CN117862737A - Antistatic tin-base alloy welding wire not easy to deform and preparation method thereof - Google Patents
Antistatic tin-base alloy welding wire not easy to deform and preparation method thereof Download PDFInfo
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- CN117862737A CN117862737A CN202311794611.3A CN202311794611A CN117862737A CN 117862737 A CN117862737 A CN 117862737A CN 202311794611 A CN202311794611 A CN 202311794611A CN 117862737 A CN117862737 A CN 117862737A
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- welding wire
- tin
- antistatic
- alloy welding
- deformable
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- 238000003466 welding Methods 0.000 title claims abstract description 64
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 39
- 239000000956 alloy Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 23
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 23
- 241001330002 Bambuseae Species 0.000 claims abstract description 23
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 23
- 239000011425 bamboo Substances 0.000 claims abstract description 23
- 239000003610 charcoal Substances 0.000 claims abstract description 23
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 13
- 239000000440 bentonite Substances 0.000 claims abstract description 13
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 15
- LGQLWSVDRFRGCP-UHFFFAOYSA-N [Mo].[Nd] Chemical compound [Mo].[Nd] LGQLWSVDRFRGCP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000498 cooling water Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 238000005121 nitriding Methods 0.000 claims description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 239000012798 spherical particle Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- PCORICZHGNSNIZ-UHFFFAOYSA-K trichloroneodymium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Nd+3] PCORICZHGNSNIZ-UHFFFAOYSA-K 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910000914 Mn alloy Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 5
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 claims description 5
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 claims description 5
- -1 aluminum-manganese Chemical compound 0.000 claims description 5
- 229940075397 calomel Drugs 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 239000004005 microsphere Substances 0.000 abstract description 10
- 239000010936 titanium Substances 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical class [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 239000011733 molybdenum Substances 0.000 abstract description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
- B23K35/286—Al as the principal constituent
- B23K35/288—Al as the principal constituent with Sn or Zn
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention discloses an antistatic tin-base alloy welding wire which is not easy to deform and a preparation method thereof, and relates to the technical field of welding wires. According to the invention, bentonite, bamboo charcoal and urea are mixed and granulated, the mixture is sintered to form the nitrogen-doped loose porous microspheres, and then the pores are utilized to adsorb butyl titanate, so that the butyl titanate can be attached to each phase structure in welding wire alloy melt and are mutually connected, the strength of a welding wire is improved, and simultaneously carbon elements and nitrogen elements in the titanium and the microspheres generate carbon-nitrogen compounds, so that the migration of grain boundaries and subgrain boundaries is pinned, grains are thinned, and the strength of the welding wire is further improved; and then, through extrusion and electrodeposition circulation treatment, molybdenum and neodymium metal elements permeate into alloy crystal boundaries of the welding wire, so that the conductivity and corrosion resistance of the welding wire are improved, and then through nitridation electrodeposition treatment, nitrogen-doped passivation films are formed on the metal elements on the surface of the welding wire, so that the corrosion resistance, strength and conductivity of the welding wire are improved.
Description
Technical Field
The invention relates to the technical field of welding wires, in particular to an antistatic tin-base alloy welding wire which is not easy to deform and a preparation method thereof.
Background
With the development of domestic and foreign engineering machinery, coal mine machinery, marine equipment, hydroelectric equipment and the like towards the directions of high quality, high strength, high toughness, large size and light weight, the welding metal material is expanded from the traditional carbon steel and low alloy steel to the field of high-strength fine grain alloy. The welding wire is used as a filler metal or simultaneously used as a metal wire welding material for electric conduction, and is used as the filler metal in gas welding and tungsten electrode gas shielded arc welding; in submerged arc welding, electroslag welding, and other consumable electrode gas shielded arc welding, the wire is both the filler metal and the wire is the conductive electrode. At present, the welding wire has single variety and can not meet the increasing requirement of steel plate shielded welding.
The properties of the welding wire directly affect the quality of the engineering in which the welding wire is used, and the corrosion of steel structures in coastal areas is serious, and the requirements on the corrosion resistance of the welding wire for the equipment are correspondingly high.
Disclosure of Invention
The invention aims to provide an antistatic tin-base alloy welding wire which is not easy to deform and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the antistatic and difficultly deformable tin-based alloy welding wire comprises the following preparation steps:
(1) Mixing and grinding bamboo charcoal, bentonite and urea to 100-140 meshes, sieving, adding deionized water with the mass of 0.1-0.3 times of that of the bamboo charcoal, stirring at 100rpm for 1-3 hours, aging at room temperature for 24 hours, granulating in a granulator to obtain spherical particles, drying at room temperature for 24 hours, sintering at 1180-1260 ℃ under normal pressure for 30-50 minutes in nitrogen atmosphere, immersing in butyl titanate ethanol solution according to a feed-liquid ratio of 1:10, performing 100W ultrasonic treatment for 30 minutes, and filtering to obtain a composite sphere;
(2) Weighing an aluminum ingot, a magnesium ingot, a copper ingot, an aluminum-iron alloy, an aluminum-manganese alloy and an aluminum-tin alloy according to mass fraction, heating and melting, spraying a composite sphere, and preserving heat for 3-5 hours to obtain an alloy melt;
(3) Casting into a casting rod with the diameter of 170mm and the length of 360-365 mm at the casting temperature of 725-755 ℃, the casting speed of 90-130 mm/min, the cooling water temperature of 10-20 ℃ and the cooling water strength of 0.05-0.1 MPa;
(4) Removing oxide skin on the surface of a casting rod by using a planing machine to obtain a casting rod with the diameter of 164-166 mm, taking the casting rod as a working electrode, taking a reference electrode as a saturated calomel electrode, taking a counter electrode as a platinum wire electrode, adopting molybdenum neodymium plating solution, depositing at 30 ℃ for 5-40 min, preserving heat at 540-555 ℃ for 6-8 h, preserving heat at 420-440 ℃ for 2-3 h, putting into an extruder, extruding at 580-620 MPa, and repeating the steps for 1-2 times to obtain a base material with the diameter of 15-19 mm;
(5) The base material, the platinum sheet and the calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode, nitriding treatment liquid is adopted for 2 hours, then the temperature is kept at 460-490 ℃ for 3-5 hours, and the tin-base alloy welding wire which is antistatic and not easy to deform is obtained by stretching through a stretching die.
Further, the mass ratio of the bamboo charcoal, bentonite and urea in the step (1) is 35:10:10-50:25:15.
Further, the spherical particles in the step (1) have a particle diameter of 1 to 10mm.
Further, the mass fraction of the butyl titanate ethanol solution in the step (1) is 3-10%.
Further, the mass fraction of the step (2) is 4.8-6.9% Sn, 0.2-1.1% Mg, 4.6-6.4% Cu, 0.10-0.35% C, 0.01-0.06% Fe, 0.15-0.26% Mn, 0.05-0.1% Ti, 0.01-0.03% N and the balance being aluminum.
Further, the melting temperature in the step (2) is 740-790 ℃.
Further, the molybdenum neodymium plating solution in the step (4) comprises 10-25 g/L of sodium molybdate dihydrate, 8-15 g/L of neodymium trichloride hexahydrate, 25-50 g/L of sodium citrate and 0.1g/L of sodium dodecyl sulfate, and the pH=4.
Further, the nitriding treatment liquid in the step (5) comprises 0.5mol/L potassium nitrate and 0.1mol/L nitric acid.
Further, the diameter of the antistatic and difficultly deformable tin-based alloy welding wire in the step (5) is 2-5 mm.
Further, the current density in the electrodeposition process of the steps (4) and (5) is 1-5 mA/cm 2 。
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, bentonite, bamboo charcoal and urea are mixed and granulated to form spheroids, nitrogen-containing gas is formed through sintering and urea decomposition, the spheroids penetrate into the interior along pore channels of the bamboo charcoal to form nitrogen-doped porous microspheres, meanwhile, in the sintering process, bentonite is melted to form liquid, the bamboo charcoal is infiltrated, so that the bamboo charcoal is bonded together, holes of the bamboo charcoal are combined, the interiors of the microspheres are loose and porous, butyl titanate is adsorbed by capillary action of the holes, then the porous holes are sprayed into alloy melt, the nearby melt is infiltrated by the loose and porous holes on the surfaces of the microspheres, n-butyl titanate in the holes can be adhered to the alloy, and the microspheres can be connected with each phase structure by virtue of the holes, so that the strength of a welding wire is improved, meanwhile, carbon elements and nitrogen elements in the titanium and the microspheres generate carbon-nitrogen compounds, and play a pinning role on migration of grain boundaries and subgrain boundaries, so that grains are refined, and the strength of the welding wire is further improved.
The invention introduces molybdenum and neodymium metal elements into the surface of the welding wire through the first electrodeposition treatment, then carries out extrusion and electrodeposition circulation treatment to uniformly cover the surface, and in the extrusion process, permeates into alloy crystal boundary of the welding wire to form firm combination, improves the conductivity and corrosion resistance of the welding wire, and then carries out nitridation treatment through the second electrodeposition treatment to ensure that NO adsorbed on the molybdenum-neodymium metal elements 3 - The nitrogen is reduced into nitrogen through electrochemistry, and reacts with metal elements to generate a nitrogen doped passivation film, which has a protective effect on a welding wire matrix, reduces surface defects and improves corrosion resistance and conductivity of the welding wire.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the detailed description, and the test methods of each index of the antistatic and non-deformable tin-based alloy welding wire manufactured in the following examples are as follows:
high strength: taking two Q690-grade structural steels welded by the same-size examples and comparative examples under the carbon dioxide atmosphere, wherein the welding current is 200A, the welding voltage is 25V, the welding speed is 0.2m/min and the gas flow is 20L/min, and then testing the mechanical properties by referring to GB/T25774.1.
Conductivity: the volume resistivity was measured using a resistivity meter for the same size examples and comparative examples.
Corrosion resistance: the same size of examples and comparative examples were placed in a constant temperature and humidity cabinet at 40℃and 60% humidity for 168 hours, and the surface corrosion was observed.
Example 1
(1) Mixing and grinding bamboo charcoal, bentonite and urea according to a mass ratio of 35:10:10 to 100 meshes, then adding deionized water with the mass of 0.1 times of that of the bamboo charcoal, stirring for 1h at 100rpm, aging for 24h at room temperature, granulating in a granulator to obtain spherical particles with the particle size of 1mm, drying for 24h at room temperature, sintering for 30min at 1180 ℃ under normal pressure in nitrogen atmosphere, soaking in 3% butyl titanate ethanol solution with the mass fraction of 1:10 according to the feed-liquid ratio, performing 100W ultrasonic treatment for 30min, and filtering to obtain a composite sphere;
(2) Weighing 4.8% of Sn, 0.2% of Mg, 4.6% of Cu, 0.10% of C, 0.01% of Fe, 0.15% of Mn, 0.05% of Ti, 0.01% of N and the balance of aluminum according to mass fraction, weighing aluminum ingots, magnesium ingots, copper ingots, aluminum-iron alloys, aluminum-manganese alloys and aluminum-tin alloys, heating and melting at 740 ℃, spraying composite spheres, and preserving heat for 3 hours to obtain alloy melt;
(3) Casting into a casting rod with the diameter of 170mm and the length of 360mm at the casting temperature of 725 ℃, the casting speed of 90mm/min, the cooling water temperature of 10 ℃ and the cooling water strength of 0.05 MPa;
(4) Removing oxide skin on the surface of the casting rod by using a planing machine to obtain a casting rod with the diameter of 164mm, wherein the casting rod is used as a working electrode, a reference electrode is a saturated calomel electrode, a counter electrode is a platinum wire electrode, a molybdenum neodymium plating solution is adopted, the temperature is 30 ℃, and the current density is 1mA/cm 2 Depositing for 5min, preserving heat at 540 ℃ for 6h and 420 ℃ for 2h, putting into an extruder, extruding under 580MPa, repeating the steps for 1 time to obtain a base material with the diameter of 15 mm; the molybdenum neodymium plating solution comprises 10g/L of sodium molybdate dihydrate, 8g/L of neodymium trichloride hexahydrate, 25g/L of sodium citrate, 0.1g/L of sodium dodecyl sulfate and pH=4;
(5) The base material, the platinum sheet and the calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode, and nitriding treatment liquid is adopted, namely 1mA/cm 2 Performing lower treatment for 2 hours, and then preserving heat at 460 ℃ for 3 hours, and stretching by a stretching die to obtain an antistatic and non-deformable tin-base alloy welding wire with the diameter of 2 mm; the nitriding treatment liquid comprises 0.5mol/L potassium nitrate and 0.1mol/L nitric acid.
Example 2
(1) Mixing and grinding bamboo charcoal, bentonite and urea according to the mass ratio of 44:19:12 to 120 mesh sieve, adding deionized water with the mass of 0.2 times of the bamboo charcoal, stirring at 100rpm for 2 hours, aging at room temperature for 24 hours, granulating in a granulator to obtain spherical particles with the particle size of 5mm, drying at room temperature for 24 hours, sintering at 1220 ℃ under normal pressure for 40 minutes, soaking in butyl titanate ethanol solution with the mass fraction of 6% according to the feed-liquid ratio of 1:10, performing 100W ultrasonic treatment for 30 minutes, and filtering to obtain a composite sphere;
(2) Weighing 5.4% of Sn, 0.6% of Mg, 5.5% of Cu, 0.29% of C, 0.03% of Fe, 0.21% of Mn, 0.08% of Ti, 0.02% of N and the balance of aluminum according to mass fraction, weighing aluminum ingots, magnesium ingots, copper ingots, aluminum-iron alloys, aluminum-manganese alloys and aluminum-tin alloys, heating and melting at 765 ℃, spraying composite spheres, and preserving heat for 4 hours to obtain alloy melt;
(3) Casting into a casting rod with the diameter of 170mm and the length of 362mm at the casting temperature of 744 ℃, the casting speed of 110mm/min, the cooling water temperature of 15 ℃ and the cooling water strength of 0.08 MPa;
(4) Removing oxide skin on the surface of the casting rod by using a planer to obtain a casting rod with the diameter of 165mm, wherein the casting rod is used as a working electrode, a reference electrode is a saturated calomel electrode, a counter electrode is a platinum wire electrode, a molybdenum neodymium plating solution is adopted, the temperature is 30 ℃, and the current density is 3mA/cm 2 Depositing for 20min, preserving heat at 548 ℃ for 7h and 430 ℃ for 2.5h, putting into an extruder, extruding under 600MPa, and repeating the steps for 2 times to obtain a base material with the diameter of 17 mm; the molybdenum neodymium plating solution comprises 18g/L of sodium molybdate dihydrate, 11g/L of neodymium trichloride hexahydrate, 39g/L of sodium citrate, 0.1g/L of sodium dodecyl sulfate and pH=4;
(5) The base material, the platinum sheet and the calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode, and nitriding treatment liquid is adopted for 3mA/cm 2 Performing lower treatment for 2 hours, then preserving heat at 475 ℃ for 4 hours, and stretching by a stretching die to obtain an antistatic and non-deformable tin-base alloy welding wire with the diameter of 3 mm; the nitriding treatment liquid comprises 0.5mol/L potassium nitrate and 0.1mol/L nitric acid.
Example 3
(1) Mixing and grinding bamboo charcoal, bentonite and urea according to a mass ratio of 50:25:15 to 140 meshes, then adding deionized water with the mass of 0.3 times of that of the bamboo charcoal, stirring at 100rpm for 3 hours, aging at room temperature for 24 hours, granulating in a granulator to obtain spherical particles with the particle size of 10mm, drying at room temperature for 24 hours, sintering at 1260 ℃ under normal pressure for 50 minutes, soaking in a butyl titanate ethanol solution with the mass fraction of 10% according to a feed-liquid ratio of 1:10, performing 100W ultrasonic treatment for 30 minutes, and filtering to obtain a composite sphere;
(2) Weighing an aluminum ingot, a magnesium ingot, a copper ingot, an aluminum-iron alloy, an aluminum-manganese alloy and an aluminum-tin alloy according to the mass fraction of 6.9% Sn, 1.1% Mg, 6.4% Cu, 0.35% C, 0.06% Fe, 0.26% Mn, 0.1% Ti, 0.03% N and the balance of aluminum, heating and melting at 790 ℃, spraying into a composite sphere, and preserving heat for 5 hours to obtain an alloy melt;
(3) Casting into a casting rod with the diameter of 170mm and the length of 365mm at the casting temperature of 755 ℃, the casting speed of 130mm/min, the cooling water temperature of 20 ℃ and the cooling water strength of 0.1 MPa;
(4) Removing oxide skin on the surface of the casting rod by using a planer to obtain a casting rod with the diameter of 166mm, wherein the casting rod is used as a working electrode, a reference electrode is a saturated calomel electrode, a counter electrode is a platinum wire electrode, a molybdenum neodymium plating solution is adopted, and the current density is 5mA/cm at 30 DEG C 2 Depositing for 40min, preserving heat at 555 ℃ for 8h, preserving heat at 440 ℃ for 3h, putting into an extruder, extruding under 620MPa, repeating the steps for 2 times to obtain a base material with the diameter of 19 mm; the molybdenum neodymium plating solution comprises 25g/L of sodium molybdate dihydrate, 15g/L of neodymium trichloride hexahydrate, 50g/L of sodium citrate, 0.1g/L of sodium dodecyl sulfate and pH=4;
(5) The base material, the platinum sheet and the calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode, and nitriding treatment liquid is adopted for 5mA/cm 2 Performing lower treatment for 2 hours, then preserving heat at 490 ℃ for 5 hours, and stretching by a stretching die to obtain an antistatic and non-deformable tin-base alloy welding wire with the diameter of 5 mm; the nitriding treatment liquid comprises 0.5mol/L potassium nitrate and 0.1mol/L nitric acid.
Comparative example 1
Comparative example 1 differs from example 2 in that step (1) was changed to: mixing and grinding bamboo charcoal and bentonite according to a mass ratio of 44:19 to 120 mesh sieve, adding deionized water with the mass of 0.2 times of the bamboo charcoal, stirring at 100rpm for 2h, aging at room temperature for 24h, granulating in a granulator to obtain spherical particles with the particle size of 5mm, drying at room temperature for 24h, sintering at 1220 ℃ under normal pressure for 40min under nitrogen atmosphere, immersing in butyl titanate ethanol solution with the mass fraction of 6% according to a feed liquid ratio of 1:10, performing 100W ultrasonic treatment for 30min, and filtering to obtain a composite sphere; the rest of the procedure is the same as in example 2.
Comparative example 2
Comparative example 2 differs from example 2 in that step (1) was changed to: mixing and grinding bamboo charcoal, bentonite and urea according to the mass ratio of 44:19:12 to 120 mesh sieve, adding deionized water with the mass of 0.2 times of that of the bamboo charcoal, stirring for 2 hours at 100rpm, aging for 24 hours at room temperature, granulating in a granulator to obtain spherical particles with the particle size of 5mm, drying for 24 hours at room temperature, and sintering for 40 minutes at 1220 ℃ under normal pressure in nitrogen atmosphere to obtain composite spheres; the rest of the procedure is the same as in example 2.
Comparative example 3
Comparative example 3 differs from example 2 in that step (4) was changed to: removing oxide skin on the surface of the casting rod by using a planer to obtain a casting rod with the diameter of 165mm, wherein the casting rod is used as a working electrode, a reference electrode is a saturated calomel electrode, a counter electrode is a platinum wire electrode, a molybdenum neodymium plating solution is adopted, the temperature is 30 ℃, and the current density is 3mA/cm 2 Depositing for 20min, then preserving heat at 548 ℃ for 7h and 430 ℃ for 2.5h to obtain a base material; the molybdenum neodymium plating solution comprises 18g/L of sodium molybdate dihydrate, 11g/L of neodymium trichloride hexahydrate, 39g/L of sodium citrate, 0.1g/L of sodium dodecyl sulfate and pH=4; the rest of the procedure is the same as in example 2.
Comparative example 4
Comparative example 4 differs from example 2 in that step (4) was changed to: removing oxide skin on the surface of a casting rod by using a planing machine to obtain a casting rod with the diameter of 165mm, preserving heat for 7h at 548 ℃, preserving heat for 2.5h at 430 ℃, putting the casting rod into an extruder, extruding under 600MPa, and repeating the steps for 2 times to obtain a base material with the diameter of 17 mm; the rest of the procedure is the same as in example 2.
Comparative example 5
Comparative example 5 differs from example 2 in that step (5) was changed to: preserving heat for 4 hours at 475 ℃, and stretching by a stretching die to obtain an antistatic and non-deformable tin-base alloy welding wire with the diameter of 3 mm; the rest of the procedure is the same as in example 2.
Effect example
The results of the performance analysis of the antistatic, less deformable tin-based alloy welding wires employing examples 1 to 3 of the present invention and comparative examples 1 to 5 are given in table 1 below.
TABLE 1
As can be found from the comparison of experimental data of the embodiment and the comparative example, the invention utilizes bentonite, bamboo charcoal and urea to mix and granulate, sinter to form nitrogen-doped loose porous microspheres, then adsorb butyl titanate in the microspheres, so that the butyl titanate can be attached to each phase of tissue and mutually connected, the strength of the welding wire is improved, and simultaneously carbon elements and nitrogen elements in the titanium and the microspheres generate carbon nitrogen compounds, and the pinning effect is achieved on migration of grain boundaries and subgrain boundaries, so that grains are thinned, and the strength of the welding wire is further improved; then through extrusion and electrodeposition circulation treatment, the molybdenum and neodymium metal elements infiltrate into the alloy grain boundary of the welding wire to form firm combination, the conductivity and corrosion resistance of the welding wire are improved, and then through secondary electrodeposition treatment, nitridation treatment is carried out, so that NO adsorbed on the molybdenum-neodymium metal elements is formed 3 - The nitrogen is reduced into nitrogen through electrochemistry, and reacts with metal elements to generate a nitrogen doped passivation film, which has a protective effect on a welding wire matrix, reduces surface defects and improves corrosion resistance and conductivity of the welding wire.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The preparation method of the antistatic and difficultly deformable tin-based alloy welding wire is characterized by comprising the following preparation steps of:
(1) Mixing and grinding bamboo charcoal, bentonite and urea to 100-140 meshes, sieving, adding deionized water with the mass of 0.1-0.3 times of that of the bamboo charcoal, stirring at 100rpm for 1-3 hours, aging at room temperature for 24 hours, granulating in a granulator to obtain spherical particles, drying at room temperature for 24 hours, sintering at 1180-1260 ℃ under normal pressure for 30-50 minutes in nitrogen atmosphere, immersing in butyl titanate ethanol solution according to a feed-liquid ratio of 1:10, performing 100W ultrasonic treatment for 30 minutes, and filtering to obtain a composite sphere;
(2) Weighing an aluminum ingot, a magnesium ingot, a copper ingot, an aluminum-iron alloy, an aluminum-manganese alloy and an aluminum-tin alloy according to mass fraction, heating and melting, spraying a composite sphere, and preserving heat for 3-5 hours to obtain an alloy melt;
(3) Casting into a casting rod with the diameter of 170mm and the length of 360-365 mm at the casting temperature of 725-755 ℃, the casting speed of 90-130 mm/min, the cooling water temperature of 10-20 ℃ and the cooling water strength of 0.05-0.1 MPa;
(4) Removing oxide skin on the surface of a casting rod by using a planing machine to obtain a casting rod with the diameter of 164-166 mm, taking the casting rod as a working electrode, taking a reference electrode as a saturated calomel electrode, taking a counter electrode as a platinum wire electrode, adopting molybdenum neodymium plating solution, depositing at 30 ℃ for 5-40 min, preserving heat at 540-555 ℃ for 6-8 h, preserving heat at 420-440 ℃ for 2-3 h, putting into an extruder, extruding at 580-620 MPa, and repeating the steps for 1-2 times to obtain a base material with the diameter of 15-19 mm;
(5) The base material, the platinum sheet and the calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode, nitriding treatment liquid is adopted for 2 hours, then the temperature is kept at 460-490 ℃ for 3-5 hours, and the tin-base alloy welding wire which is antistatic and not easy to deform is obtained by stretching through a stretching die.
2. The method for preparing the antistatic tin-base alloy welding wire which is not easy to deform according to claim 1, wherein the mass ratio of the bamboo charcoal to the bentonite to the urea in the step (1) is 35:10:10-50:25:15.
3. The method for producing an antistatic, less deformable tin-based alloy wire according to claim 1, wherein the spherical particles in step (1) have a particle size of 1 to 10mm.
4. The method for preparing the antistatic and non-deformable tin-base alloy welding wire according to claim 1, wherein the mass fraction of the butyl titanate ethanol solution in the step (1) is 3-10%.
5. The method for preparing an antistatic and non-deformable tin-based alloy welding wire according to claim 1, wherein the mass fraction of the tin-based alloy welding wire in the step (2) is 4.8-6.9% of Sn, 0.2-1.1% of Mg, 4.6-6.4% of Cu, 0.10-0.35% of C, 0.01-0.06% of Fe, 0.15-0.26% of Mn, 0.05-0.1% of Ti, 0.01-0.03% of N and the balance of aluminum.
6. The method for producing an antistatic, less deformable tin-based alloy welding wire as claimed in claim 1, wherein said melting temperature in step (2) is 740-790 ℃.
7. The method for preparing an antistatic and non-deformable tin-based alloy welding wire according to claim 1, wherein the molybdenum-neodymium plating solution in the step (4) comprises 10-25 g/L of sodium molybdate dihydrate, 8-15 g/L of neodymium trichloride hexahydrate, 25-50 g/L of sodium citrate, 0.1g/L of sodium dodecyl sulfate, and ph=4.
8. The method for producing an antistatic, less deformable tin-based alloy welding wire according to claim 1, wherein the nitriding treatment liquid in step (5) comprises 0.5mol/L potassium nitrate, 0.1mol/L nitric acid.
9. The method for producing an antistatic non-deformable tin-based alloy welding wire according to claim 1, wherein the diameter of the antistatic non-deformable tin-based alloy welding wire in step (5) is 2-5 mm.
10. A according to claim 1The preparation method of the antistatic and difficultly deformable tin-base alloy welding wire is characterized in that the current density in the electrodeposition process in the steps (4) and (5) is 1-5 mA/cm 2 。
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| CN117965078A (en) * | 2024-01-02 | 2024-05-03 | 江苏龙辉建筑劳务有限公司 | Waterproof fireproof high-performance coating and preparation method thereof |
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