CN104611609B - A kind of non-ferrous metal electrodeposition preparation method of the low polynary anode material of argentalium alloy - Google Patents
A kind of non-ferrous metal electrodeposition preparation method of the low polynary anode material of argentalium alloy Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 100
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 239000010405 anode material Substances 0.000 title claims abstract description 33
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 23
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 44
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010936 titanium Substances 0.000 claims abstract description 42
- 229910000978 Pb alloy Inorganic materials 0.000 claims abstract description 33
- 238000012545 processing Methods 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910052738 indium Inorganic materials 0.000 claims abstract description 19
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 18
- YZASAXHKAQYPEH-UHFFFAOYSA-N indium silver Chemical compound [Ag].[In] YZASAXHKAQYPEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- QNZFKUWECYSYPS-UHFFFAOYSA-N lead zirconium Chemical compound [Zr].[Pb] QNZFKUWECYSYPS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000005096 rolling process Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005272 metallurgy Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000010891 electric arc Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 8
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 8
- DNUURYZWCQXQOR-UHFFFAOYSA-N [In][Ag][Pb] Chemical compound [In][Ag][Pb] DNUURYZWCQXQOR-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002701 Ag-Co Inorganic materials 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 15
- 239000011701 zinc Substances 0.000 abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052725 zinc Inorganic materials 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000005363 electrowinning Methods 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 238000009499 grossing Methods 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000009854 hydrometallurgy Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- OEZQCMMAFSEXQW-UHFFFAOYSA-N calcium silver Chemical compound [Ca].[Ag] OEZQCMMAFSEXQW-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The present invention relates to a kind of non-ferrous metal electrodeposition preparation method with the low polynary anode material of argentalium alloy, the percentage by weight of described anode material is silver 0.1～0.2%, and indium 0.1～1%, stannum 0.1～0.5%, zirconium 0.1～0.3%, titanium 0.01～0.4%, surplus is lead.The fabrication processing of anode plate body is: be initially charged stannum titanium intermediate alloy after being melted by lead, part lead is added after to be melted, silver indium and lead zirconium intermediate alloy is added after to be melted, the lead adding surplus after to be melted obtains metal liquid to fusing, is then poured into a mould by metal liquid, obtains blank flat after cooling, rolling afterwards obtains lead alloy plate, carry out lead alloy plate again increasing list processing, then smooth, shear, after activated process, obtain production board.The anode material of the present invention uses at higher current densities has excellent corrosion resistance, and at wet method electrowinning zinc, bath voltage is greatly reduced, reduces energy consumption during the electrometallurgy such as wet method electro deposited copper and manganese.
Description
Technical field
The present invention relates to a kind of novel anode material for electro-deposition of nonferrous metals preparation method technical field, be specifically related to a kind of preparation method being electrolysed the low polynary anode material of argentalium alloy used for non-ferrous metal.
Background technology
In whole commercial production, metallurgical industry remains big power consumer, and energy consumption is high, and its main specific energy consumption average specific Foreign Advanced Lerel is high by 40%.In the smelting process of non-ferrous metal, the zinc of about more than 80% is extracted by hydrometallurgical technology.In Zinc Hydrometallurgy Process, electrodeposition operation has consumed whole zinc and has extracted the energy consumption of process 2/3, and the energy consumption of zinc hydrometallurgy is 3800～4200kwh/t.Zn, produces per year in terms of 5,000,000 tons of zinc by the whole nation in 2007, power consumption is 20,300,000,000 kilowatt hours, accounts for the 0.64～0.75% of whole nation industry total electricity consumption.Especially in the case of current global economy depression, to reducing metallurgical industry energy consumption, improve enterprise independent innovation ability and the upgrading industrial structure is significant, one is to alleviate China's energy-intensive situation, two is to exploit in a large number and reserves minimizing, grade of ore reduction, rise in price, corresponding exploitation processing cost increase in mineral resources, and can increase the competitive advantage of enterprise under the situation of product price degradation.Both at home and abroad above-mentioned electrolytic deposition process of metal insoluble anode is conducted in-depth research and develops.The most current research and service condition are as follows:
1, Ca system lead based alloy anodes low Ag multicomponent alloy, the interpolation of calcium is favorably improved the mechanical property of anode, reduces anode silver content, but anode is easily generated local corrosion in electrolytic process, surface anode mud crust is hard, is difficult to remove and cause tank voltage high, and when anode reclaims, the loss of silver calcium is big.
2, the low Ag of Co system lead based alloy anodes or without Ag alloy, Co has good electro-catalysis effect, Pb-Co3O4With Pb-Ag (0.2%)-Sn (0.12%)-Co (0.06%) alloy anode, there is the overpotential for oxygen evolution lower than Pb-Ag (1.0%) anode and higher decay resistance, but the dissolubility that Co is in lead melt is atomic, preparation method is complicated.
3, DSA is with Fe, Pt, pottery etc. as substrate, and wherein Ti base DSA is study hotspot, and overall dimensions is stable, the short circuit problem caused without bending；Zinc percentage of product is high；Pole plate is lightweight, and convenient carrying and process are changed；Can be used for multiple electric effusion system；It is applicable to high current density (4.5～6.0kA/m2) and the electrodeposition condition of narrow die opening (about 5mm).But service life is short, the metal that Titanium base is easily passivated and uses in anodic coating easily causes burning plate phenomenon etc..
4, lead base composite anode is at Pb matrix surface composite noble metal oxide catalyst, IrOx, RuO2With good analysis oxygen electro catalytic activity and electrochemical stability, but the preparation cost of anode and anode make a breakthrough service life not yet, limit the popularization and application of such anode.
In order to overcome the weakness of lead-based multi-component alloy, people study the degenerative element that corrosion resistance is strong further, its object is to improve the recrystallization temperature of lead, the crystal grain of refinement lead, improve mechanical strength and bending resistance, the tensile strength of lead, and keep good electric conductivity and resistance to corrosion.Such as, Ivanov " Ivanov I, Stefanov Y, Noncheva Z, Petrova M, Dobrev Ts,
Mirkova L, Vermeersch R, Demaerel J.-P. Insoluble anodes used in
hydrometallurgy Part I. Anodic behaviour of lead and lead-alloy anodes[J].
Hydrometallurgy, 2000,57:109-124 " literary composition reviews the anti-corrosion of different lead based alloy anodes and electrocatalysis characteristic.Finding that the anode forming ternary alloy three-partalloy in Ti addition pb-ag alloy has good corrosion resistance, along with the increase of Ti content, the dissolving in sulfuric acid solution of the Pb metal reduces, and the proportioning of best corrosion resistance is Pb-0.75%Ag-0.5%Ti.W. Zhang " Zhang W,
Houlachi G. Electrochemical studies of the performance of different Pb-Ag
anodes during and after zinc electrowinning[J]. Hydrometallurgy, 2010,
104 (2): 129-35 " literary composition is thought alterant element Zr can be formed in sulphuric acid corrosion resistance strong Cubic ZrO2.But their preparation method has no report.R. H. NEWNHAM is at " Newnham
R H. Corrosion rates of lead based anodes for zinc electrowinning at high
Current densities. Journal of Applied Electrochemistry, 1992,22 (2): 116-124 " one the article pointed out, at 5000A/m2High current density polarization find Pb-(0.37%) Ag-(0.99%) Tl-0.12%Ca anode it is considered to be a kind of perfect alloy anode, corrosion resistance increases by four times, and the dissolubility of Pb reduces by five times.But Tl has the highest toxicity, is unfavorable for industrial applicability.And along with the increase of labor cost, improve electric current density and can reduce labour force, it is easy to changing electrolysis bath, maintenance time is short, and electrolyte is not easy to reveal, and more can energy-saving consumption-reducing.But traditional lead-silver anode is the most perishable, the lead contamination negative electrode of generation, it is impossible to satisfy social needs.
Summary of the invention
The invention aims to the shortcoming overcoming the existence of above-mentioned prior art, a kind of non-ferrous metal electrodeposition low polynary anode material of argentalium alloy and preparation method thereof is provided, makes the anode prepared use at higher current densities and have that electro catalytic activity is good and the advantage of length electrode life.
The purpose of the present invention is achieved through the following technical solutions:
A kind of non-ferrous metal electrodeposition preparation method of the low polynary anode material of argentalium alloy, described anode material is low silver-lead indium stannum zirconium Ti alloyed anode plate body, the composition of this plate body alloy material is silver 0.1～0.2% by weight percentage, indium 0.1～1%, stannum 0.1～0.5%, zirconium 0.1～0.3%, titanium 0.01～0.4%, surplus is lead；The fabrication processing of anode plate body is: be initially charged stannum titanium intermediate alloy after being melted by the lead of total lead weight 2/3, part lead is added after to be melted, silver indium and lead zirconium intermediate alloy is added after to be melted, the lead adding surplus after to be melted obtains metal liquid to fusing, is then poured into a mould by metal liquid, obtains blank flat after cooling, rolling afterwards obtains lead alloy plate, carry out lead alloy plate again increasing list processing, then smooth, shear, after activated process, obtain production board.
Silver indium intermediate alloy of the present invention uses fine vacuum electric arc melting method to be molten into containing indium mass percent 40～the AI alloy of 60%.Described lead zirconium intermediate alloy uses vacuum metallurgy method to be molten into the lead zircaloy containing zirconium mass percent 20%.Described stannum titanium intermediate alloy uses vacuum metallurgy method to be molten into the stannum titanium alloy of titaniferous mass percent 9%.The pouring type of metal liquid is aluminium alloy to pour into quick water-cooled erect in mould, is cooled to room temperature.It is 0.1～0.25 millimeter that lead alloy plate increases the pattern depth after list processing, and decorative pattern width is 2.5～4.0 millimeters.Described activation processing is that the lead alloy plate after increasing list processing is placed on containing in cobalt nitrate liquid fused salt, soaks 0.5～3h under the conditions of temperature 90～160 DEG C.The lead alloy plate that described activation processing can also be after increasing list processing is placed in the nitrate solution of Ag and Co or Ag-Co alloy immersion 0.5～3h, then being placed in heat treatment tank type stove heat treatment 1～28h under 100～300 DEG C of temperature conditionss, nitrate solution concentration is 0.01g/L～10g/L.Acetum can be used to clean lead alloy plate before activation processing.
The present invention has the advantage that compared to existing technology
1) corrosion resistance that can improve metal due to alterant silver and indium and the tank voltage reduced in electrolytic process, doping Ag and In plays collaborative effect, lead based alloy anodes can be made to have minimum overpotential for oxygen evolution and best corrosion resistance；
2) silver indium intermediate alloy uses the fusing of fine vacuum electric arc melting method can reduce the scaling loss of noble metal and make alloying component uniform；
3) lead zirconium and stannum titanium intermediate alloy use vacuum smelting method can reduce the scaling loss of zirconium and titanium；
4) introducing has alterant element titanium and zirconium, can greatly strengthen the corrosion resistance of anode；
5) use quick water-cooled to erect die casting and prepare lead-based multi-component alloy, quickly cooling makes the alloy material normal desolvation process of not free generation, can be dissolved in when liquid in another material, when solid-state the most insoluble, thus prepare the homogeneous mixture of all elements, the corrosion resistance making alloy is greatly improved, and performance is homogeneous；
6) use activation processing can improve the catalysis activity of anode surface, make anode be more easy at higher current densities release oxygen, reduce tank voltage；
The anode material of the present invention is especially suitable for using at higher current densities, can improve production capacity, reduces the labour force of cleaning trough, it is easy to safeguard.Also can reduce the quantity of additive, and improve the overpotential of liberation of hydrogen, favourable to current efficiency, and it is obtained in that the cathode product that crystallization is careful.
Detailed description of the invention
Embodiment
1
A kind of non-ferrous metal electrodeposition is low silver-lead indium stannum zirconium Ti alloyed anode plate body with the low polynary anode material of argentalium alloy, this anode material, and the composition of this plate body alloy material is silver 0.18% by weight percentage, indium 0.6%, stannum 0.3%, zirconium 0.21%, titanium 0.09%, surplus is lead.Plate body is manufactured into 240mm(high) ×
160mm(width) × 6mm(thickness) sample, manufacture method comprises the steps:
A, electrolysis lead that purity is 99.9% is melted in intermediate frequency furnace under the conditions of 340 DEG C, it is rapidly heated after fusing 860～980 DEG C and adds stannum titanium intermediate alloy, stir after to be melted, add part lead, after temperature 700 DEG C, add silver indium, lead zirconium intermediate alloy, to be melted and be stirring evenly and then adding into surplus lead to fusing obtain metal liquid.Lead adds in three times, and addition is the 2/3 of total lead weight for the first time, after twice leading play the effect reducing temperature, it is according to temperature and improves efficiency and determines.Stannum titanium intermediate alloy is the stannum titanium alloy of the titaniferous mass percent 9% using the fusing of vacuum metallurgy method, silver indium intermediate alloy is the AI alloy containing indium mass percent 40% using the fusing of fine vacuum electric arc melting method, and lead zirconium intermediate alloy is the lead zircaloy containing zirconium mass percent 20% using the fusing of vacuum metallurgy method；
B, by after the metal liquid of gained magnetic agitation respectively and mechanical agitation 20min, drag for slag, proceed to quick water-cooled and erect in die device, obtain blank flat, lead alloy plate is obtained through rolling, then carry out lead alloy plate increasing list processing, through increasing the pattern depth 0.1 of lead alloy plate after list processing～0.25 millimeter, decorative pattern width 2.5～4.0 millimeters, finally by smoothing, after shearing use weight percent concentration 10% acetum clean, then washing after be dipped in 150 DEG C containing in cobalt nitrate liquid fused salt soak 2h, hot water clean after obtain production board.
By the above-mentioned low polynary positive plate of argentalium alloy at electrowinning zinc bath system (Zn2+50g/L, H2SO4150 g/L, Mn2+5g/L, temperature is 35 DEG C) in application, with 5000A/m2Electric current density be electrolysed, compared with traditional alloy lead anode plate, the tank voltage of this low polynary anode of argentalium alloy reduces by 14%, and rate of corrosion reduces 60%.To energy saving, the consumption reducing lead anode has obvious action.
Embodiment
2
A kind of non-ferrous metal electrodeposition is low silver-lead indium stannum zirconium Ti alloyed anode plate body with the low polynary anode material of argentalium alloy, this anode material, and the composition of this plate body alloy material is silver 0.2% by weight percentage, indium 0.1%, stannum 0.5%, zirconium 0.21%, titanium 0.2%, surplus is lead.Plate body is manufactured into 240mm(high) ×
160mm(width) × 8mm(thickness) sample, manufacture method comprises the steps:
A, electrolysis lead that purity is 99.9% is melted under the conditions of 340 DEG C in intermediate frequency furnace (electrolysis lead weight is the 2/3 of total lead), it is rapidly heated after fusing 860～980 DEG C and adds stannum titanium intermediate alloy, stir after to be melted, add part lead, after temperature 700 DEG C, be separately added into silver indium, lead zirconium intermediate alloy, to be melted after be stirring evenly and then adding into surplus lead to fusing obtain metal liquid；Stannum titanium intermediate alloy is the stannum titanium alloy of the titaniferous mass percent 9% using the fusing of vacuum metallurgy method, silver indium intermediate alloy is the AI alloy containing indium mass percent 50% using the fusing of fine vacuum electric arc melting method, and lead zirconium intermediate alloy is the lead zircaloy containing zirconium mass percent 20% using the fusing of vacuum metallurgy method；
B, after the metal liquid of gained magnetic agitation respectively and mechanical agitation 20min, drag for slag, proceed to quick water-cooled and erect in die device, obtain blank flat, lead alloy plate is obtained through rolling, then carry out lead alloy plate increasing list processing, through increasing the pattern depth 0.1 of lead alloy plate after list processing～0.25 millimeter, decorative pattern width 2.5～4.0 millimeters, finally by smoothing, the acetum using 10% after shearing cleans, it is dipped in the most after washing in the silver nitrate solution of volumetric concentration 0.2g/L soaking 3h, then being placed in heat treatment tank type stove with temperature is to obtain production board after 200 DEG C of heat treatment 20h cool down.
By the above-mentioned low polynary positive plate of argentalium alloy at electro deposited copper bath system (Cu2+40g/L, H2SO4180 g/L, temperature is 60 DEG C) in application, with 2000A/m2Electric current density be electrolysed, compared with traditional alloy lead anode plate, the tank voltage of this low polynary anode of argentalium alloy reduces by 20%, and rate of corrosion reduces 80%.
Embodiment
3
A kind of non-ferrous metal electrodeposition is low silver-lead indium stannum zirconium Ti alloyed anode plate body with the low polynary anode material of argentalium alloy, this anode material, and the composition of this plate body alloy material is silver 0.1% by weight percentage, indium 1 %, stannum 0.3%, zirconium 0.3%, titanium 0.01%, surplus is lead.
Plate body manufacture method is as follows:
A, electrolysis lead that purity is 99.9% is melted in intermediate frequency furnace under the conditions of 340 DEG C, it is rapidly heated after fusing 860～980 DEG C and adds stannum titanium intermediate alloy, stir after to be melted, add part lead, after temperature 700 DEG C, add silver indium, lead zirconium intermediate alloy, to be melted and be stirring evenly and then adding into surplus lead to fusing obtain metal liquid；；Stannum titanium intermediate alloy is the stannum titanium alloy of the titaniferous mass percent 9% using the fusing of vacuum metallurgy method, silver indium intermediate alloy is the AI alloy containing indium mass percent 45% using the fusing of fine vacuum electric arc melting method, and lead zirconium intermediate alloy is the lead zircaloy containing zirconium mass percent 20% using the fusing of vacuum metallurgy method；
B, by after the metal liquid of gained magnetic agitation respectively and mechanical agitation 20min, drag for slag, proceed to quick water-cooled and erect in die device, obtain blank flat, lead alloy plate is obtained through rolling, then carry out lead alloy plate increasing list processing, through increasing the pattern depth 0.1 of lead alloy plate after list processing～0.25 millimeter, decorative pattern width 2.5～4.0 millimeters, finally by smoothing, after shearing use weight percent concentration 10% acetum clean, then washing after be dipped in 160 DEG C containing in cobalt nitrate liquid fused salt soak 0.5h, hot water clean after obtain production board.
Embodiment
4
A kind of non-ferrous metal electrodeposition is low silver-lead indium stannum zirconium Ti alloyed anode plate body with the low polynary anode material of argentalium alloy, this anode material, and the composition of this plate body alloy material is silver 0.18% by weight percentage, indium 0.8 %, stannum 0.3%, zirconium 0.2%, titanium 0.3%, surplus is lead.
Plate body manufacture method is as follows:
A, electrolysis lead that purity is 99.9% is melted in intermediate frequency furnace under the conditions of 340 DEG C, it is rapidly heated after fusing 860～980 DEG C and adds stannum titanium intermediate alloy, stir after to be melted, add part lead, after temperature 700 DEG C, be separately added into silver indium, lead zirconium intermediate alloy, to be melted after be stirring evenly and then adding into surplus lead to fusing obtain metal liquid；Stannum titanium intermediate alloy is the stannum titanium alloy of the titaniferous mass percent 9% using the fusing of vacuum metallurgy method, silver indium intermediate alloy is the AI alloy containing indium mass percent 55% using the fusing of fine vacuum electric arc melting method, and lead zirconium intermediate alloy is the lead zircaloy containing zirconium mass percent 20% using the fusing of vacuum metallurgy method；
B, after the metal liquid of gained magnetic agitation respectively and mechanical agitation 20min, drag for slag, proceed to quick water-cooled and erect in die device, obtain blank flat, lead alloy plate is obtained through rolling, then carry out lead alloy plate increasing list processing, through increasing the pattern depth 0.1 of lead alloy plate after list processing～0.25 millimeter, decorative pattern width 2.5～4.0 millimeters, finally by smoothing, the acetum using 10% after shearing cleans, be dipped in the most after washing volumetric concentration 0.01g/L containing in cobalt nitrate dissolved salt liquid soak 2h, then being placed in heat treatment tank type stove with temperature is to obtain production board after 300 DEG C of heat treatment 1h cool down.
Embodiment
5
A kind of non-ferrous metal electrodeposition is low silver-lead indium stannum zirconium Ti alloyed anode plate body with the low polynary anode material of argentalium alloy, this anode material, and the composition of this plate body alloy material is silver 0.15% by weight percentage, indium 0.5 %, stannum 0.1%, zirconium 0.1%, titanium 0.4%, surplus is lead.
Plate body manufacture method is as follows:
A, electrolysis lead that purity is 99.9% is melted in intermediate frequency furnace under the conditions of 340 DEG C, it is rapidly heated after fusing 860～980 DEG C and adds stannum titanium intermediate alloy, stir after to be melted, add part lead, after temperature 700 DEG C, be separately added into silver indium, lead zirconium intermediate alloy, to be melted after be stirring evenly and then adding into surplus lead to fusing obtain metal liquid；Stannum titanium intermediate alloy is the stannum titanium alloy of the titaniferous mass percent 9% using the fusing of vacuum metallurgy method, silver indium intermediate alloy be use fine vacuum electric arc melting method fusing containing indium mass percent 40～the AI alloy of 60%, lead zirconium intermediate alloy be use vacuum metallurgy method fusing the lead zircaloy containing zirconium mass percent 20%；
B, after the metal liquid of gained magnetic agitation respectively and mechanical agitation 20min, drag for slag, proceed to quick water-cooled and erect in die device, obtain blank flat, lead alloy plate is obtained through rolling, then carry out lead alloy plate increasing list processing, through increasing the pattern depth 0.1 of lead alloy plate after list processing～0.25 millimeter, decorative pattern width 2.5～4.0 millimeters, finally by smoothing, the acetum using 10% after shearing cleans, it is dipped in the most after washing in the cobalt nitrate solution of volumetric concentration 10g/L soaking 0.5h, then being placed in heat treatment tank type stove with temperature is to obtain production board after 100 DEG C of heat treatment 28h cool down.
Embodiment
6
A kind of non-ferrous metal electrodeposition is low silver-lead indium stannum zirconium Ti alloyed anode plate body with the low polynary anode material of argentalium alloy, this anode material, and the composition of this plate body alloy material is silver 0.1% by weight percentage, indium 0.5 %, stannum 0.4%, zirconium 0.3%, titanium 0.2%, surplus is lead.
Plate body manufacture method is as follows:
A, electrolysis lead that purity is 99.9% is melted in intermediate frequency furnace under the conditions of 340 DEG C, it is rapidly heated after fusing 860～980 DEG C and adds stannum titanium intermediate alloy, stir after to be melted, add part lead, after temperature 700 DEG C, add silver indium, lead zirconium intermediate alloy, to be melted and be stirring evenly and then adding into surplus lead to fusing obtain metal liquid；；Stannum titanium intermediate alloy is the stannum titanium alloy of the titaniferous mass percent 9% using the fusing of vacuum metallurgy method, silver indium intermediate alloy is the AI alloy containing indium mass percent 45% using the fusing of fine vacuum electric arc melting method, and lead zirconium intermediate alloy is the lead zircaloy containing zirconium mass percent 20% using the fusing of vacuum metallurgy method；
B, by after the metal liquid of gained magnetic agitation respectively and mechanical agitation 20min, drag for slag, proceed to quick water-cooled and erect in die device, obtain blank flat, lead alloy plate is obtained through rolling, then carry out lead alloy plate increasing list processing, through increasing the pattern depth 0.1 of lead alloy plate after list processing～0.25 millimeter, decorative pattern width 2.5～4.0 millimeters, finally by smoothing, after shearing use weight percent concentration 10% acetum clean, then washing after be dipped in 90 DEG C containing in cobalt nitrate liquid fused salt soak 2h, hot water clean after obtain production board.
Claims (9)
1. the non-ferrous metal electrodeposition preparation method of the low polynary anode material of argentalium alloy, it is characterized in that, described anode material is low silver-lead indium stannum zirconium Ti alloyed anode plate body, the composition of this plate body alloy material is silver 0.1～0.2% by weight percentage, indium 0.1～1%, stannum 0.1～0.5%, zirconium 0.1～0.3%, titanium 0.01～0.4%, surplus is lead；The fabrication processing of anode plate body is: be initially charged stannum titanium intermediate alloy after being melted by the lead of total lead weight 2/3, part lead is added after to be melted, silver indium and lead zirconium intermediate alloy is added after to be melted, the lead adding surplus after to be melted obtains metal liquid to fusing, is then poured into a mould by metal liquid, obtains blank flat after cooling, rolling afterwards obtains lead alloy plate, carry out lead alloy plate again increasing list processing, then smooth, shear, after activated process, obtain production board.
A kind of non-ferrous metal electrodeposition the most according to claim 1 preparation method of the low polynary anode material of argentalium alloy, it is characterised in that described silver indium intermediate alloy uses fine vacuum electric arc melting method to be molten into containing indium mass percent 40～the AI alloy of 60%.
A kind of non-ferrous metal electrodeposition the most according to claim 1 preparation method of the low polynary anode material of argentalium alloy, it is characterised in that described lead zirconium intermediate alloy uses vacuum metallurgy method to be molten into the lead zircaloy containing zirconium mass percent 20%.
A kind of non-ferrous metal electrodeposition the most according to claim 1 preparation method of the low polynary anode material of argentalium alloy, it is characterised in that described stannum titanium intermediate alloy uses vacuum metallurgy method to be molten into the stannum titanium alloy of titaniferous mass percent 9%.
A kind of non-ferrous metal electrodeposition the most according to claim 1 preparation method of the low polynary anode material of argentalium alloy, it is characterised in that the pouring type of metal liquid is aluminium alloy to pour into quick water-cooled erect in mould, is cooled to room temperature.
A kind of non-ferrous metal electrodeposition the most according to claim 1 preparation method of the low polynary anode material of argentalium alloy, it is characterised in that it is 0.1～0.25 millimeter that lead alloy plate increases the pattern depth after list processing, and decorative pattern width is 2.5～4.0 millimeters.
A kind of non-ferrous metal electrodeposition the most according to claim 1 preparation method of the low polynary anode material of argentalium alloy, it is characterized in that, described activation processing is that the lead alloy plate after increasing list processing is placed on containing in cobalt nitrate liquid fused salt, soaks 0.5～3h under the conditions of temperature 90～160 DEG C.
A kind of non-ferrous metal electrodeposition the most according to claim 7 preparation method of the low polynary anode material of argentalium alloy, it is characterized in that, described activation processing is that the lead alloy plate after increasing list processing is placed in the nitrate solution of Ag and Co or Ag-Co alloy immersion 0.5～3h, then being placed in heat treatment tank type stove heat treatment 1～28h under 100～300 DEG C of temperature conditionss, nitrate solution concentration is 0.01g/L～10g/L.
9. according to the preparation method of the low polynary anode material of argentalium alloy of a kind of non-ferrous metal electrodeposition according to any one of claim 1-8, it is characterised in that use acetum to clean lead alloy plate before activation processing.
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| CN108728872B (en) * | 2018-06-13 | 2020-03-27 | 昆明理工大学 | Aluminum bar Pb-Sn-Sb/α -PbO for copper electrodeposition2-Co3O4Composite electrode material and preparation method thereof |
| CN114232035A (en) * | 2021-12-21 | 2022-03-25 | 贵州省新材料研究开发基地 | Modified anode for hydrometallurgy and preparation method thereof |
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