of the present invention, the flux powder is prepared, and the flux adopts the common sintered flux production method, that is: dry mixing, wet mixing, granulation, low-temperature drying, and high-temperature drying of the powder composed of the components. The sintered flux is prepared by sintering, sieving, etc., and the particle size of the finished product is within the range of φ0.5-5mm. Considering the decomposition characteristics of carbonate, the sintering temperature is controlled in the range of 600-800 °C, and its composition is shown in Table 1.
表1 焊剂的具体成分（按重量百分比） Table 1 The specific composition of flux (by weight percentage)
所研制出的焊剂与直径为3.2mm镍基合金埋弧焊丝配合试验，采用MZ-1000型直流埋弧自动焊机，焊接试板为10mm厚镀镍钢板，进行熔覆焊缝金属的化学成分分析见表2. The developed flux and the nickel-based alloy submerged arc welding wire with a diameter of 3.2mm are used for cooperating tests. The MZ-1000 DC submerged arc automatic welding machine is used. The welding test plate is a 10mm thick nickel-plated steel plate, and the chemical composition of the cladding weld metal is carried out. The analysis is shown in Table 2.
表2 熔覆金属主要化学成分（wt%） Table 2 Main chemical composition of cladding metal (wt%)
上述实例焊剂在焊接过程中电弧稳定，脱渣性良好，成形美观，与母材金属结合良好，经过超声波检测，焊缝金属内无裂纹、气孔、夹杂等缺陷。本发明烧结焊剂配镍基合金埋弧焊接具有良好的冶金性能，合金含量高，具有良好的使用性能。 The flux in the above example has a stable arc during the welding process, good slag removal, beautiful shape, and good bonding with the base metal. After ultrasonic testing, there are no cracks, pores, inclusions and other defects in the weld metal. The submerged arc welding of the sintered flux combined with the nickel base alloy of the invention has good metallurgical properties, high alloy content and good service performance.
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| CN104668816B (en) * | 2015-01-09 | 2017-01-11 | 天津重型装备工程研究有限公司 | Submerged-arc welding flux for low-alloy-steel narrow-gap welding and preparation method thereof |
| CN105195924A (en) * | 2015-09-25 | 2015-12-30 | 机械科学研究院哈尔滨焊接研究所 | Nickel baseband pole electroslag surfacing sintering flux and preparation method |
| CN105252172A (en) * | 2015-09-28 | 2016-01-20 | 洛阳双瑞特种合金材料有限公司 | Preparation method for sintered flux used for nickel base strip electrode submerged arc surfacing |
| TWI573654B (en) * | 2015-12-16 | 2017-03-11 | 國立屏東科技大學 | Welding flux for austenitic stainless steel |
| CN106514054A (en) * | 2016-11-29 | 2017-03-22 | 洛阳双瑞特种合金材料有限公司 | Sintered flux for band electrode submerged arc surfacing of nickel-based 625 alloy and preparation method of sintered flux |
| CN111037156A (en) * | 2019-12-24 | 2020-04-21 | 胡隆燕 | Preparation method of regulating particles for sintered flux |
| CN111151918B (en) * | 2019-12-27 | 2022-07-01 | 中国第一重型机械集团大连加氢反应器制造有限公司 | E316H type stainless steel submerged arc welding material for manufacturing fast neutron reactor equipment and preparation method thereof |
| CN113319470A (en) * | 2021-06-21 | 2021-08-31 | 中国船舶重工集团公司第七二五研究所 | Bonding flux capable of transferring alloy elements and used for nickel-based welding wire and preparation method thereof |
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|---|---|---|---|---|
| US3551137A (en) * | 1968-01-10 | 1970-12-29 | Electro Slag Inst | Flux for electroslag consumable remelting of nickel base super alloys and certain iron base alloys |
| JP3458452B2 (en) * | 1994-06-06 | 2003-10-20 | Ｊｆｅスチール株式会社 | High heat input latent arc welding method for thick steel plate with excellent toughness of weld metal |
| CN101564804A (en) * | 2009-06-05 | 2009-10-28 | 中国船舶重工集团公司第七二五研究所 | Hard surfacing sintered flux and manufacturing method thereof |
| CN101804525A (en) * | 2010-03-25 | 2010-08-18 | 河海大学常州校区 | Sintered flux for submerged arc welding of FCW with martensitic stainless steel hard surface |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156145A (en) * | 1976-06-21 | 1977-12-26 | Nippon Steel Corp | Bonded flux for three o*clock submerged arc welding |
| JPS5964193A (en) * | 1982-10-01 | 1984-04-12 | Naisu Kk | Flux for belt-like electrode |
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2013
- 2013-07-19 CN CN201310302234.7A patent/CN103394822B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3551137A (en) * | 1968-01-10 | 1970-12-29 | Electro Slag Inst | Flux for electroslag consumable remelting of nickel base super alloys and certain iron base alloys |
| JP3458452B2 (en) * | 1994-06-06 | 2003-10-20 | Ｊｆｅスチール株式会社 | High heat input latent arc welding method for thick steel plate with excellent toughness of weld metal |
| CN101564804A (en) * | 2009-06-05 | 2009-10-28 | 中国船舶重工集团公司第七二五研究所 | Hard surfacing sintered flux and manufacturing method thereof |
| CN101804525A (en) * | 2010-03-25 | 2010-08-18 | 河海大学常州校区 | Sintered flux for submerged arc welding of FCW with martensitic stainless steel hard surface |
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| CN103394822A (en) | 2013-11-20 |
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