CN114059143A - Special anode for alkaline electro-deposition of zinc and zinc alloy and preparation method thereof - Google Patents
Special anode for alkaline electro-deposition of zinc and zinc alloy and preparation method thereof Download PDFInfo
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- CN114059143A CN114059143A CN202010756089.XA CN202010756089A CN114059143A CN 114059143 A CN114059143 A CN 114059143A CN 202010756089 A CN202010756089 A CN 202010756089A CN 114059143 A CN114059143 A CN 114059143A
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- 239000011701 zinc Substances 0.000 title claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 238000005137 deposition process Methods 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004512 die casting Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910000531 Co alloy Inorganic materials 0.000 claims description 2
- YABNZXGMDMFJCX-UHFFFAOYSA-N [Co].[Ti].[Fe] Chemical compound [Co].[Ti].[Fe] YABNZXGMDMFJCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 22
- 238000007747 plating Methods 0.000 abstract description 20
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 238000009713 electroplating Methods 0.000 abstract description 6
- 238000009825 accumulation Methods 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000005282 brightening Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000009689 gas atomisation Methods 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 5
- 229910004534 SiMn Inorganic materials 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229910000978 Pb alloy Inorganic materials 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- -1 amine compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
Abstract
The invention provides an anode special for alkaline electro-deposition of zinc and zinc alloy nickel and a preparation method thereof, belonging to the field of electroplating anodes. The anode provided by the invention takes iron as a matrix and is doped with titanium, cobalt and cerium to prepare an alloy material. By utilizing the oxygen storage capacity of the cerium oxide particles, part of free oxygen generated by water decomposition at the anode is adsorbed at the oxygen vacancy of the cerium oxide particles, accumulated and collided into oxygen, and released to form plating solution, so that the damage rate of the anode is effectively reduced, and the replacement frequency is reduced. The prepared anode can effectively reduce the decomposition of organic matters such as amines, brightening agents and the like, the accumulation of cyanide is reduced, the content of the cyanide in the plating solution can be controlled below 0.5mg/L, and the cost of the subsequent treatment of the cyanide is greatly reduced.
Description
Technical Field
The invention relates to the field of electroplating anodes, in particular to an anode special for alkaline electrodeposition of zinc and zinc alloy and a preparation method thereof.
Background
In the production process of alkaline galvanization, the concentration of zinc ions in the plating solution tends to rise gradually, because the soluble zinc anode plate is dissolved faster, particularly when the content of sodium hydroxide is high; in addition, the zinc anode is not taken out when the production line is stopped, so that the zinc anode plate can be subjected to self-dissolution, and the normal maintenance of the electrogalvanizing plating solution is seriously influenced by the uncontrollable dissolution mode of zinc ions.
Therefore, insoluble anodes are often used in alkaline zinc plating processes to control the zinc ion concentration in the bath. Conventional insoluble anodes coated with PbO2Pure lead anodes of thin films are representative, in the electrogalvanizing process, PbO2The film is easy to fall off from the substrate, which causes the problems that the plating solution seriously corrodes the substrate, the deposited zinc layer blackens and the binding force is poor. The problem of pure lead anodes is becoming more and more obvious, and the research on anodes of lead alloy, stainless steel, iron plates and the like is gradually concerned. The anode plate contains metal impurities such as chromium, nickel and the like, and the impurities can be dissolved into the plating solution to cause harm in the production process; iron plates hung in the plating tank for a long time may generate iron impurities due to dissolution. While oxidation reaction mainly occurs at the insoluble anode, the side oxidation reaction occurs at the anode by the additive of other amine compounds such as ethanolamine, enamine and the like, which causes the accumulation of cyanide, and the accumulation can reach 1000mg/L in the zinc-nickel electroplating process. According to the currently compiled 'discharge standard of pollutants in the electroplating industry' in China, the highest discharge standard of total cyanide in electroplating is 0.5mg/L, so that a cyanide treatment device is inevitably required to be additionally arranged, and the processing cost is increased.
In order to solve the above problems, experts and scholars have conducted a great deal of research, and have concentrated on the use of an ion exchange membrane to separate a cathode region from an anode region, thereby preventing a complexing agent from reaching the anode region and reducing oxidation reactions. Or a separator with small holes is used to selectively allow the cathode to move towards the anode. The contact between the cathode and the anode is separated in a diaphragm mode, so that the side reaction of organic additives such as brightening agents and the like is reduced, and the generation of cyanide is reduced. However, this method only partially reduces the production of cyanide and does not completely prevent the production of cyanide. Meanwhile, the ion exchange membrane and the polyethylene partition plate with holes are complex in equipment, difficult to maintain and high in installation and maintenance cost.
In addition, some patents provide cells for the anodic oxidation of cyanide in aqueous solution, the particulate bed of the anode of which is formed by particles of manganese or titanium oxide or a mixture of these particles, capable of reducing the formation of cyanide complexes. Meanwhile, in the process of electroplating zinc and nickel, the weight loss of the anode is mainly caused by the falling off of a metal oxide film, the oxygen absorption reaction is the main reaction at the anode, and part of absorbed oxygen can diffuse into the crystal lattice of the anode material to form metal oxide. Because the bonding force between the oxide and the matrix is poor, the film layer is loose, and finally the anode protective film falls off to aggravate the damage of the anode.
Disclosure of Invention
The invention aims to overcome the defects that organic matters are seriously decomposed, the generation amount of cyanide is large and an anode film is easy to fall off in the existing process of alkaline electrodeposition of zinc and zinc alloy nickel, and provides a special anode for alkaline electrodeposition of zinc and zinc alloy and a preparation method thereof.
The invention adopts the following technical scheme:
an anode special for alkaline electro-deposition of zinc and zinc alloy comprises the following components and structures:
the invention provides a cerium oxide doped iron-titanium-cobalt alloy anode, which comprises the following components in percentage by weight:
Fe 80-98%
Ti 1-12%
Co 2-6%
Ce 0.5-1.5%
preferably, it is
Fe 82-94%
Ti 3-8%
Co 2-5.5%
Ce 0.7-1.8%
More preferably
Fe 85-91%
Ti 3-8%
Co 2-5.5%
Ce 0.8 -1.8%
Wherein the cerium oxide particles are commercially available (crystal sharp) powder, and the particle size is 10-80nm, preferably 15-72nm, and more preferably 30-50 nm.
The invention also provides a preparation method of the anode, which mainly comprises the following steps: 1. preparing and synthesizing Fe, Ti and Co metal powder with the granularity of 1-9 mu m by an atomization method; 2. putting 85-91% of iron metal powder, 3-8% of titanium metal powder and 2-5.5% of cobalt metal powder into a high-temperature melting furnace for melting, wherein the melting time is not less than 50min, and more preferably not less than 70 min; 3. multi-stage die casting the molten fluid into a strip in a mold, forming and cooling, the thickness is preferably 1-3 μm, more preferably 1.8-2.5 μm; 4. the die-cast strip was baked in an electric furnace and argon was introduced as a shielding gas. The calcination time is preferably 3 to 8 hours, more preferably 4 to 6 hours. The firing temperature is preferably 700-1300 ℃, more preferably 900-1300 ℃. The flow rate of the argon gas is preferably 120-250ml/min, more preferably 180-230 ml/min; 5. cerium oxide particles were deposited on the surface of the strip using a deposition process to obtain the final anode.
As a preferred embodiment of the method for producing the anode of the present invention, the atomization method in the step 1 may be a gas atomization method.
The protective gas selected by the gas atomization method is argon, and the atomizer is a molten metal discharge spout or a metal ceramic discharge spout.
The invention discloses a special anode for alkaline electro-deposition of zinc and zinc alloy, which is an alloy material prepared by doping titanium and cobalt with iron as a matrix. The prepared anode can effectively reduce the decomposition of organic matters such as amines, brightening agents and the like, the accumulation of cyanide is reduced, the content of the cyanide in the plating solution can be controlled below 0.5mg/L, and the cost of the subsequent treatment of the cyanide is greatly reduced. Since cerium has a specific electron shell structure, cerium oxide particles have excellent oxygen storage capacity, and Ce ions thereof are easily converted between +3 and +4 valences, thereby easily forming oxygen vacancies in cerium oxide lattices. The formation of a large number of oxygen vacancies is favorable for the rapid transmission of electrons, so that the electrocatalytic capacity of the cerium dioxide is enhanced, and the adsorption of free oxygen atoms is facilitated. Partial free oxygen generated by water decomposition at the anode is adsorbed at the oxygen vacancy of the nano cerium oxide particles, accumulated collision is oxygen, plating solution is released, the anode damage rate can be effectively reduced, the replacement frequency is reduced, and the production cost is reduced.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following is a detailed description based on specific examples.
Example 1.
And (3) testing conditions are as follows: preparing an alkaline zinc-nickel plating solution, wherein
Zn 8.3g/L，
Ni 0.9g/L
NaOH 122g/L
Ethylene diamine 0.3ml/L
Triethanolamine 28ml/L
Dimethylamine 0.8ml/L
Current density 4A/dm2
The temperature is 25 DEG C
Cathode material: steel fastener (35 SiMn)
Anode material:
Fe 88%
Ti 7%
Co 3.5%
Ce 1.5%
the cerium oxide particles are commercially available (sharp) powder with a particle size of about 34 nm.
The method comprises the following main preparation steps:
1. preparing and synthesizing Fe, Ti and Co metal powder by adopting a gas atomization method, wherein the granularity is about 3 mu m; 2. putting 88% of iron metal powder, 7% of titanium metal powder and 3.5% of cobalt metal powder into a high-temperature melting furnace for melting for about 55 min; 3. multi-stage die casting the molten fluid into a strip in a mold, forming and cooling, wherein the thickness is preferably 2.3 mu m; 4. the die-cast strip was baked in an electric furnace and argon was introduced as a shielding gas. The roasting time is 4h, and the roasting temperature is 950 ℃. The flow of argon gas is 190 ml/min; 5. cerium oxide particles were deposited on the surface of the strip using a deposition process to obtain the final anode.
Plating solution maintenance: the components are supplemented every 10AH/L, wherein zinc is added in the form of zinc oxide, nickel is added in the form of nickel sulfate, and sodium hydroxide is adjusted to be about 122g/L after titration analysis.
The cyanide content of the plating solution was measured after applying currents of 150AH/L and 200 AH/L.
Example 2.
And (3) testing conditions are as follows: preparing an alkaline zinc-nickel plating solution, wherein
Zn 9.2g/L，
Ni 1.1g/L
NaOH 125g/L
Ethylene diamine 0.5ml/L
Triethanolamine 26.5ml/L
Dimethylamine 1ml/L
Current density 6A/dm2
The temperature is 25 DEG C
Cathode material: steel fastener (35 SiMn)
Anode material:
Fe 88%
Ti 8%
Co 3.2%
Ce 0.8%
the cerium oxide particles are commercially available (sharp) powder with the particle size of about 40 nm.
The method comprises the following main preparation steps: 1. preparing and synthesizing Fe, Ti and Co metal powder by a gas atomization method, wherein the granularity is about 4 mu m; 2. putting 88% of iron metal powder, 8% of titanium metal powder and 3.2% of cobalt metal powder into a high-temperature melting furnace for melting for about 70 min; 3. multi-stage die casting the molten fluid into a strip in a mold, forming and cooling, wherein the thickness is preferably 1.8 mu m; 4. the die-cast strip was baked in an electric furnace and argon was introduced as a shielding gas. The roasting time is 4.5h, and the roasting temperature is 1100 ℃. The flow of argon gas is 200 ml/min; 5. cerium oxide particles were deposited on the surface of the strip using a deposition process to obtain the final anode.
Plating solution maintenance: adding the components every 10AH/L, wherein zinc is added in the form of zinc oxide, nickel is added in the form of nickel sulfate, and sodium hydroxide is adjusted to be about 125g/L after titration analysis.
The cyanide content of the plating solution was measured after applying currents of 150AH/L and 200 AH/L.
Comparative example 1.
And (3) testing conditions are as follows: preparing an alkaline zinc-nickel plating solution, wherein
Zn 9.2g/L，
Ni 1.1g/L
NaOH 125g/L
Ethylene diamine 0.5ml/L
Triethanolamine 26.5ml/L
Dimethylamine 1ml/L
Current density 6A/dm2
The temperature is 25 DEG C
Cathode material: steel fastener (35 SiMn)
Anode material:
Fe 88%
Ti 8%
Co 3.2%
Ce 0.8%
the cerium oxide particles are commercially available (sharp) powder with the particle size of about 40 nm.
The method comprises the following main preparation steps:
1. the Fe, Ti and Co metal powder is prepared and synthesized by a gas atomization method, and the granularity is about 4 mu m.
2. And (3) putting 88% of iron metal powder, 8% of titanium metal powder and 3.2% of cobalt metal powder into a high-temperature melting furnace for melting for about 70 min.
3. The molten fluid is die cast in multiple stages in a mold into a strip, the shape is cooled and the thickness is preferably 1.8 μm.
4. The die-cast strip was baked in an electric furnace and argon was introduced as a shielding gas. The roasting time is 4.5h, and the roasting temperature is 1100 ℃. The flow of argon was 200 ml/min.
5. Cerium oxide particles were deposited on the surface of the strip using a deposition process to obtain the final anode.
Plating solution maintenance: adding the components every 10AH/L, wherein zinc is added in the form of zinc oxide, nickel is added in the form of nickel sulfate, and sodium hydroxide is adjusted to be about 125g/L after titration analysis.
The contrast anode 1 is bright nickel-plated steel; a steel sheet having a nickel coating of 30 μm on the surface thereof.
Comparative anode 2: lead alloy anode: the component is Pb-5% Sn
The cyanide content (mg/L) in the plating solution was measured after applying currents of 150AH/L and 200 AH/L.
The ethylene diamine content (mg/L) in the bath was measured after applying currents of 150AH/L and 200 AH/L.
Comparative example 2.
And (3) testing conditions are as follows: preparing an alkaline zinc-nickel plating solution, wherein
Zn 9.7g/L
Ni 1.2g/L
NaOH 130g/L
Ethylene diamine 0.7ml/L
Triethanolamine 28ml/L
Dimethylamine 1.2ml/L
Current density 5.5A/dm2
The temperature is 25 DEG C
Cathode material: steel fastener (35 SiMn)
Anode material:
and (3) implementing an anode: the anode provided in example 2.
The contrast anode 1 is bright nickel-plated steel; a steel sheet having a nickel coating of 30 μm on the surface thereof.
Comparative anode 2: lead alloy anode: the component is Pb-5% Sn
The cyanide content of the bath was measured after applying a current of 1000AH/L, as well as triethanolamine.
The weight loss of the anode was measured after applying a current of 1000 AH/L.
As can be seen, the weight loss and breakage of the comparative anode 1 and the comparative anode 2 are significant; the anode provided by the invention has the minimum weight loss and the slowest breakage rate.
Claims (4)
1. An alkaline electrodeposition zinc and zinc alloy special anode and a preparation method thereof are characterized in that: the anode is a cerium oxide doped iron-titanium-cobalt alloy anode and comprises the following components:
Fe 80-98%；
Ti 1-12%；
Co 2-6%；
Ce 0.5-1.5%。
2. the special anode for alkaline electrodeposition of zinc and zinc alloys and the preparation method thereof according to claim 1, characterized in that: a preparation method of the anode is provided, which mainly comprises the following steps:
1) preparing and synthesizing Fe, Ti and Co metal powder with the granularity of 1-9 mu m by adopting an atomization method;
2) melting 80-98% of iron metal powder, 1-12% of titanium metal powder and 2-6% of cobalt metal powder in a high-temperature melting furnace for not less than 50min, preferably not less than 70 min;
3) multi-stage die casting the molten fluid into a strip in a mold, and forming and cooling the strip to a thickness of preferably 1 to 3 μm, more preferably 1.8 to 2.5 μm;
4) the die-cast strip is fired in an electric furnace, argon is introduced as a protective gas, the firing time is preferably 3 to 8 hours, more preferably 4 to 6 hours,
the calcination temperature is preferably 700-1300 ℃, more preferably 900-1300 ℃, and the argon gas flow is preferably 120-250ml/min, more preferably 180-230 ml/min;
5) depositing cerium oxide particles on the surface of the strip using a deposition process to obtain a final anode.
3. The special anode for alkaline electrodeposition of zinc and zinc alloys and the preparation method thereof according to claim 1, characterized in that: the anode preferably has a composition
Fe 82-94%；
Ti 3-8%；
Co 2-5.5%；
Ce 0.7-1.8%。
4. The special anode for alkaline electrodeposition of zinc and zinc alloys and the preparation method thereof according to claim 1, characterized in that: the anode is more preferably composed of
Fe 85-91%；
Ti 3-8%；
Co 2-5.5%；
Ce 0.8 -1.8%。
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| CN1575348A (en) * | 2001-10-23 | 2005-02-02 | 住友金属工业株式会社 | Hot press forming method, and a plated steel material therefor and its manufacturing method |
| CN105189831A (en) * | 2013-03-21 | 2015-12-23 | 安美特德国有限公司 | Apparatus and method for electrolytic deposition of metal layers on workpieces |
| US20160024683A1 (en) * | 2013-03-21 | 2016-01-28 | Atotech Deutschland Gmbh | Apparatus and method for electrolytic deposition of metal layers on workpieces |
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