CN105401168A - Method for preparing copper-nickel alloy by electro-deposition of low-grade copper and nickel mixed ore - Google Patents
Method for preparing copper-nickel alloy by electro-deposition of low-grade copper and nickel mixed ore Download PDFInfo
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Abstract
The invention discloses a method for preparing copper-nickel alloy by electro-deposition of low-grade copper and nickel mixed ore. The method comprises the following steps: by taking the low-grade copper and nickel mixed ore as a raw material, sequentially performing oxidizing roasting and chloridizing roasting to prepare a copper-nickel electrolysis precursor; taking choline chloride/urea ion liquid as an electrolyte; putting excess copper-nickel electrolysis precursor; in the ion liquid to form an ion liquid-copper and nickel salt composite electrolyte solution; performing electro-deposition by adopting a three-electrode system, namely adopting a platinum disk electrode as a counter electrode; adopting a polished and acidic-activated to-be-plated titanium sheet metal base body as a working electrode; adopting a platinum electrode as a reference electrode; performing electro-deposition reaction for 60min to 120min at the temperature of 60 to 90 DEG C and at the voltage of -1.30V to -1.50V. By regulating any parameters of the reaction temperature, the cathode potential and the deposition time, the growth shape and size of the copper-nickel alloy can be effectively controlled. The method disclosed by the invention has the characteristics of short technological process, low energy consumption, high efficiency, low raw material cost and the like and is applied to the technical field of an environment-friendly electro-deposition technique.
Description
Technical field
The present invention relates to a kind of cupronickel preparation technology, particularly a kind ofly pre-treatment is carried out to copper nickel composite ore and directly prepares the method for cupronickel in conjunction with hydrometallurgical processes, be applied to the Technology field that the green metallurgical comprehensive of mineral utilizes.
Background technology
Non-ferrous metal is widely used in the every field of the national economy such as national defence, aerospace, electron electric power, communications and transportation, petrochemical complex, in national economy and national defense construction, have important strategic position.But deepening continuously along with nonferrous metal resource exploitation, China's nonferrous metal resource shortage problem becomes increasingly conspicuous, and the degree of self-sufficiency of the coloured resource of China also declines year by year, and import dependency significantly increases, and if things go on like this, will form potential threat to national security.Causing the reason of above serious situation to be the explored nonferrous metal resources of China about 75% to be at present cannot the difficult Mineral resources such as low-grade, multi-metal complex ore deposit of economic utilization, and this part difficult Mineral resources mainly low-grade oxidation-sulfuration composite ore.
Complex multi-metal composite ore, its composition of ores is various, and valuable metal thing is mainly the sulfide minerals such as chalcopyrite, pyrrhotite, pentlandite mutually, in addition containing the oxide mineral such as magnetite, serpentine and gangue.Metallurgical industry in modern times is over more than 100 year, tradition non-ferrous metal selecting and smelting technology is mainly for the treatment of sulphide ores, mostly adopt copper nickel bulk flotation-melting-converter mattes fragmentation, ore grinding-copper nickel flotation separation at present, prepare nickelous sulfide/copper electrode through pyrometallurgical smelting and blowing again, then carry out the technique that electrorefining obtains electro deposited nickel/copper respectively.For high-grade cu-ni sulphide ore, this kind for the treatment of process technical maturity, production efficiency is high.But when processing low-grade composite ore, there is nickel recovery by pyrogenic attack low, the problems such as production cost is high.And the main stream approach of wet processing is acidleach-selectivity electrodeposition process, but when iron in ore magnesium calcium contents height, this technique acid consumption is comparatively large, and subsequent purification dedoping step is comparatively complicated.So composite ore adopts traditional selecting and smelting technology high efficiency separation to extract, main metal recovery rate is lower, seeks the inevitable requirement that new short route clean metallurgical technique has been coloured resources effective utilization.
Cupronickel comparatively other copper alloys machineries and physicals all abnormal good, its ductility is good, hardness is high, color and luster is attractive in appearance, corrosion-resistant, be rich in deep drawability, be widely used in the fields such as shipbuilding, petrochemical complex, electrical equipment, instrument, medicine equipment, art.The preparation method of current cupronickel mainly contains mechanical alloying method, reduction method, supersonic method, powder metallurgic method, the hot method of hydrothermal/solvent, Static pressure synthesis method etc.These synthetic methods, although successfully can synthesize cupronickel, its major part prepared is the powder of cupronickel.Main adding elements nickel in cupronickel is a kind of rare strategic materials, expensive, and the method for direct large batch of use melting synthesis prepares that cupronickel cost is large, cost is high, thus limits the widespread use of cupronickel.Current galvanostatic deposition is prepared cupronickel and is received increasing concern, but the nickel needed for galvanic deposit/copper source remains the compounds such as single nickel salt/copper, nickelous chloride/copper, nickelous nitrate/copper, and needs a large amount of promoting agents and complexing agent.Metal target is directly prepared in recent years and alloy receives increasing concern from complex ore, research and development low temperature, novel green hydrometallurgical processes that is efficient, short route have become mineral and have studied important research direction, and the technique how utilizing low-grade copper nickel composite ore directly to prepare cupronickel becomes galvanic deposit urgently to be resolved hurrily and prepares metallic copper nickel technical problem.
Summary of the invention
In order to solve prior art problem, the object of the invention is to the deficiency overcoming prior art existence, a kind of method being prepared cupronickel by the galvanic deposit of low-grade copper nickel composite ore is provided, for specific low-grade copper nickel composite ore, first selective oxidation and chlorination is carried out, form the chlorinating intermediate of copper nickel and be dissolved in ionic liquid, cupronickel is isolated finally by electrochemistry controllable deposition method, ionic liquid electrolyte solution is reusable, do not produce other by products, raw material and intermediate treatment process simple, reaction conditions easily realizes, the inventive method has process control, efficiency is high, with low cost, the features such as energy consumption is low.
Creating object for reaching foregoing invention, adopting following technical proposals:
Prepared a method for cupronickel by the galvanic deposit of low-grade copper nickel composite ore, step is as follows:
A. the preparation of ionic liquid electrolyte solution: with choline chloride 60 and urea for initial feed, the ratio being 1:2 in the feed composition mol ratio of choline chloride 60 and urea carries out raw material mixing, at 80 ~ 100 DEG C, constant temperature stirs 10 ~ 12 hours, until formed evenly, water white transparency shape ionic liquid is as electrolyte solution;
B. copper nickel composite ore pre-treatment: carry out levigate to copper nickel mixed ore, and divide post-drying by 200 mesh sieves, then dried breeze is carried out oxidizing roasting 1 ~ 2 hour in oxidizing atmosphere at 600 ~ 700 DEG C of temperature, again the mixed mineral powder after oxidizing roasting is carried out chloridizing roasting, chloridizing roasting is carried out in HCl atmosphere, the temperature of chloridizing roasting is 350 ~ 450 DEG C, the chloridizing roasting time is 0.5 ~ 1 hour, after completing chloridizing roasting, cool to the product of chloridizing roasting with the furnace room temperature, obtain chloridizing roasting mineral dust; When carrying out pre-treatment to copper nickel composite ore, the oxidizing atmosphere gas that oxidizing roasting process adopts preferably adopts air; When carrying out pre-treatment to copper nickel composite ore, in oxidizing roasting process, the air flow rate of preferred controlled oxidization atmosphere is close to 80mL/min, and in chloridizing roasting process, preferred control HCl gas flow is close to 80mL/min.
C. the preparation of the saturated ionic liquid of copper nickel: chloridizing roasting mineral dust pretreated in described step b is placed in the ionic liquid prepared in described step a and carries out mixing and dissolving, at 60 ~ 100 DEG C, constant temperature stirs 8 ~ 10 hours, obtains ionic liquid-copper nickel salt composite electrolytic solution that copper nickel is saturated;
D. the formation of cell system: using polytetrafluoroethylene beaker as electrolyzer, platinum disk electrode is to electrode, be negative electrode working electrode through polishing, acidic activated plating metal matrix, take platinum electrode as reference electrode, using the saturated ionic liquid-copper nickel salt composite electrolytic solution of the copper nickel prepared in described step c as electrolyte solution, form cell system; Preferably using titanium sheet as cell system negative electrode;
E. the galvanic deposit preparation process of cupronickel: the electrolytic reaction temperature of the cell system formed in described steps d is remained on 60 ~ 90 DEG C, then applying electromotive force to cell system is the direct current of-1.30 ~-1.50V, controlling electrodeposition time is 60 ~ 120 minutes, carries out galvanic deposit; In the galvanic deposit preparation process of cupronickel, preferably by any several the processing parameters in regulation and control electrolytic reaction temperature, electromotive force and electrodeposition time parameter, realize the control to cupronickel sedimentation velocity and deposit thickness;
F. the product through described step e galvanic deposit gained is taken out from electrolyzer, first clean with deionized water, repeatedly clean with dehydrated alcohol again, until galvanic deposit products therefrom is cleaned, finally oven drying at low temperature is carried out to the product of galvanic deposit gained, namely obtain cupronickel at plating metal matrix surface, achieve direct enrichment from low-grade composite ore and extract cupronickel.
principle of the present invention:
The present invention makes the cuprous chloride that dissolves in ionogen and nickelous chloride be reduced into cupronickel at working electrode by the electromotive force that electrochemistry three-electrode system accurately controls working electrode.The present invention adopts and prepares the enrichment that ionic liquid method realizes copper nickel object element in low-grade copper nickel composite ore, ionic liquid has that electrochemical window is wide, chemical heat stability is high, specific conductivity is high, without vapour pressure, non-combustible, the excellent properties such as repeatedly can to recycle, be a kind of novel green solvent.Compared to fused salt, the aqueous solution and organic solvent, when adopting ionic liquid to carry out galvanic deposit, there are wider electrochemical window, higher current efficiency, lower temperature of reaction and lower corrodibility.Due to advantages such as good economy performance, added value are high, recoverables, in ionic liquid, galvanic deposit is prepared metal and alloy and is at home and abroad received and pay close attention to widely in recent years, is particularly that raw material electrodeposit metals and alloy research in ionic liquid are the most extensive with muriate.Metal oxide, sulfide or other compounds under certain condition greatly can be very strong with chemically reactive chlorine react, and control the selective chlorination that reaction conditions can realize valuable elements in minerals.Therefore, the present invention is directed to specific difficult composite ore, carry out the selective chlorination of valuable element, form chlorinating intermediate and carry out selective dissolution by specific ion liquid to chlorination mineral constituent again, last combined with electrochemical deposition can realize controlled extraction or the alloying of valency constituent element.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the present invention with low-grade copper nickel composite ore for main raw material, short route is adopted to prepare cupronickel, by having valency constituent element to be selectively converted to metal chloride by low-grade copper nickel composite ore, and then selective dissolution prepares cupronickel in ionic liquid by galvanic deposit;
2. the present invention adopts HCl gas as chlorizating agent, and chlorination efficiency is high, and controlling reaction conditions can the selective chlorination of realize target constituent element, and product is water vapour and produces without other obnoxious flavoures, and the HCl in tail gas can recycle;
3. the present invention adopts choline chloride/urea ionic liquid as electrolytic solution, have economy, environmental protection, preparation simple, can the advantage that uses of recirculation, and by regulating electrochemical process parameter, accurately can control the forming core process of growth of deposited copper nickelalloy;
4. the invention solves a difficult problem for low-grade copper nickel composite ore comprehensive utilization, adopt that this art breading composite ore simple operation, flow process are simple, process control and without other side reactions, be a kind of efficient low-consume of subzero treatment copper nickel mixed mineral, the novel process of environmental protection.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention one prepares the schematic flow sheet of the method for cupronickel by the galvanic deposit of low-grade copper nickel composite ore.
Fig. 2 is surface topography scanning electron microscope (SEM) figure of the low-grade copper nickel composite ore that the embodiment of the present invention one adopts.
Fig. 3 is X-ray diffraction (XRD) figure of the low-grade copper nickel composite ore that the embodiment of the present invention one adopts.
Fig. 4 is surface topography scanning electron microscope (SEM) figure of the artificial mineral's presoma embodiment of the present invention one made after chloridizing roasting by low-grade copper nickel composite ore.
Fig. 5 is X-ray diffraction (XRD) figure of artificial mineral's presoma that low-grade copper nickel composite ore is made by the embodiment of the present invention one after chloridizing roasting.
Fig. 6 is that the embodiment of the present invention one adopts electro-deposition method to prepare surface topography scanning electron microscope (SEM) figure of cupronickel.
Fig. 7 is that the embodiment of the present invention one adopts electro-deposition method to prepare power spectrum (EDS) figure of cupronickel.
Fig. 8 is that the embodiment of the present invention one and embodiment two adopt electro-deposition method to prepare the current density-time plot of cupronickel process.
Fig. 9 is that the embodiment of the present invention two adopts electro-deposition method to prepare power spectrum (EDS) figure of cupronickel.
Figure 10 is that the embodiment of the present invention two adopts electro-deposition method to prepare power spectrum (EDS) figure of cupronickel.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
embodiment one:
In the present embodiment, see Fig. 1 ~ 8, a kind of method being prepared cupronickel by the galvanic deposit of low-grade copper nickel composite ore, step is as follows:
A. the preparation of ionic liquid electrolyte solution: with choline chloride 60 and urea for initial feed, first take 58.18g choline chloride 60 and 50g urea and mix in 200mL beaker, then at 80 DEG C, thermostatic electromagnetic stirs 12 hours, generate to even, water white transparency shape ionic liquid, in the ionic liquid of synthesis, measure 50mL be placed in polytetrafluoroethylene beaker stand-by;
B. copper nickel composite ore pre-treatment: low-grade mixed ore is broken, be ground to all mineral dusts and sieved by 200 orders and dry, levigate breeze is nickeliferous 2.2%, cupric 2.5%, iron content 39.9%, shown in the SEM figure of breeze and XRD figure 2 and Fig. 3, containing nickel, copper, iron, sulphur multiple associated minerals phase element in known breeze, form stable or metastable sulfide mineral and oxide mineral mixed mineral, the porcelain boat that levigate mineral dust is housed is placed in controlled atmosphere kiln and carries out roasting, roasting divides two sections to carry out, first 600 DEG C of continued oxidation roastings 1 hour is warming up to, controlling air gas flow is 80mL/min, cool to 400 DEG C again with the furnace, in controlled atmosphere kiln, pass into HCl gas carry out chloridizing roasting, control HCl gas flow is 80mL/min, continue roasting 1 hour again, after roasting terminates, cool to the product of chloridizing roasting with the furnace room temperature again, from controlled atmosphere kiln, take out roasting mineral dust and seal preservation, the SEM figure of roasting breeze and XRD figure are as shown in Figure 4 and Figure 5, the product of known low-grade mixed ore powder after chloridizing roasting is primarily of nickelous chloride, cuprous chloride and ferric oxide composition, achieve the selective chlorination of target nickel element and copper,
C. the preparation of the saturated ionic liquid of copper nickel: excessive pretreated chloridizing roasting mineral dust in described step b is placed in the choline chloride/urea ionic liquid prepared in described step a and carries out mixing and dissolving, at 60 DEG C, constant temperature stirs 10 hours, obtains the choline chloride/urea ionic liquid containing saturated copper nickel;
D. the formation of cell system: using polytetrafluoroethylene beaker as electrolyzer, three-electrode system is adopted to carry out galvanic deposit, be to electrode with platinum disk electrode, to be of a size of 0.4cm × 0.5cm titanium sheet for working electrode through polishing, acidic activated length and width, take platinum electrode as reference electrode, and above-mentioned three electrodes are fixed in tetrafluoroethylene electrolyzer, using the saturated ionic liquid of copper nickel prepared in described step c as electrolyte solution, assembling forms electro-deposition system;
E. the galvanic deposit preparation process of cupronickel: the temperature adopting HCP-803 type electrochemical workstation, constant-temperature temperature-control instrument and electric mantle to regulate and control electrodeposition process working electrode potential and electrolyzer Inner electrolysis plastome respectively carries out galvanic deposit, the electrolytic reaction temperature of the cell system formed in described steps d is remained on 80 DEG C, adopting three-electrode system to control working electrode potential is-1.30V voltage, makes electrodeposit reaction carry out 120 minutes; Current density-the time curve of electrodeposition process as shown in Figure 8; Because choline chloride/urea ionic liquid has relatively high solubleness to cuprous chloride and nickelous chloride, and complex compound is formed in the process of dissolving, weaken the bonding force of copper nickel and chlorine in cuprous chloride and nickelous chloride, facilitate the carrying out of electrodeposit reaction, improve reaction efficiency, only there is the deposition of metallic copper nickel and analyse chlorine reaction in whole reaction system, choline chloride/urea ionic liquid decomposes, and ionogen is capable of circulation repeatedly to be used;
F. the product through described step e galvanic deposit gained is taken out from electrolyzer, first clean with deionized water, repeatedly clean with dehydrated alcohol again, until galvanic deposit products therefrom is cleaned, finally oven drying at low temperature is carried out to the product of galvanic deposit gained, namely obtain cupronickel at plating metal matrix surface, achieve direct enrichment from low-grade composite ore and extract cupronickel.
The SEM figure and EDS Fig. 6 of the cupronickel product that the present embodiment obtains as shown in Figure 7, can find out that the present embodiment can obtain cupronickel at negative electrode titanium sheet substrates from the microscopic appearance of product and energy spectrum analysis, demonstrate the present embodiment fully and utilize the success of choline chloride/urea ionic liquid to prepare cupronickel from the galvanic deposit of low-grade copper nickel composite ore.The present embodiment, by control temperature and the parameter such as electromotive force, time, realizes cupronickel growth morphology, the isoparametric effective control of size, for producing the controlled synthesis novel method providing a kind of brand-new cupronickel.The present embodiment is for specific low-grade copper nickel composite ore, first selective oxidation and chlorination is carried out, form the chlorinating intermediate of copper nickel and be dissolved in ionic liquid, cupronickel is isolated finally by electrochemistry controllable deposition method, ionic liquid electrolyte solution is reusable, do not produce other by products, simply, reaction conditions easily realizes for raw material and intermediate treatment process.The present embodiment technique has the features such as flow process is short, energy consumption is low, efficiency is high, low in raw material price.
embodiment two:
The present embodiment is substantially identical with embodiment one, and special feature is:
In the present embodiment, see Fig. 8 ~ 10, a kind of method being prepared cupronickel by the galvanic deposit of low-grade copper nickel composite ore, step is as follows:
A. the preparation of ionic liquid electrolyte solution: this step is identical with embodiment one;
B. copper nickel composite ore pre-treatment: this step is identical with embodiment one;
C. the preparation of the saturated ionic liquid of copper nickel: this step is identical with embodiment one;
D. the formation of cell system: this step is identical with embodiment one;
E. the galvanic deposit preparation process of cupronickel: the temperature adopting HCP-803 type electrochemical workstation, constant-temperature temperature-control instrument and electric mantle to regulate and control electrodeposition process working electrode potential and electrolyzer Inner electrolysis plastome respectively carries out galvanic deposit, the electrolytic reaction depositing temperature of the cell system formed in described steps d is remained on 80 DEG C, adopting three-electrode system to control working electrode potential is-1.50V voltage, makes electrodeposit reaction carry out 120 minutes; Current density-the time curve of electrodeposition process as shown in Figure 8;
F. the product through described step e galvanic deposit gained is taken out from electrolyzer, first clean with deionized water, repeatedly clean with dehydrated alcohol again, until galvanic deposit products therefrom is cleaned, finally oven drying at low temperature is carried out to the product of galvanic deposit gained, namely obtain cupronickel at plating metal matrix surface, achieve direct enrichment from low-grade composite ore and extract cupronickel.
The SEM figure and EDS Fig. 9 of the cupronickel product that the present embodiment obtains as shown in Figure 10, can find out that the present embodiment can obtain cupronickel at negative electrode titanium sheet substrates from the microscopic appearance of product and energy spectrum analysis, demonstrate the present embodiment and utilize the success of choline chloride/urea ionic liquid to prepare cupronickel from the galvanic deposit of low-grade copper nickel composite ore.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; multiple change can also be made according to the object of innovation and creation of the present invention; change, the modification made under all spirit according to technical solution of the present invention and principle, substitute, combination or simplify; all should be the substitute mode of equivalence; as long as goal of the invention according to the invention; only otherwise deviate from the present invention prepares the method for cupronickel know-why and inventive concept by the galvanic deposit of low-grade copper nickel composite ore, all protection scope of the present invention is belonged to.
Claims (5)
1. prepared a method for cupronickel by the galvanic deposit of low-grade copper nickel composite ore, it is characterized in that, step is as follows:
A. the preparation of ionic liquid electrolyte solution: with choline chloride 60 and urea for initial feed, the ratio being 1:2 in the feed composition mol ratio of choline chloride 60 and urea carries out raw material mixing, at 80 ~ 100 DEG C, constant temperature stirs 10 ~ 12 hours, until formed evenly, water white transparency shape ionic liquid is as electrolyte solution;
B. copper nickel composite ore pre-treatment: carry out levigate to copper nickel mixed ore, and divide post-drying by 200 mesh sieves, then dried breeze is carried out oxidizing roasting 1 ~ 2 hour in oxidizing atmosphere at 600 ~ 700 DEG C of temperature, again the mixed mineral powder after oxidizing roasting is carried out chloridizing roasting, chloridizing roasting is carried out in HCl atmosphere, the temperature of chloridizing roasting is 350 ~ 450 DEG C, the chloridizing roasting time is 0.5 ~ 1 hour, after completing chloridizing roasting, cool to the product of chloridizing roasting with the furnace room temperature, obtain chloridizing roasting mineral dust;
C. the preparation of the saturated ionic liquid of copper nickel: chloridizing roasting mineral dust pretreated in described step b is placed in the ionic liquid prepared in described step a and carries out mixing and dissolving, at 60 ~ 100 DEG C, constant temperature stirs 8 ~ 10 hours, obtains ionic liquid-copper nickel salt composite electrolytic solution that copper nickel is saturated;
D. the formation of cell system: using polytetrafluoroethylene beaker as electrolyzer, platinum disk electrode is to electrode, be negative electrode working electrode through polishing, acidic activated plating metal matrix, take platinum electrode as reference electrode, using the ionic liquid prepared in described step c-copper nickel salt composite electrolytic solution as electrolyte solution, form cell system;
E. the galvanic deposit preparation process of cupronickel: the electrolytic reaction temperature of the cell system formed in described steps d is remained on 60 ~ 90 DEG C, then applying electromotive force to cell system is the direct current of-1.30 ~-1.50V, controlling electrodeposition time is 60 ~ 120 minutes, carries out galvanic deposit;
F. the product through described step e galvanic deposit gained is taken out from electrolyzer, first clean with deionized water, repeatedly clean with dehydrated alcohol again, until galvanic deposit products therefrom is cleaned, finally oven drying at low temperature is carried out to the product of galvanic deposit gained, namely obtain cupronickel at plating metal matrix surface, achieve direct enrichment from low-grade composite ore and extract cupronickel.
2. prepared the method for cupronickel according to claim 1 by the galvanic deposit of low-grade copper nickel composite ore, it is characterized in that: when carrying out pre-treatment to copper nickel composite ore in described step b, the oxidizing atmosphere gas that oxidizing roasting process adopts is air.
3. according to claim 1 or 2, the method for cupronickel is prepared by the galvanic deposit of low-grade copper nickel composite ore, it is characterized in that: in the galvanic deposit preparation process of described step e cupronickel, by any several the processing parameters in regulation and control electrolytic reaction temperature, electromotive force and electrodeposition time parameter, realize the control to cupronickel sedimentation velocity and deposit thickness.
4. according to claim 1 or 2, the method for cupronickel is prepared by the galvanic deposit of low-grade copper nickel composite ore, it is characterized in that: when pre-treatment being carried out to copper nickel composite ore in described step b, in oxidizing roasting process, the air flow rate of controlled oxidization atmosphere is close to 80mL/min, and in chloridizing roasting process, control HCl gas flow is close to 80mL/min.
5. according to claim 1 or 2, prepared the method for cupronickel by the galvanic deposit of low-grade copper nickel composite ore, it is characterized in that: in described steps d, using titanium sheet as cell system negative electrode.
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| CN109174436B (en) * | 2018-09-11 | 2020-11-17 | 中国恩菲工程技术有限公司 | Smelting method of nickel sulfide ore |
| WO2020108188A1 (en) * | 2018-11-29 | 2020-06-04 | 华南理工大学 | Apparatus and method for recovering variable valence metals from hazardous solid wastes by low-temperature reductive chlorination |
| CN110029370A (en) * | 2019-04-17 | 2019-07-19 | 上海大学 | By the method for low value cupro-nickel composite ore electro-deposition preparation high level ternary alloy three-partalloy |
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