CN85100663B - Nickel-based brazing material for nuclear industry - Google Patents
Nickel-based brazing material for nuclear industry Download PDFInfo
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- CN85100663B CN85100663B CN85100663A CN85100663A CN85100663B CN 85100663 B CN85100663 B CN 85100663B CN 85100663 A CN85100663 A CN 85100663A CN 85100663 A CN85100663 A CN 85100663A CN 85100663 B CN85100663 B CN 85100663B
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- nickel
- brazing
- brazing material
- nuclear industry
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- 238000005219 brazing Methods 0.000 title abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 25
- 239000000463 material Substances 0.000 title abstract description 22
- 229910052759 nickel Inorganic materials 0.000 title abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000679 solder Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 abstract description 15
- 230000008018 melting Effects 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 239000000956 alloy Substances 0.000 abstract description 9
- 230000005855 radiation Effects 0.000 abstract description 7
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 4
- 239000007769 metal material Substances 0.000 abstract description 3
- 229910000601 superalloy Inorganic materials 0.000 abstract description 3
- 229910001252 Pd alloy Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000007747 plating Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910000816 inconels 718 Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910019819 Cr—Si Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Ceramic Products (AREA)
Abstract
本发明系核工业用镍基钎焊料。特别适用于钎焊核工业反应堆用不锈钢、耐蚀合金和高温合金等金属材料的薄壁构件。本发明是以镍为基的，含有Ｃｒ、Ｓｉ、Ｇｅ、Ｆｅ、Ｐ、Ｐｄ的合金。其熔化温度范围为１０４０～１０８０℃。且具有熔点低、强度高、熔蚀小以及抗腐蚀和抗中子辐照性能等优异的特点，是一种新颖的核工业用镍基钎焊料。The invention is a nickel-based brazing material for nuclear industry. It is especially suitable for brazing thin-walled components of metal materials such as stainless steel, corrosion-resistant alloys and superalloys for nuclear industrial reactors. The invention is based on nickel and contains Cr, Si, Ge, Fe, P, Pd alloy. Its melting temperature ranges from 1040 to 1080°C. And it has the characteristics of low melting point, high strength, small erosion, corrosion resistance and neutron radiation resistance, etc. It is a novel nickel-based brazing material for nuclear industry.
Description
本发明系一种新颖的核工业用镍基钎焊料。特别适用于钎焊核工业反应堆用不锈钢、耐蚀合金和高温合金等金属材料的薄壁构件。The invention is a novel nickel-based brazing material for nuclear industry. It is especially suitable for brazing thin-walled components of metal materials such as stainless steel, corrosion-resistant alloys and superalloys for nuclear industrial reactors.
目前，国际上核工业反应堆有关构件通用的制造方法有两种：一种是熔化焊焊接方法;另一种是钎焊焊接的方法，从60年代以来，大、中型反应堆的格架制造大部分采用钎焊。而且所使用的钎焊料主要是BNi-7系列（即Ni-Cr-P系）焊料。象美国、英国和西德就一直使用这种钎焊料制造格架。表1列出有几个主要国家所采用的BNi-7系列焊料成分和熔点、钎焊温度。At present, there are two common manufacturing methods for relevant components of nuclear industrial reactors in the world: one is the fusion welding method; the other is the brazing welding method. Since the 1960s, most of the grids of large and medium-sized reactors Brazing is used. And the brazing material used is mainly BNi-7 series (ie Ni-Cr-P series) solder. Such as the United States, Britain and West Germany have been using this brazing material to make grids. Table 1 lists the BNi -7 series solder composition, melting point, and brazing temperature used in several major countries.
表1 一些国家所采用的BNi-7系钎焊料成分及熔点Table 1 Composition and melting point of BNi -7 brazing filler metals used in some countries
BNi-7系列钎焊料的特点是熔点较低。这利于改善钎焊工艺性能并可减少母材因受热而降低性能的影响。但其缺点是强度低（＜20Kg/mm2），塑性差（扭转试验的扭转角小于270℃），并对一些活性元素含量较高的高温合金，其钎焊工艺性能差，使得被焊接部件需要镀镍才能进行钎焊。造成工艺复杂。同时，由于含磷量高，钎焊料的熔蚀较大（＞20μm），有损于基体材料的强度，特别是对薄壁材料。BNi -7 series brazing materials are characterized by a low melting point. This is conducive to improving the performance of the brazing process and can reduce the influence of the performance of the base metal due to heat. But its disadvantages are low strength (<20Kg/mm 2 ), poor plasticity (the torsion angle of the torsion test is less than 270°C), and for some high-temperature alloys with high content of active elements, the brazing process performance is poor, making the welded parts Nickel plating is required for brazing. Make the process complicated. At the same time, due to the high phosphorus content, the erosion of the brazing material is large (> 20μm), which damages the strength of the base material, especially for thin-walled materials.
另外，国外研究和使用的另一大类核反应堆用钎焊料是BNi-5系列（即Ni-Cr-Si系）表2列出了这一系列的一些焊料的具体成分及熔点。In addition, another major type of brazing material for nuclear reactors researched and used abroad is the BNi -5 series (ie Ni-Cr-Si system). Table 2 lists the specific components and melting points of some solders in this series.
BNi-5系钎焊料的优点是强度较高，可达30Kg/mm2，熔蚀也较小，一般在20μm以下，但主要缺点是熔点太高，从而使钎焊温度大大The advantage of BNi -5 series brazing material is that it has high strength, which can reach 30Kg/mm 2 , and the erosion is also small, generally below 20μm, but the main disadvantage is that the melting point is too high, so that the brazing temperature is greatly increased.
表2 BNi-5系列焊料具体成分及熔点 Table 2 Specific composition and melting point of BNi -5 series solder
超过了许多变形材料的再结晶温度，导致基体合金性能的变化，特别是在焊接薄壁材料时，显得更加严重。 The recrystallization temperature of many deformed materials is exceeded, resulting in changes in the properties of the base alloy, especially when welding thin-walled materials, which are more serious.
本发明的目的在于提出了一种熔点低、强度高、熔蚀小以及抗腐蚀性能和抗中子辐照性能优异的钎焊料，特别适用于钎焊核工业反应堆用不锈钢，耐蚀合金和高温合金等金属材料的薄壁构件。The purpose of the present invention is to propose a brazing material with low melting point, high strength, low corrosion resistance, excellent corrosion resistance and neutron radiation resistance, which is especially suitable for brazing nuclear industrial reactor stainless steel, corrosion-resistant alloys and Thin-walled components of metal materials such as superalloys.
本发明是以Ni为基的，含有Cr\Si\Ge\Fe\P\Pd的钎焊料，其具体成分范围如下：11～19%Cr\8.5～10%Si、1～4%Ge、4～10%Fe、1～4.9%Pd、＜2.0%P、余为Ni。合金元素的主要作用如下：加入11～19%Cr是为了提高强度，改善耐腐蚀性能;加入Ge能降低熔点，改善钎焊工艺性能;加入Pd能改善机械性能，特别是塑性，在一定程度上还能改善工艺性能;加入Si也是为了提高机械性能，同时可降低熔点，改善流动性;Fe的作用是提高机械性能。The present invention is based on Ni and contains Cr\Si\Ge\Fe\P\Pd brazing filler metal, and its specific composition range is as follows: 11～19%Cr\8.5～10%Si, 1～4%Ge, 4~10%Fe, 1~4.9%Pd, <2.0%P, the rest is Ni. The main functions of alloying elements are as follows: adding 11-19% Cr is to increase strength and improve corrosion resistance; adding Ge can lower melting point and improve brazing process performance; adding Pd can improve mechanical properties, especially plasticity, to a certain extent It can also improve the process performance; the addition of Si is also to improve the mechanical properties, and at the same time can reduce the melting point and improve the fluidity; the role of Fe is to improve the mechanical properties.
本发明的熔化区域为1040～1080℃。钎焊工艺性能良好，可对含Al\Ti的高温合金（如Inconel 718）在不镀镍的情况下直接进行钎焊，省去了复杂的镀镍工序，焊料熔蚀小于20微米，且能良好地润湿该合金。用本发明制作部件时，钎焊缝成形性好，表面光洁，特别适用于大面积多焊缝的钎焊。The melting range of the present invention is 1040-1080°C. The performance of the brazing process is good, and it can directly braze the high-temperature alloy containing Al\Ti (such as Inconel 718) without nickel plating, which saves the complicated nickel plating process, and the solder erosion is less than 20 microns, and can Wet the alloy well. When the invention is used to make parts, the brazing seam has good formability and smooth surface, and is especially suitable for brazing with large area and multiple welding seams.
采用本发明进行钎焊，其接头具有较高的机械性能，钎焊接头在350℃下的抗拉强度可达35～40公斤/毫米2，扭转试验的扭转角大于360°。同时，抗腐蚀性能，特别是抗应力腐蚀性能优良，三点拱形试样在8、15、25公斤/毫米2三种应力条件下，在含有氯离子的介质中进行试验，均未发现应力腐蚀象。本发明还具有优异的抗中子辐照性能，在高通量中子辐照下，于350℃进行辐照试验，辐照后，钎焊接头性能仍然良好，即辐照前后性能上没有大的变化。Brazing by using the present invention, the joint has higher mechanical properties, the tensile strength of the brazed joint at 350°C can reach 35-40 kg/mm 2 , and the torsion angle of the torsion test is greater than 360°. At the same time, the corrosion resistance, especially the stress corrosion resistance, is excellent. The three-point arched sample was tested in a medium containing chloride ions under three stress conditions of 8, 15, and 25 kg/ mm2 , and no stress was found. Corrosion icon. The invention also has excellent anti-neutron radiation performance. Under high-flux neutron radiation, the radiation test was carried out at 350°C. After radiation, the performance of the brazed joint is still good, that is, there is no significant difference in performance before and after radiation. The change.
本发明生产工艺简单。可采用真空感应炉冶炼，钢水可铸入生铁模内，脱模后，通过破碎机制成小于120目的粉末，过筛就可得到可用的粉末钎焊料。 The production process of the invention is simple. It can be smelted in a vacuum induction furnace. The molten steel can be cast into a pig iron mold. After demoulding, it can be made into a powder of less than 120 mesh by a crusher, and the usable powder brazing material can be obtained by sieving.
实施例一Embodiment one
以11.3%Cr、9.0%Si、4.0%Ge、8.5%Fe、4.7%Pd、余为Ni的成分配比备料，在真空感应炉上冶炼，随后制成钎焊料，钎接Inconel 718合金。焊前用双氧水。HCl和H2O各1/3的溶液进行洗后，再浸入丙酮进一步清洗，随后烘干。在冷壁真空炉内直接进行钎焊，被焊材料不镀镍。钎焊规范为：真空度1×10-4乇，加热温度1100℃，保温时间10分钟，炉冷。所得的钎接接头具有良好的机械性能，350℃时的抗拉强度为15公斤/毫米2，熔蚀小于20微米。The material is prepared with a composition ratio of 11.3%Cr, 9.0%Si, 4.0%Ge, 8.5%Fe, 4.7%Pd, and Ni is smelted on a vacuum induction furnace, and then brazing material is made to braze Inconel 718 alloy. Use hydrogen peroxide before welding. After washing with 1/3 solutions of HCl and H 2 O, immerse in acetone for further cleaning, and then dry. Brazing is performed directly in a cold-wall vacuum furnace, and the material to be welded is not nickel-plated. The brazing specification is: vacuum degree 1×10 -4 Torr, heating temperature 1100°C, holding time 10 minutes, furnace cooling. The obtained brazed joint has good mechanical properties, the tensile strength at 350°C is 15 kg/mm 2 , and the erosion is less than 20 microns.
实施例二Embodiment two
按重量比为15%Cr、10%Si、10%Fe、1%Ge、1%Pd1.6%P、余为Ni的成分进行配料，经真空感应炉冶炼后制成钎焊料，用该钎焊料焊接厚度为0.1毫米的18-8不锈钢环形薄壁构件，构件外径为400毫米。焊前用稀盐酸及丙酮清洗，然后烘干，在冷壁真空炉内进行钎焊，钎焊规范为：加热温度1120℃，保温时间15分钟，真空度1×10-4乇。钎接接头性能良好，室温抗拉强度为36公斤/毫米2，500℃的高温抗拉强度为13公斤/毫米2。熔蚀小于20微米。According to the weight ratio of 15%Cr, 10%Si, 10%Fe, 1%Ge, 1%Pd1.6%P, and the rest is Ni, the ingredients are mixed, and the brazing material is made after smelting in a vacuum induction furnace. 18-8 stainless steel annular thin-walled components with a thickness of 0.1 mm are welded by brazing material, and the external diameter of the components is 400 mm. Clean with dilute hydrochloric acid and acetone before welding, then dry, and braze in a cold-wall vacuum furnace. The performance of the brazed joint is good, the tensile strength at room temperature is 36 kg/mm 2 , and the high temperature tensile strength at 500°C is 13 kg/mm 2 . Corrosion is less than 20 microns.
实施例三 Embodiment three
按表3所列成分配比，在真空感应炉上冶炼了4个不同成分的镍基钎焊料，并按实施例一进行钎焊。According to the composition ratio listed in Table 3, 4 nickel-based brazing materials with different compositions were smelted on a vacuum induction furnace, and brazed according to Example 1.
表3.table 3.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100663A CN85100663B (en) | 1985-04-01 | 1985-04-01 | Nickel-based brazing material for nuclear industry |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100663A CN85100663B (en) | 1985-04-01 | 1985-04-01 | Nickel-based brazing material for nuclear industry |
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| Publication Number | Publication Date |
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| CN85100663A CN85100663A (en) | 1985-09-10 |
| CN85100663B true CN85100663B (en) | 1985-09-10 |
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| CN85100663A Expired CN85100663B (en) | 1985-04-01 | 1985-04-01 | Nickel-based brazing material for nuclear industry |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102699569A (en) * | 2012-06-18 | 2012-10-03 | 北京有色金属研究总院 | High temperature nickel base brazing solder paste in nuclear industry and preparing method of high temperature nickel base brazing solder paste |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992331B (en) * | 2010-10-25 | 2012-05-23 | 山东大学 | Vacuum Brazing Process of Super Nickel Laminates and Cr18-Ni8 Stainless Steel |
| JP6860410B2 (en) * | 2017-04-25 | 2021-04-14 | 山陽特殊製鋼株式会社 | Ni—Cr based alloy brazing material containing a small amount of V |
| CN107309573B (en) * | 2017-06-20 | 2020-06-02 | 华北水利水电大学 | High-strength nickel-based brazing filler metal containing boron alkene and smelting method thereof |
| CN113948265B (en) * | 2021-10-20 | 2024-08-13 | 泉州天智合金材料科技有限公司 | Iron-based amorphous soft magnetic alloy powder and preparation method thereof |
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1985
- 1985-04-01 CN CN85100663A patent/CN85100663B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102699569A (en) * | 2012-06-18 | 2012-10-03 | 北京有色金属研究总院 | High temperature nickel base brazing solder paste in nuclear industry and preparing method of high temperature nickel base brazing solder paste |
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