CN101892502A - Copper-chromium-molybdenum ternary alloy coating and preparation method thereof - Google Patents
Copper-chromium-molybdenum ternary alloy coating and preparation method thereof Download PDFInfo
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- CN101892502A CN101892502A CN 201010238309 CN201010238309A CN101892502A CN 101892502 A CN101892502 A CN 101892502A CN 201010238309 CN201010238309 CN 201010238309 CN 201010238309 A CN201010238309 A CN 201010238309A CN 101892502 A CN101892502 A CN 101892502A
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Abstract
The invention discloses a copper-chromium-molybdenum ternary alloy coating and a preparation method thereof. The preparation method comprises the following steps of: dissolving a nitric acid with distilled water, adding sodium molebdate hexahydrate for stirring and dissolving, adjusting a pH value to be 1.5 to 3.3, sequentially adding lanthanum chloride, ammonium sulfate and ammonium formate, adjusting the pH value to be 2.1 to 4.0, sequentially adding blue copperas, chromium sulfate hexahydrate and a boric acid, adding the remaining distilled water, and adjusting the pH value to be 2.0 to 3.8 to obtain electroplating solution; performing polishing and chemical washing on the surface of a substrate, placing the treated substrate into an electroplating bath, dipping the substrate into the electroplating solution, electroplating and depositing the substrate for 30 to 60 minutes at 40 to 55 DEG C, taking the substrate out after the electroplating is finished, and washing and drying the substrate to obtain the copper-chromium-molybdenum ternary alloy coating. In the copper-chromium-molybdenum ternary alloy coating and the preparation method thereof, the alloy components of the surface can be changed according to specific requirements so as to improve the hardness, strength and wear-resisting property of the surface, while the component of a core part is also Cu with high electrical conductivity and thermal conductivity.
Description
Technical field
The invention belongs to the electroplated film disk technical field, particularly a kind of copper-chromium-molybdenum (Cu-Cr-Mo) ternary alloy coating and preparation method thereof.
Background technology
Mechanotronics high speed development now, many mechanic and electrical materials need be led at high electricity, move under high thermal conductance and the high strength operating mode.As commutator, electric car and the electric power train aerial condutor of direct-current generator, electrician's plug, switch, electric motor ring header etc.This class material adopts melting QCr0.5 usually or adds a small amount of Zr, Mg on this basis at present, reduces under few situation in specific conductivity that makes Cu and thermal conductivity, improves wear resisting property by hardness and the intensity that improves Cu.The specific conductivity and the thermal conductivity of fine copper are best, but intensity and hardness are low, are easy to wearing and tearing.Along with adding Cr, the Mo among the Cu, the increase of W equivalent, the intensity of Cu and wear resistance increase, but specific conductivity, thermal conductivity reduce.Improve Cr, Mo, W content in the Cu matrix, also cause the melting segregation to increase, the crackle notch sensitivity increases, hot-work difficulty etc.Thereby increase by melting in Cu that whole alloy content improves hardness and intensity is unrealistic.
The present invention adopts alloy electroplating method, deposits Cr, Mo, W alloy on the Cu matrix, can change the surface alloy composition according to specific requirement, improve surface hardness, intensity and wear resisting property, and heart portion still is the Cu of high conductivity and thermal conductivity.Cross quick-wearing for the part that aerial condutors such as electric power train cause because of the frequent operation of regionality in the process under arms, also available this method is repaired, and practicality is wider.
Summary of the invention
In order to overcome the shortcoming and defect that prior art exists, primary and foremost purpose of the present invention is to provide a kind of copper-chromium-molybdenum ternary alloy coating; Elemental chromium in this copper-chromium-molybdenum ternary alloy coating, molybdenum content is high and can its content be changed in the larger context by changing deposition parameter, disperses comparatively evenly, more than the Mo content to 1% in the raising coating, can put forward the high pressure blow-out performance of point of contact.
Another object of the present invention is to provide the preparation method of above-mentioned copper-chromium-molybdenum ternary alloy coating.
Purpose of the present invention realizes by following technical proposals: a kind of copper-chromium-molybdenum ternary alloy coating, described alloy layer are the surface electrical deposition one deck electroplate liquids at base material; Described electroplate liquid comprises main salt, complexing agent, conducting salt, stablizer and induction and deposition agent.
Described main salt is bivalent cupric ion salt, trivalent chromic ion salt and molybdate; Described complexing agent is inorganic complexing agent or organic complexing agent; Described conducting salt is an ammonium salt; Described stablizer is a boric acid; Described induction and deposition agent is Lanthanum trichloride (LaCl
3.nH
2O, oxide compound total amount of rare earth TRE2O3 〉=45%).
Described inorganic complexing agent is an ammonium sulfate; Described organic complex is citric acid or citric acid+ammonium formiate.
The preparation method of above-mentioned a kind of copper-chromium-molybdenum ternary alloy coating comprises following operation steps:
(1) preparation of electroplate liquid:
With distilled water with citric acid (C
6H
8O
7) dissolving, add six water Sodium orthomolybdate (Na
2MoO
46H
2O) carry out abundant stirring and dissolving, regulate pH value to 1.5～3.3; Add LaCl more successively
3NH
2O, ammonium sulfate ((NH
4)
2SO
4) and ammonium formiate (NH
4COOH), regulate pH value to 2.1～4.0; Add cupric sulfate pentahydrate (CuSO then successively
45H
2O), six water chromium sulphate (Cr
2(SO
4)
36H
2O) and boric acid (H
3BO
3), described six water chromium sulphates dissolve the back fully at cupric sulfate pentahydrate and add, and described boric acid dissolves the back fully at six water chromium sulphates and adds, and adds remaining distilled water at last, regulates pH value to 2.0～3.8, obtains electroplate liquid;
Described electroplate liquid is made up of following component by mass volume ratio:
Six water chromium sulphates, 70～80gL
-1,
Cupric sulfate pentahydrate 70～80gL
-1,
Ammonium sulfate 20～70gL
-1
Six water Sodium orthomolybdates, 15～30gL
-1
Lanthanum trichloride 3～5gL
-1
Citric acid 10～20gL
-1
Ammonium formiate 0～50gL
-1
Boric acid 30～40gL
-1
All the other are distilled water;
(2) with substrate surface after polishing and matting, put into plating tank, be immersed in the electroplate liquid, under 40～55 ℃ of conditions, electroplating deposition 30～60min electroplates the back that finishes and takes out base material, flushing is dried, and obtains the Cu-Cr-Mo ternary alloy coating; The pulse square wave electroplating power supply is adopted in described plating, and square wave frequency is 400～1200Hz, and dutycycle is 5～30%, and average current density is 3～7A/dm
2
The described adjusting of step (1) pH value is to adopt sulfuric acid to regulate.
The described base material of step (2) is the fine copper sheet.
Insoluble anode is adopted in the described plating of step (2), and negative electrode and annode area ratio are 1: 2, keeps negative electrode parallel with anode; Described insoluble anode is that graphite, platinum or tin quality percentage composition are 5% Lead-tin alloy.
The described polishing of step (2) adopts 1000
#Sand paper; The technology of described matting is: grinded base material is washed down with distilled water, is that 3～4% dilute hydrochloric acid cleaned 0.5～1 minute with mass percent concentration then, clean with distilled water flushing at last.
The solid solubility of metal in Cu such as principle of the present invention: Cr, Mo, W are very low, also Just because of this, just make and contain Cr, Mo, W among the Cu specific conductivity and the thermal conductivity of Cu reduced seldom; But because of the wettability of Cr, Mo, W and Cu very poor (by the very low decision of solid solubility), Cr, Mo, W are equivalent to the mechanics defective in Cu, Cr, Mo, W too high levels can make the loose aggravation of Cu coating among the Cu, wear resistance sharply reduces, specific conductivity and thermal conductivity also descend significantly simultaneously, so Cr, Mo among the Cu, W content are unsuitable too high, surpass 9% and just make cladding wearability poor; Cr and Mo are the very negative elements of current potential, the Cr change in concentration is very little to Cr content influence in the coating, but the content of Sodium orthomolybdate has bigger influence, does not have Sodium orthomolybdate, is difficult to deposit the Cu-Cr alloy, add Sodium orthomolybdate and cooperate and increase complexing agent, available revulsion increases the content of Cr, but increasing degree is less, and on the contrary the content of Mo increases significantly, but can molybdenum deposit the content that does not mainly depend on Sodium orthomolybdate, and depend on complex compound.
The content of Cr is more stable in copper of the present invention-chromium-molybdenum ternary alloy coating, between 0.8～1.2%wt.; The content of Mo can be with NH in the plating bath
4COOH and (NH
4)
2SO
4NH is worked as in the variation of content and changing
4COOH content is brought up to 50g/L and (NH from 0g/L
4)
2SO
4Content when 20g/L brings up to 70g/L, Mo content is brought up to 7.45%wt. from 0.25%wt.; Increase CH
4The COOH amount needs to increase simultaneously (NH
4)
2SO
4Content, the content of Mo increases in the coating, but coating compactness slightly reduces.
The present invention is with respect to prior art, have following advantage and beneficial effect: preparation method of the present invention is simple, elemental chromium in gained copper-chromium-molybdenum ternary alloy coating, molybdenum content is high and can its content be changed in the larger context by changing parameter, disperses comparatively even; In addition, the present invention deposits Cr, Mo, W alloy on the Cu matrix, can change the surface alloy composition according to specific requirement, improve surface hardness, intensity and wear resisting property, and heart portion still is the Cu of high conductivity and thermal conductivity.
Description of drawings
Fig. 1 is the surperficial secondary electron shape appearance figures of embodiment 3 prepared samples with the copper-chromium-molybdenum coating of electronic probe (EPMA) analysis.
The EDS on Fig. 2 whole surface of Fig. 1 that to be embodiment 3 prepared samples make of electronic probe (EPMA) can spectrogram.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but the working of an invention mode is not limited thereto.
Embodiment 1
(1) get the beaker that a usefulness distilled water is cleaned, add the distilled water of 60ml therein, weighing also adds the C of the 1.5g of institute
6H
8O
7(citric acid) treats C
6H
8O
7The dissolving back adds the Na of 2.5g fully
2MoO
46H
2O fully stirs and makes Na
2MoO
46H
2O dissolves fully, adds the pH value to 2.6 of sulfuric acid regulation solution then, regulates the LaCl that adds 0.4g after finishing successively
3NH
2(the NH of O and 2g
4)
2SO
4,, add the CuSO of 7.5g then successively with the pH value to 3.0 of sulfuric acid regulation solution
45H
2The Cr of O, 7.5g
2(SO
4)
36H
2The H of O and 3g
3BO
3, after a kind of medicine dissolves fully in the requirement, can add down a kind of medicine again, and adding distil water is adjusted to 2.5 with sulfuric acid with pH value at last once more to 100ml, obtain electroplate liquid, electroplate liquid is placed coating bath;
(2) do plating piece with the fine copper sheet of 20 * 10mm, to electroless plating face (back side) with insullac protection, with the fine copper sheet through 1000
#Coated abrasive working after, wash down with distilled water, be that 3% dilute hydrochloric acid cleaned 2 minutes with mass percent concentration then, wash down with distilled water again, make fine copper sheet surface active; At last the fine copper sheet is put into coating bath, under 45 ℃, make anode with high purity graphite, negative electrode and annode area ratio are 1: 2, keep negative electrode parallel with anode, and the fine copper sheet is treated that the one side of deposit alloy is over against anode, with square wave frequency is 500Hz, and dutycycle is 10%, and current density is 5A/dm
2, electroplate 50min; Take out the fine copper sheet then,, in thermostatic drying chamber, dry, promptly obtain Cu-Cr-Mo ternary alloy coating of the present invention with the tap water flushing.Gained coating is made energy spectrum composition analysis with the EDS on the electronic probe EPMA, and Coating composition is 1.12wt.%Cr, 0.25wt.%Mo, and all the other are Cu.
Embodiment 2
(1) get the beaker that a usefulness distilled water is cleaned, add the distilled water of 60ml therein, weighing also adds the C of the 1.5g of institute
6H
8O
7(citric acid) treats C
6H
8O
7The dissolving back adds the Na of 2.5g fully
2MoO
46H
2O fully stirs and makes Na
2MoO
46H
2O dissolves fully, and the pH value that adds sulfuric acid regulation solution is then regulated the LaCl that adds 0.4g after finishing successively to lower by 2.7 than needed
3NH
2The NH of O, 3g
4(the NH of COOH and 5g
4)
2SO
4,, with the pH value to 2.8 of sulfuric acid regulation solution, add the CuSO of 7.5g then successively
45H
2The Cr of O, 7.5g
2(SO
4)
36H
2The H of O and 4g
3BO
3After a kind of medicine dissolves fully in the requirement, can add down a kind of medicine again, and adding distil water is adjusted to 3.2 with sulfuric acid with pH value at last once more to 100ml, obtains electroplate liquid, electroplate liquid is placed coating bath;
(2) do plating piece with the fine copper sheet of 20 * 10mm, to electroless plating face (back side) with insullac protection, with the fine copper sheet through 1000
#Coated abrasive working after, wash down with distilled water, be that 4% dilute hydrochloric acid cleaned 2 minutes with mass percent concentration then, wash down with distilled water again, make fine copper sheet surface active; At last the fine copper sheet is put into coating bath, under 50 ℃, make anode with platinum, negative electrode and annode area ratio are 1: 2, keep negative electrode parallel with anode, and the fine copper sheet is treated that the one side of deposit alloy is over against anode, with square wave frequency is 1000HZ, and dutycycle is 20%, and current density is 3A/dm
2, electroplate 20min; Take out the fine copper sheet,, in thermostatic drying chamber, dry, promptly obtain Cu-Cr-Mo ternary alloy coating of the present invention with the tap water flushing.Gained coating is made energy spectrum composition analysis with the EDS on the electronic probe EPMA, and the coating surface composition is 1.02wt.%Cr, 2.15wt.%Mo, and all the other are Cu.
(1) get the beaker that a usefulness distilled water is cleaned, add the distilled water of 60ml therein, weighing also adds the C of the 1.5g of institute
6H
8O
7(citric acid) treats C
6H
8O
7The dissolving back adds the Na of 1.5g fully
2MoO
46H
2O fully stirs and makes Na
2MoO
46H
2O dissolves fully, and the pH value that adds sulfuric acid regulation solution is then regulated the LaCl that adds 0.4g after finishing successively to lower by 2.7 than needed
3NH
2The NH of O, 5g
4(the NH of COOH and 7g
4)
2SO
4,, add the CuSO of 7.5g then successively with the pH value to 2.1 of sulfuric acid regulation solution
45H
2The Cr of O, 7.5g
2(SO
4)
36H
2The H of O and 4g
3BO
3, after a kind of medicine dissolves fully in the requirement, can add down a kind of medicine again, and adding distil water is adjusted to 3.2 with sulfuric acid with pH value at last once more to 100ml, obtain electroplate liquid, electroplate liquid is placed coating bath;
(2) do plating piece with the fine copper sheet of 20 * 10mm, to electroless plating face (back side) with insullac protection, with the fine copper sheet through 1000
#Coated abrasive working after, wash down with distilled water, be that 3.5% dilute hydrochloric acid cleaned 2 minutes with mass percent concentration then, wash down with distilled water again, make fine copper sheet surface active; At last the fine copper sheet is put into coating bath, under 46 ℃, with tin quality percentage composition is that 5% Lead-tin alloy is made anode, negative electrode and annode area ratio are 1: 2, keep negative electrode parallel with anode, the one side that the fine copper sheet is treated deposit alloy is 1200HZ over against anode with square wave frequency, dutycycle is 20%, and current density is 7A/dm
2, electroplate 40min; Take out the fine copper sheet,, in thermostatic drying chamber, dry, promptly obtain Cu-Cr-Mo ternary alloy coating of the present invention with the tap water flushing.Gained coating is made energy spectrum composition analysis with the EDS on the electronic probe EPMA, and the coating surface composition is 1.22wt.%Cr, 7.45wt.%Mo, and all the other are Cu.The surperficial secondary electron shape appearance figure of copper-chromium-molybdenum coating that prepared sample usefulness electronic probe (EPMA) is analyzed as shown in Figure 1; EDS on the electronic probe EPMA makes the energy spectrogram as shown in Figure 2.Table 1 is to calculate resulting each constituent content of whole coating surface according to the EDS power spectrum of Fig. 2 gained.
Table 1 copper-each constituent content of chromium-molybdenum coating surface
| ?Element | Wt％ | At％ |
| OK | 03.33 | 10.69 |
| CrK | 01.22 | 01.49 |
| MoL | 07.45 | 04.877 |
| CuK | 88.01 | 82.94 |
| Matrix | Correction | ZAF |
Embodiment 4
(1) get the beaker that a usefulness distilled water is cleaned, add the distilled water of 60ml therein, weighing also adds the C of the 1.5g of institute
6H
8O
7(citric acid) treats C
6H
8O
7The dissolving back adds the Na of 1.5g fully
2MoO
46H
2O fully stirs and makes Na
2MoO
46H
2O dissolves fully, adds the pH value to 3.3 of sulfuric acid regulation solution then, regulates the LaCl that adds 0.4g after finishing successively
3NH
2The NH of O, 3g
4(the NH of COOH and 5g
4)
2SO
4, with the pH value to 4.0 of sulfuric acid regulation solution, the CuSO of 7.5g
45H
2The Cr of O, 7.5g
2(SO
4)
36H
2The H of O and 4g
3BO
3After a kind of medicine dissolves fully in the requirement, can add down a kind of medicine again, and adding distil water is adjusted to 3.8 with sulfuric acid with pH value at last once more to 100ml, obtains electroplate liquid, electroplate liquid is placed coating bath;
(2) do plating piece with the fine copper sheet of 20 * 10mm, to electroless plating face (back side) with insullac protection, with the fine copper sheet through 1000
#Coated abrasive working after, wash down with distilled water, be that 4% dilute hydrochloric acid cleaned 2 minutes with mass percent concentration then, wash down with distilled water again, make fine copper sheet surface active; At last the fine copper sheet is put into coating bath, under 49 ℃, make anode with high purity graphite, negative electrode and annode area ratio are 1: 2, keep negative electrode parallel with anode, and the fine copper sheet is treated that the one side of deposit alloy is over against anode, with square wave frequency is 400HZ, and dutycycle is 5%, and current density is 4A/dm
2, electroplate 30min; Take out the fine copper sheet,, in thermostatic drying chamber, dry, promptly obtain Cu-Cr-Mo ternary alloy coating of the present invention with the tap water flushing.Gained coating is made energy spectrum composition analysis with the EDS on the electronic probe EPMA, and the coating surface composition is 1.08wt.%Cr, 1.85wt.%Mo, and all the other are Cu.
Embodiment 5
(1) get the beaker that a usefulness distilled water is cleaned, add the distilled water of 60ml therein, weighing also adds the C of the 1.5g of institute
6H
8O
7(citric acid) treats C
6H
8O
7The dissolving back adds the Na of 3.0g fully
2MoO
46H
2O fully stirs and makes Na
2MoO
46H
2O dissolves fully, adds the pH value to 1.5 of sulfuric acid regulation solution then, regulates the LaCl that adds 0.4g after finishing successively
3NH
2The NH of O, 3g
4(the NH of COOH and 5g
4)
2SO
4, with the pH value to 2.2 of sulfuric acid regulation solution, the CuSO of 7.5g
45H
2The Cr of O, 7.5g
2(SO
4)
36H
2The H of O and 4g
3BO
3After a kind of medicine dissolves fully in the requirement, can add down a kind of medicine again, and adding distil water is adjusted to 2.0 with sulfuric acid with pH value at last once more to 100ml, obtains electroplate liquid, electroplate liquid is placed coating bath;
(2) do plating piece with the fine copper sheet of 20 * 10mm, to electroless plating face (back side) with insullac protection, with the fine copper sheet through 1000
#Coated abrasive working after, wash down with distilled water, be that 3% dilute hydrochloric acid cleaned 2 minutes with mass percent concentration then, wash down with distilled water again, make fine copper sheet surface active; At last the fine copper sheet is put into coating bath, under 50 ℃, make anode with high purity graphite, negative electrode and annode area ratio are 1: 2, keep negative electrode parallel with anode, and the fine copper sheet is treated that the one side of deposit alloy is over against anode, with square wave frequency is 1000HZ, and dutycycle is 30%, and current density is 6A/dm
2, electroplate 60min; Take out the fine copper sheet,, in thermostatic drying chamber, dry, promptly obtain Cu-Cr-Mo ternary alloy coating of the present invention with the tap water flushing.Gained coating is made energy spectrum composition analysis with the EDS on the electronic probe EPMA, and the coating surface composition is 1.12wt.%Cr, 2.27wt.%Mo, and all the other are Cu.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. copper-chromium-molybdenum ternary alloy coating is characterized in that: described alloy layer is the surface electrical deposition one deck electroplate liquid at base material; Described electroplate liquid comprises main salt, complexing agent, conducting salt, stablizer and induction and deposition agent.
2. a kind of copper according to claim 1-chromium-molybdenum ternary alloy coating is characterized in that: described main salt is bivalent cupric ion salt, trivalent chromic ion salt and molybdate; Described complexing agent is inorganic complexing agent or organic complexing agent; Described conducting salt is an ammonium salt; Described stablizer is a boric acid; Described induction and deposition agent is a Lanthanum trichloride.
3. a kind of copper according to claim 2-chromium-molybdenum ternary alloy coating is characterized in that: described inorganic complexing agent is an ammonium sulfate; Described organic complex is citric acid or citric acid+ammonium formiate.
4. the preparation method of a kind of copper according to claim 1-chromium-molybdenum ternary alloy coating is characterized in that comprising following operation steps:
(1) preparation of electroplate liquid:
With distilled water citric acid is dissolved, add six water Sodium orthomolybdates and carry out abundant stirring and dissolving, regulate pH value to 1.5～3.3; Add LaCl more successively
37H
2O, ammonium sulfate and ammonium formiate are regulated pH value to 2.1～4.0; Add cupric sulfate pentahydrate, six water chromium sulphate and boric acid then successively, described six water chromium sulphates dissolve the back fully at cupric sulfate pentahydrate and add, and described boric acid dissolves the back fully at six water chromium sulphates and adds, and adds remaining distilled water at last, regulate pH value to 2.0～3.8, obtain electroplate liquid;
Described electroplate liquid is made up of following component by mass volume ratio:
Six water chromium sulphates, 70～80gL
-1,
Cupric sulfate pentahydrate 70～80gL
-1,
Ammonium sulfate 20～70gL
-1
Six water Sodium orthomolybdates, 15～30gL
-1
Lanthanum trichloride 3～5gL
-1
Citric acid 10～20gL
-1
Ammonium formiate 0～50gL
-1
Boric acid 30～40gL
-1
All the other are distilled water;
(2) with substrate surface after polishing and matting, put into plating tank, be immersed in the electroplate liquid, under 40～55 ℃ of conditions, electroplating deposition 30～60min electroplates the back that finishes and takes out base material, flushing is dried, and obtains the Cu-Cr-Mo ternary alloy coating; The pulse square wave electroplating power supply is adopted in described plating, and square wave frequency is 400～1200Hz, and dutycycle is 5～30%, and average current density is 3～7A/dm
2
5. preparation method according to claim 4 is characterized in that: the described adjusting of step (1) pH value is to adopt sulfuric acid to regulate.
6. preparation method according to claim 4 is characterized in that: the described base material of step (2) is the fine copper sheet.
7. preparation method according to claim 4 is characterized in that: insoluble anode is adopted in the described plating of step (2), and negative electrode and annode area ratio are 1: 2, keeps negative electrode parallel with anode.
8. preparation method according to claim 7 is characterized in that: described insoluble anode is that graphite, platinum or tin quality percentage composition are 5% Lead-tin alloy.
9. preparation method according to claim 4 is characterized in that: the described polishing of step (2) adopts 1000
#Sand paper; The technology of described matting is: grinded base material is washed down with distilled water, is that 3～4% dilute hydrochloric acid cleaned 0.5～1 minute with mass percent concentration then, clean with distilled water flushing at last.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103726084A (en) * | 2014-01-22 | 2014-04-16 | 贵州大学 | Electro-deposition method for Cu-Mo-Ni/Co alloy clad layer |
| WO2015091863A1 (en) * | 2013-12-19 | 2015-06-25 | Schlenk Metallfolien Gmbh & Co. Kg | Method for electrolytic surface modification of flat metal workpieces in copper-sulfate treatment liquid containing sulfate-metallates |
| CN107522229A (en) * | 2017-07-24 | 2017-12-29 | 桂林理工大学 | One kind (Y1‑xLnx)2(MoO4)3The direct preparation method of film |
| CN111074209A (en) * | 2019-12-27 | 2020-04-28 | 西安交通大学 | Surface coating of contact material of vacuum arc-extinguishing chamber and treatment method thereof |
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| 《东北大学硕士学位论文》 20071231 滕莹雪 电化学法沉积铜铬合金的研究 第9、26-28页 1-3 , 2 * |
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| CN103726084B (en) * | 2014-01-22 | 2016-05-25 | 贵州大学 | The method of electro-deposition Cu-Mo-Ni/Co alloy layer |
| CN107522229A (en) * | 2017-07-24 | 2017-12-29 | 桂林理工大学 | One kind (Y1‑xLnx)2(MoO4)3The direct preparation method of film |
| CN107522229B (en) * | 2017-07-24 | 2019-10-11 | 桂林理工大学 | One kind (Y1-xLnx)2(MoO4)3The direct preparation method of film |
| CN111074209A (en) * | 2019-12-27 | 2020-04-28 | 西安交通大学 | Surface coating of contact material of vacuum arc-extinguishing chamber and treatment method thereof |
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| CN101892502B (en) | 2012-02-01 |
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