CN113088982A - Production method of glossy copper rod - Google Patents
Production method of glossy copper rod Download PDFInfo
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- CN113088982A CN113088982A CN202110353850.XA CN202110353850A CN113088982A CN 113088982 A CN113088982 A CN 113088982A CN 202110353850 A CN202110353850 A CN 202110353850A CN 113088982 A CN113088982 A CN 113088982A
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- Prior art keywords
- copper
- copper rod
- pickling
- polyoxyethylene ether
- rod
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- 239000010949 copper Substances 0.000 title claims abstract description 133
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 132
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 26
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 26
- 238000002791 soaking Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001509 sodium citrate Substances 0.000 claims abstract description 16
- 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 abstract description 16
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 13
- 235000019795 sodium metasilicate Nutrition 0.000 claims abstract description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005554 pickling Methods 0.000 claims description 64
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- -1 polydithio Polymers 0.000 claims description 12
- 108010010803 Gelatin Proteins 0.000 claims description 10
- 229920000159 gelatin Polymers 0.000 claims description 10
- 239000008273 gelatin Substances 0.000 claims description 10
- 235000019322 gelatine Nutrition 0.000 claims description 10
- 235000011852 gelatine desserts Nutrition 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 241000054822 Lycaena cupreus Species 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000002156 adsorbate Substances 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229960005339 acitretin Drugs 0.000 claims description 2
- IHUNBGSDBOWDMA-AQFIFDHZSA-N all-trans-acitretin Chemical compound COC1=CC(C)=C(\C=C\C(\C)=C\C=C\C(\C)=C\C(O)=O)C(C)=C1C IHUNBGSDBOWDMA-AQFIFDHZSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 13
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000009920 chelation Effects 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 206010067484 Adverse reaction Diseases 0.000 abstract description 3
- 230000006838 adverse reaction Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000007127 saponification reaction Methods 0.000 abstract description 2
- 150000002191 fatty alcohols Chemical class 0.000 abstract 2
- 150000003333 secondary alcohols Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000004190 Avilamycin Substances 0.000 description 6
- 229930192734 Avilamycin Natural products 0.000 description 6
- XIRGHRXBGGPPKY-OTPQUNEMSA-N [(2r,3s,4r,6s)-6-[(2'r,3's,3ar,4r,4'r,6s,7ar)-6-[(2s,3r,4r,5s,6r)-2-[(2r,3s,4s,5s,6s)-6-[(2r,3as,3'ar,6'r,7r,7's,7ar,7'ar)-7'-acetyl-7'-hydroxy-6'-methyl-7-(2-methylpropanoyloxy)spiro[4,6,7,7a-tetrahydro-3ah-[1,3]dioxolo[4,5-c]pyran-2,4'-6,7a-dihydro-3ah- Chemical compound O([C@H]1[C@H](O)C[C@@H](O[C@@H]1C)O[C@H]1[C@H](O)CC2(O[C@]3(C)C[C@@H](O[C@H](C)[C@H]3O2)O[C@H]2[C@@H](OC)[C@@H](C)O[C@H]([C@@H]2O)O[C@H]2[C@H](O)[C@H](OC)[C@H](OC3[C@@H]([C@@H]4O[C@]5(O[C@H]4CO3)[C@@H]3OCO[C@H]3[C@@](O)([C@@H](C)O5)C(C)=O)OC(=O)C(C)C)O[C@@H]2COC)O[C@@H]1C)C(=O)C1=C(C)C(Cl)=C(O)C(Cl)=C1OC XIRGHRXBGGPPKY-OTPQUNEMSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229960005185 avilamycin Drugs 0.000 description 6
- 235000019379 avilamycin Nutrition 0.000 description 6
- 238000005406 washing Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention discloses a glossy copper rod and a production method thereof, wherein the method of alkaline soaking-pre-pickling-acid soaking is used for removing residual oil stain on the surface of the copper rod in the processing process, the surface of the copper rod is filmed after acid soaking, the surface smoothness of the copper rod is prolonged, the oxidation of the copper rod is reduced, and the method of alkaline soaking-pre-pickling-acid soaking avoids the problem of surface depression of the copper rod, alkaline sodium hydroxide is used as a main saponification agent, sodium citrate and sodium metasilicate are used as auxiliary agents, fatty alcohol polyoxyethylene ether and secondary alcohol polyoxyethylene ether are used as surfactants, sodium citrate has strong coordination capacity to various metal ions and chelation to the heavy metal ions, the adverse reaction of ions in water to oil removal can be inhibited, the sodium metasilicate has good wettability and emulsibility, and is used together with the sodium citrate, can enhance the comprehensive performance of the fatty alcohol polyoxyethylene ether and the secondary alcohol polyoxyethylene ether.
Description
Technical Field
The invention relates to the technical field of copper rod production and copper rod surface treatment, in particular to a production method of a glossy copper rod.
Background
Copper is widely applied to the fields of electric power, light industry, mechanical manufacturing, building industry, national defense industry and the like because of good ductility, good electric conduction and heat conduction, diamagnetism, durability and convenience in recovery, but because the existing treatment method has no obvious improvement on the treatment of the copper surface, the attention on the copper color is not enough, the problems of poor purification, poor oxidation resistance and the like exist, the surface glossiness of a copper finished product is influenced, and the requirements of the existing copper product industry cannot be met, therefore, the purity and the appearance treatment of the copper product need to be better improved, and the attractiveness of the copper product finished product is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a glossy copper rod and a production method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme,
a method of producing a lustrous copper rod, comprising the steps of:
s1, after purifying raw material copper, putting the raw material copper into a smelting furnace in an argon atmosphere, and heating at a constant temperature of 1000-1200 ℃ to obtain liquid alloy;
s2, conveying the liquid alloy into casting equipment for casting to obtain a copper rod;
s3, preparing an oil removing solvent from 1-4% of sodium metasilicate, 0.5-2% of sodium citrate, 0.1-0.2% of sodium hydroxide, 0.06-0.15% of fatty alcohol-polyoxyethylene ether, 0.04-0.08% of secondary alcohol-polyoxyethylene ether and the balance of water by mass percent, heating the oil removing solvent to 30-50 ℃, and soaking the copper rod in the heated oil removing solvent for 5-20 min;
s4, placing the deoiled copper rod into a pre-pickling solution for pre-pickling;
and S5, placing the copper rod after pre-pickling into pickling solution for pickling, and airing after pickling to obtain a finished copper rod.
Preferably, the preparation method of the raw material copper in step S1 includes:
further purifying the crude copper to prepare a crude copper plate serving as an anode and pure copper serving as a cathode, putting the crude copper plate into an electrolyte containing a copper sulfate solution, and electrolyzing to obtain an adsorbate on the cathode as the raw material copper;
according to the required addition amount of each ton of copper, the electrolyte also comprises 30-55 g of gelatin, 30-75 g of thiourea, 20-50 g of acitretin, 160-190 g of hydrochloric acid and 30-50 g of polyethylene glycol.
Preferably, the pickling solution in the step S5 mainly comprises the following components in percentage by mass: 16 to 20 percent of sulfuric acid, 0.01 to 0.5 percent of hydrofluoric acid, 0.1 to 1 percent of 0.02 to 0.2 percent of hydrochloric acid and the balance of water.
Preferably, the pickling solution further comprises 0.03-1% of sodium polydithio-dipropyl sulfonate.
Preferably, the pre-pickling solution in the step S4 is, by mass, 2-4% of sulfuric acid, 1-3% of citric acid, and the balance water.
Compared with the prior art, the invention has the advantages that:
1. the method comprises the steps of removing residual oil stains on the surface of a copper rod in the machining process by using an alkali soaking-pre-pickling-acid soaking method, forming a film on the surface of the copper rod after acid soaking, prolonging the surface smoothness of the copper rod, and reducing the oxidation of the copper rod;
2. when the soap is soaked in alkali, alkaline sodium hydroxide is used as a saponification main agent, sodium citrate and sodium metasilicate are used as auxiliary agents, fatty alcohol-polyoxyethylene ether and secondary alcohol-polyoxyethylene ether are used as surfactants, the sodium citrate has strong coordination capacity to various metal ions and has strong chelation effect on heavy metal ions, adverse reaction of ions existing in water to oil removal can be inhibited, and the sodium metasilicate has good wettability and emulsibility and can enhance the comprehensive performance of the fatty alcohol-polyoxyethylene ether and the secondary alcohol-polyoxyethylene ether when being used together with the sodium citrate.
Detailed Description
The invention is further described in the following description and specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Comparative example 1:
s1, after purifying the crude copper, putting the crude copper into a smelting furnace in an argon atmosphere to heat at a constant temperature of 1150 ℃ to prepare a liquid alloy;
s2, conveying the liquid alloy into casting equipment for casting to obtain a copper rod;
s3, placing the copper rod into a pre-pickling solution for pre-pickling;
s4, placing the copper rod subjected to pre-pickling into a pickling solution for pickling, and drying after pickling to obtain a finished copper rod;
due to direct acid washing, oil stains are remained on most of the copper rods, and finally, the copper rods after acid washing are mottled, uneven and uneven.
Example 1:
a production method of a copper rod comprises the following steps:
s1, after purifying the crude copper, putting the crude copper into a smelting furnace in an argon atmosphere to heat at a constant temperature of 1150 ℃ to prepare a liquid alloy;
s2, conveying the liquid alloy into casting equipment for casting to obtain a copper rod;
s3, preparing an oil removing solvent from 3% of sodium metasilicate, 1% of sodium citrate, 0.2% of sodium hydroxide, 0.06% of fatty alcohol-polyoxyethylene ether, 0.08% of secondary alcohol-polyoxyethylene ether and the balance of water by mass percent, heating the oil removing solvent to 40 ℃, and soaking the copper rod in the heated oil removing solvent for 10 min;
s4, placing the deoiled copper rod into a pre-pickling solution for pre-pickling;
and S5, placing the copper rod after pre-pickling into pickling solution for pickling, and airing after pickling to obtain a finished copper rod.
Example 2:
a lustrous copper rod and a production method thereof comprise the following steps:
s1, further purifying the crude copper to prepare a crude copper plate serving as an anode, putting the crude copper plate serving as a cathode into an electrolyte containing a copper sulfate solution, and electrolyzing to obtain an adsorbate on the cathode as the raw material copper;
according to the required addition amount of each ton of copper, the electrolyte also comprises 40g of gelatin, 65g of thiourea, 30g of avilamycin, 170g of hydrochloric acid and 40g of polyethylene glycol;
putting the obtained raw material copper into a smelting furnace in an argon atmosphere, and heating at a constant temperature of 1150 ℃ to obtain liquid alloy;
s2, conveying the liquid alloy into casting equipment for casting to obtain a copper rod;
s3, preparing an oil removing solvent from 3% of sodium metasilicate, 1% of sodium citrate, 0.2% of sodium hydroxide, 0.06% of fatty alcohol-polyoxyethylene ether, 0.08% of secondary alcohol-polyoxyethylene ether and the balance of water by mass percent, heating the oil removing solvent to 40 ℃, and soaking the copper rod in the heated oil removing solvent for 13 min;
s4, placing the deoiled copper rod into a pre-pickling solution for pre-pickling;
and S5, placing the copper rod after pre-pickling into pickling solution for pickling, and airing after pickling to obtain a finished copper rod.
Example 3:
s1, further purifying the crude copper to prepare a crude copper plate serving as an anode, putting the crude copper plate serving as a cathode into an electrolyte containing a copper sulfate solution, and electrolyzing to obtain an adsorbate on the cathode as the raw material copper;
according to the required addition amount of each ton of copper, the electrolyte also comprises 40g of gelatin, 65g of thiourea, 30g of avilamycin, 170g of hydrochloric acid and 40g of polyethylene glycol;
putting the obtained raw material copper into a smelting furnace in an argon atmosphere, and heating at a constant temperature of 1150 ℃ to obtain liquid alloy;
s2, conveying the liquid alloy into casting equipment for casting to obtain a copper rod;
s3, preparing an oil removing solvent from 3% of sodium metasilicate, 1% of sodium citrate, 0.2% of sodium hydroxide, 0.06% of fatty alcohol-polyoxyethylene ether, 0.08% of secondary alcohol-polyoxyethylene ether and the balance of water by mass percent, heating the oil removing solvent to 40 ℃, and soaking the copper rod in the heated oil removing solvent for 13 min;
s4, placing the deoiled copper rod into a pre-pickling solution for pre-pickling;
s5, preparing a pickling solution from 15% of sulfuric acid, 0.3% of hydrofluoric acid, 0.08% of hydrochloric acid and the balance of water by mass percent, putting the copper rod after pre-pickling into the pickling solution for pickling, and airing after pickling to obtain the finished copper rod.
Example 4
S1, further purifying the crude copper to prepare a crude copper plate serving as an anode, putting the crude copper plate serving as a cathode into an electrolyte containing a copper sulfate solution, and electrolyzing to obtain an adsorbate on the cathode as the raw material copper;
according to the required addition amount of each ton of copper, the electrolyte also comprises 40g of gelatin, 65g of thiourea, 30g of avilamycin, 170g of hydrochloric acid and 40g of polyethylene glycol;
putting the obtained raw material copper into a smelting furnace in an argon atmosphere, and heating at a constant temperature of 1150 ℃ to obtain liquid alloy;
s2, conveying the liquid alloy into casting equipment for casting to obtain a copper rod;
s3, preparing an oil removing solvent from 3% of sodium metasilicate, 1% of sodium citrate, 0.2% of sodium hydroxide, 0.06% of fatty alcohol-polyoxyethylene ether, 0.08% of secondary alcohol-polyoxyethylene ether and the balance of water by mass percent, heating the oil removing solvent to 40 ℃, and soaking the copper rod in the heated oil removing solvent for 13 min;
s4, placing the deoiled copper rod into a pre-pickling solution for pre-pickling;
s5, preparing a pickling solution from 15% of sulfuric acid, 0.3% of hydrofluoric acid, 0.08% of hydrochloric acid, 0.08% of sodium polydithio dipropyl sulfonate and the balance of water by mass percent, putting the copper rod after pre-pickling into the pickling solution for pickling, and airing after pickling to obtain the finished copper rod.
Example 5
S1, further purifying the crude copper to prepare a crude copper plate serving as an anode, putting the crude copper plate serving as a cathode into an electrolyte containing a copper sulfate solution, and electrolyzing to obtain an adsorbate on the cathode as the raw material copper;
according to the required addition amount of each ton of copper, the electrolyte also comprises 40g of gelatin, 65g of thiourea, 30g of avilamycin, 170g of hydrochloric acid and 40g of polyethylene glycol;
putting the obtained raw material copper into a smelting furnace in an argon atmosphere, and heating at a constant temperature of 1150 ℃ to obtain liquid alloy;
s2, conveying the liquid alloy into casting equipment for casting to obtain a copper rod;
s3, preparing an oil removing solvent from 3% of sodium metasilicate, 1% of sodium citrate, 0.2% of sodium hydroxide, 0.06% of fatty alcohol-polyoxyethylene ether, 0.08% of secondary alcohol-polyoxyethylene ether and the balance of water by mass percent, heating the oil removing solvent to 40 ℃, and soaking the copper rod in the heated oil removing solvent for 13 min;
s4, placing the deoiled copper rod into an acid washing solution prepared from 2% sulfuric acid, 1.5% citric acid and the balance of water for pre-acid washing;
s5, preparing a pickling solution from 15% of sulfuric acid, 0.3% of hydrofluoric acid, 0.08% of hydrochloric acid, 0.08% of sodium polydithio dipropyl sulfonate and the balance of water by mass percent, putting the copper rod after pre-pickling into the pickling solution for pickling, and airing after pickling to obtain the finished copper rod.
The gloss of comparative example 1 and examples 1-2 were tested in a 20 ° geometry, with the results shown in table 1:
TABLE 1
| Comparative example 1 | Example 1 | Example 2 | |
| Glossiness (GU) | 349.2 | 537.5 | 594.1 |
After comparative example 1 and examples 2-5 were tested at 20 ° geometry, the samples were soaked in simulated seawater (3% NaCl aqueous solution) for 24 hours, and then the 20 ° geometry gloss test was performed again on comparative example 1 and examples 2-5 after soaking, and the results were recorded, and the specific test results are shown in table 2:
TABLE 2
| Comparative example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Before soaking | See Table 1 | See Table 1 | 596.2GU | 602.3GU | 607.4GU |
| After soaking | 185.2GU | 487.3GU | 549.7GU | 563.6GU | 576.1GU |
Referring to tables 1-2, and the contents of the above comparative examples and examples, comparing comparative example 1 with example 1, it can be seen that, in comparative example 1, the conventional crude copper purification-cast copper rod-direct pickling method is adopted, although the brightness is higher than that of the copper rod which is not pickled, but oil stains are remained on most of the copper rods due to direct pickling, and finally the copper rods are mottled and uneven after most of the pickling, in example 1, the method of alkali soaking-pre-pickling-acid soaking is adopted to remove the oil stains remained on the surfaces of the copper rods during the processing process, after acid soaking, a film is formed on the surfaces of the copper rods, so that the surface smoothness of the copper rods is prolonged, the oxidation of the copper rods is reduced, no mottled is found on the copper rods, the brightness is far greater than that of the copper rods prepared in comparative example 1 due to no mottled, and during the alkali soaking, alkaline sodium hydroxide is used as a main saponifying agent, sodium citrate and sodium metasilicate, the fatty alcohol-polyoxyethylene ether and the secondary alcohol-polyoxyethylene ether are used as surfactants, sodium citrate has strong coordination capacity to various metal ions, has strong chelation effect on heavy metal ions, can inhibit adverse reaction of ions existing in water to oil removal, simultaneously sodium metasilicate has good wettability and emulsibility, and can be used with sodium citrate to enhance the comprehensive performance of the fatty alcohol-polyoxyethylene ether and the secondary alcohol-polyoxyethylene ether;
comparing the embodiment 1 and the embodiment 2, it can be known that the embodiment 2 further optimizes the crude copper purification step on the basis of the embodiment 1, adopts an electrolytic purification method, is convenient, the brightness of the purified raw material copper is higher, the brightness of the finished product is directly improved from the raw material, the electrolyte is further optimized, gelatin, thiourea, avilamycin, hydrochloric acid and polyethylene glycol are added, the gelatin is used as a main additive and is dissociated into cations in the acid electrolyte, polymerization is formed on the protruding surface of the cathode, the growth of the protruding surface crystal grains is prevented, new crystal nuclei are generated, the final crystal grains of the cathode are more regular and compact, the inhibition effect of the gelatin on the protruding crystal grains on the surface of the cathode is effectively increased under the combined action of the thiourea, the avilamycin and the gelatin, the chloride ions generated by the hydrochloric acid reaction have the depolarization effect, the anode passivation is reduced, the crystal is further refined, and the crystal purity is higher;
comparing example 2 with example 3, it is known that in example 3, based on example 2, the components of the pickling solution are further optimized, sulfuric acid, hydrofluoric acid, and hydrochloric acid are used as the pickling solution, when the copper rod is placed, the apparent copper oxide reacts with the sulfuric acid, hydrofluoric acid, and hydrochloric acid to generate an organic complex in the solution, and the copper oxide with mottled surface of the copper rod is dissolved, so that the surface of the copper rod is better glossy, and the film is formed on the surface of the copper rod, and hydrogen ions generated by the reaction of the hydrofluoric acid, hydrochloric acid, and sulfuric acid make the film density better, and the film forming speed is slightly reduced, so that the film surface is more flat and regular;
comparing example 3 with example 4, it is seen that example 4 has a sodium polydithio dipropyl sulfonate component added to the pickling solution in addition to example 3, and the sodium polydithio dipropyl sulfonate is used in combination with a hydride formed from hydrofluoric acid and hydrochloric acid, so that the brightening property is better, and the brightening property is better than that of Cu formed during pickling2+Forming complexation resistance, refining the formation of the film surface on the surface of the copper rod, wherein the film surface can only generate or form new crystal nuclei along the side surface in an extension way, so that the final film formation on the copper rod is more regular, the film surface is smoother, and the brightness of the surface of a finished product is better;
comparing example 4 with example 5, it can be seen that in example 5, on the basis of example 4, the copper rod is pre-pickled by using sulfuric acid and citric acid, and the sulfuric acid and citric acid act synergistically to neutralize the alkalinity of the alkali soaking in a weak acid manner to ensure the subsequent pickling effect, and the metal chelation effect specific to citric acid can purify the heavy metal substances remained in the alkali soaking, so that the surface gloss of the copper rod is better, and the pickling film forming effect is better;
as can be seen from the above, example 5 is considered to be the most preferable example of the present invention because the copper rod produced in example 5 has the best brightness, the best oxidation and corrosion resistance, and the best brightness maintaining effect, compared to examples 1 to 4.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (5)
1. A method for producing a lustrous copper rod, characterized by comprising the following steps:
s1, putting raw material copper into a smelting furnace in an argon atmosphere, and heating at a constant temperature of 1000-1200 ℃ to prepare liquid alloy;
s2, conveying the liquid alloy into casting equipment for casting to obtain a copper rod;
s3, preparing an oil removing solvent from 1-4% of sodium metasilicate, 0.5-2% of sodium citrate, 0.1-0.2% of sodium hydroxide, 0.06-0.15% of fatty alcohol-polyoxyethylene ether, 0.04-0.08% of secondary alcohol-polyoxyethylene ether and the balance of water by mass percent, heating the oil removing solvent to 30-50 ℃, and soaking the copper rod in the heated oil removing solvent for 5-20 min;
s4, placing the deoiled copper rod into a pre-pickling solution for pre-pickling;
and S5, placing the copper rod after pre-pickling into pickling solution for pickling, and airing after pickling to obtain a finished copper rod.
2. The method for producing a lustrous copper rod as claimed in claim 1, wherein the method for preparing the raw material copper in the step S1 includes:
further purifying the crude copper to prepare a crude copper plate serving as an anode and pure copper serving as a cathode, putting the crude copper plate into an electrolyte containing a copper sulfate solution, and electrolyzing to obtain an adsorbate on the cathode as the raw material copper;
according to the required addition amount of each ton of copper, the electrolyte also comprises 30-55 g of gelatin, 30-75 g of thiourea, 20-50 g of acitretin, 160-190 g of hydrochloric acid and 30-50 g of polyethylene glycol.
3. The method for producing a lustrous copper rod as claimed in claim 1, wherein the pickling solution in step S5 includes the following main components by mass percent: 16 to 20 percent of sulfuric acid, 0.01 to 0.5 percent of hydrofluoric acid, 0.02 to 0.2 percent of hydrochloric acid and the balance of water.
4. The method for producing a lustrous copper rod as claimed in claim 1, wherein the pickling solution further includes 0.03-1% of sodium polydithio dipropyl sulfonate.
5. The method for producing a lustrous copper rod as claimed in claim 1, wherein the pre-pickling solution in step S4 includes 2-4% sulfuric acid, 1-3% citric acid, and the balance water, by mass.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117626281A (en) * | 2023-10-20 | 2024-03-01 | 东方蓝天钛金科技有限公司 | Solution and method for removing oxidation color on surface of GH4169 alloy bolt |
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