CN105088287A - Electrolyte prepared based on deep eutetic ion liquid and water and electroplating method thereof - Google Patents
Electrolyte prepared based on deep eutetic ion liquid and water and electroplating method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electroplating, and specifically relates to an electrolyte prepared based on deep eutetic ion liquid and water and its an electroplating method thereof. The electrolyte contains choline chloride, hydrogen bond donor, primary salt, additive and water, wherein the molar ratio of the choline chloride to the hydrogen bond donor is (1:4)-(1:0.5), each 1000ml of the electrolyte contains 0.01-1 molar mol of primary salt, 0.1-150 grams of additive and 1-500 grams of water. The electrolyte is low in viscosity and high in conductivity; electroplating can be performed in atmospheric environment, the operation temperature range is wide, the electroplating speed is quick, and the current efficiency is high; the prepared electroplating layer is good in compactness and high in purity. Moreover, the electrolyte prepared based on deep eutetic ion liquid and water and the electroplating method thereof have features of low cost, environmental protection, and easy implementation of large-scale production.
Description
Technical field
The invention belongs to field of electroplating, be specifically related to a kind of electrolytic solution and the electro-plating method thereof that are total to melt type ionic liquid and water preparation based on the degree of depth.
Background technology
Ionic liquid refer to by formed after organic salt and inorganic salts mixed melting, the ion melt that is made up of organic cation and inorganic anion, also referred to as room temperature fused salt.Ionic liquid is because having unique physicochemical property and distinctive function, as non-volatile, low melting point (can-100 DEG C be reached), wide liquid journey, wide electrochemical window, selective dissolution power and designability etc., it is made to have good application prospect in organic synthesis, catalysis, compartment analysis and the field such as purifying, electrochemistry.For plating, ionic liquid has then had both the advantage of high-temperature molten salt and the aqueous solution: have wider electrochemical window, at room temperature can obtain galvanic deposit just getable metal and alloy in high-temperature molten salt, but the severe corrosive not having high-temperature molten salt such; Meanwhile, go back electrodepositable and obtain most of metal that can obtain in aqueous, but do not have side reaction in ionic liquid, the metal quality thus obtained is better, and current efficiency is higher, even can reach 100%.In addition, ionic liquid is a kind of green solvent, for the exploitation of environment-friendly type electroplating technology provides new approaches.
Ionic liquid can be divided into by generated time sequencing: first-generation AlCl
3the non-AlCl of type ionic liquid, the s-generation
3type ionic liquid and third generation novel ion liquid.The literature search of prior art is found: the sixties and the ionic liquid plating research seventies mainly concentrate on first-generation AlCl
3type ionic liquid, but this kind of ionic liquid is very responsive to water, and stability is bad, needs to electroplate in inert protective gas.The non-AlCl of the s-generation nineties
3type ionic liquid synthesizes, non-AlCl
3type ionic liquid stability increases, but can decompose rotten after water suction certain hour, and the low (10mScm of the specific conductivity of this kind of ionic liquid
-1), metal salt solubilities is not high.In addition, the cost of the first-generation and s-generation ionic liquid is all very high, which has limited its mass-producing application.Along with the synthesis of third generation novel ion liquid, particularly a kind of degree of depth is total to the synthesis of melt type ionic liquid, due to this kind of ionic liquid good stability, with low cost, and preparation is simple, makes ionic liquid become possibility in the mass-producing application of field of electroplating.But also there is following problem in the degree of depth altogether melt type ionic liquid plating: 1) compare the first-generation and s-generation ionic liquid, the degree of depth is total to the lower (<10mScm of specific conductivity of melt type ionic liquid
-1), viscosity higher (>1Pas); 2) compare the first-generation and s-generation ionic liquid, cost lowers obviously, but higher than traditional aqueous; 3) although melt type ionic liquid stability is better altogether for the degree of depth, current plating research is all also carried out in inert protective gas.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of electrolytic solution and the preparation and application thereof that are total to melt type ionic liquid and water preparation based on the degree of depth, to overcome the degree of depth technical problems such as melt type ionic liquid specific conductivity is low altogether, viscosity is high, cost is high and cannot operate in atmospheric environment in prior art.
For achieving the above object and other objects, the present invention is achieved by the following technical solutions:
A first aspect of the present invention, provide electrolytic solution, containing choline chloride 60, hydrogen bond donor, main salt, additive and water, the mol ratio of described choline chloride 60 and hydrogen bond donor is (1:4) ~ (1:0.5), the water of the additive of the main salt containing (0.01 ~ 1) mole in every 1000ml electrolytic solution, (0.1 ~ 150) gram and (1 ~ 500) gram.
Preferably, the main salt containing (0.01 ~ 0.5) mole in every 1000ml electrolytic solution.
Preferably, the water containing (6 ~ 490) gram in every 1000ml electrolytic solution.More preferably, the water containing (10 ~ 490) gram in every 1000ml electrolytic solution.
Preferably, described hydrogen bond donor is selected from one or more in urea, ethylene glycol, ethanamide, methane amide, glycerine, oxalic acid, propanedioic acid, toluylic acid, trichoroacetic acid(TCA), p-methyl benzenesulfonic acid, p-methyl phenol or m-methyl phenol.
Preferably, described main salt is selected from one or more in nickel salt, zinc salt, mantoquita, chromic salts or pink salt.
Preferably, described nickel salt is selected from one or more in nickel oxide, nickelous chloride, single nickel salt or nickel sulfamic acid.
Preferably, described zinc salt is selected from one or more in zinc oxide, zinc chloride or zinc sulfate.
Preferably, described mantoquita is selected from one or more in cupric oxide, cupric chloride, copper sulfate or cupric nitrate.
Preferably, described chromic salts is selected from one or more in chromium chloride or chromium nitrate.
Preferably, described pink salt is selected from one or more in stannic oxide, tin protochloride or stannous sulfate.
Preferably, described additive is selected from one or more in nicotinic acid, EDTA, citric acid, oxalic acid, oxysuccinic acid, tartrate, asccharin, lithium chloride, lithium fluoride, Sodium Bromide, Potassium Bromide.
A second aspect of the present invention, provides the preparation method of aforementioned electrolyte, comprises the steps:
(1) by proportioning by choline chloride 60 and hydrogen bond donor, mixing, heating, obtain ionic liquid;
(2) in gained ionic liquid in step (1), add water by proportioning, obtain mixed solution;
(3) add in gained mixed solution in step (2) by proportioning and become owner of salt and additive, heating for dissolving, obtain electrolytic solution.
Preferably, in step (1), the temperature of heating controls at 40-80 DEG C.
Preferably, in step (1), carry out while heating stirring until form colourless transparent liquid.
Preferably, in step (2), water is added while stirring.
Preferably, in step (3), the temperature of heating controls at 30-80 DEG C.
Preferably, in step (3), carry out while heating stirring until form clarified liq.
A third aspect of the present invention, provides the application of aforementioned electrolyte in field of electroplating, electropolishing field, chemical conversion film field.
A fourth aspect of the present invention, further provides a kind of electro-plating method, comprises the steps:
(1) treatment before plating: by the pretreatment process process in body material conveniently electroplating technology;
(2) pretreated body material is put into aforementioned electrolyte to electroplate;
(3) take out sample, flushing dries up.
Preferably, in step (1), body material can be selected from conventional any body material that can be used for carrying out electroplating, such as copper, magnesium, stainless steel etc.
Preferably, in step (2), the mode of direct current electrode position or pulse plating is adopted to electroplate.
Preferably, in step (2), the service temperature of plating is 30-80 DEG C.Electroplating time is 10-120min.Current density is 0.1-5A/dm
2.
Preferably, in step (3), adopt running water.
Compared with prior art, beneficial effect of the present invention is:
(1) electrolytic solution of the present invention has high conductivity, low viscosity, environmental protection, the feature of low cost when electroplating, and can carry out the advantage of electroplating operations in atmospheric environment.
(2) compactness of electroplating prepared when adopting electrolytic solution of the present invention to electroplate is good, and purity is high, and current efficiency is up to more than 95%.Overcome many disadvantages of the prior art and creative.
Accompanying drawing explanation
Fig. 1: after adding a certain amount of water, electrolytic solution viscosity obviously reduces, and can see from viscometric properties, can lower electroplating temperature after adding water.
Fig. 2: after adding a certain amount of water, electrolytic conductivity obviously raises, also can see from specific conductivity character, obviously can lower electroplating temperature after adding water.
Fig. 3: it be loose for not adding water and electroplating the nickel coating that obtains, and add in the electrolytic solution that a certain amount of water configures and electroplate that to obtain plated layer compact even.
Fig. 4: after adding a certain amount of water, the current efficiency of plating significantly improves, particularly when cold galvanising clearly,
Fig. 5: be the SEM photo of the electronickelling coating of preparation in the embodiment of the present invention 2.
Fig. 6: be the EDXS collection of illustrative plates of the electronickelling coating of preparation in the embodiment of the present invention 2.
Fig. 7: be the SEM photo of the electro-galvanizing coating of preparation in the embodiment of the present invention 3.
Fig. 8: be the EDXS collection of illustrative plates of the electro-galvanizing coating of preparation in the embodiment of the present invention 3.
Fig. 9: be the SEM photo of the electro-galvanizing coating of preparation in the embodiment of the present invention 4.
Figure 10: be the SEM photo of the nickel-zinc coating of preparation in the embodiment of the present invention 5.
Figure 11: be the EDXS collection of illustrative plates of the nickel-zinc coating of preparation in the embodiment of the present invention 5.
Figure 12: be the SEM photo of the electro-coppering coating of preparation in the embodiment of the present invention 6.
Figure 13: be the EDXS collection of illustrative plates of the electro-coppering coating of preparation in the embodiment of the present invention 6.
Figure 14: be the SEM photo of the electronickelling copper coating of preparation in the embodiment of the present invention 7.
Figure 15: be the EDXS collection of illustrative plates of the electronickelling copper coating of preparation in the embodiment of the present invention 7.
Figure 16: be the SEM photo of the electrodeposited chromium coating of preparation in the embodiment of the present invention 8.
Figure 17: be the EDXS collection of illustrative plates of the electrodeposited chromium coating of preparation in the embodiment of the present invention 8.
Embodiment
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
Notice, in the following example, the concrete processing unit that indicates or device all adopt conventional equipment in this area or device; All force value and scope all refer to absolute pressure.
In addition should be understood that the one or more method stepss mentioned in the present invention do not repel and can also to there is additive method step or can also insert additive method step before and after described combination step between these steps clearly mentioned, except as otherwise noted; Will also be understood that, the relation that is connected between the one or more equipment/devices mentioned in the present invention is not repelled and can also to be there are other equipment/devices or can also insert other equipment/devices before and after described clustered aggregates/device between these two equipment/devices clearly mentioned, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
Embodiment 1 investigates the impact added for viscosity of il, specific conductivity, current efficiency of water
First, electrolytic solution is prepared:
(1) 1:2 takes 70g choline chloride 60 and 60g urea in molar ratio, both is mixed with glass stick; Be placed in by the mixture obtained in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 70 DEG C, until form colourless transparent liquid, obtains the degree of depth melt type ionic liquid altogether of 125mL;
(2) water of different volumes is measured, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth that water-content is respectively 0wt%, 1wt%, 3wt%, 6wt% altogether mixed solution that formed of melt type ionic liquid and water.
(3) take 7.49g Nickel dichloride hexahydrate, joined the degree of depth (2) prepared and be total in the mixed solution of melt type ionic liquid and water, constant temperature 40 ~ 65 DEG C is stirred to whole dissolving, forms the electrolytic solution containing 0.2M nickel ion of green clarification.
Then, the electrolytic solution plating prepared is adopted:
(1) by Copper substrate at 65wt.%HNO
3clean 1 minute in the salpeter solution of (40%, V/V), then wash 1 minute, stand-by;
(2) pretreated Copper substrate is put into the electrolytic solution prepared to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 55 DEG C, and electroplating time is 60min, and current density is 0.5A/dm
2;
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
As shown in Figure 1, after adding a certain amount of water, electrolytic solution viscosity obviously reduces, and can see from viscometric properties, can lower electroplating temperature after adding water.Such as, the viscosity of the electrolytic solution adding 6wt.% water 40 DEG C time can be suitable with the viscosity of non-aqueous eletrolyte 65 DEG C time.Therefore, when adopting the electrolytic solution of the present invention's configuration to electroplate, not only quality of coating and performance improve, and energy-conserving and environment-protective more.
As shown in Figure 2, after adding a certain amount of water, electrolytic conductivity obviously raises, and also can see from specific conductivity character, obviously can lower electroplating temperature after adding water.The Conductivity Ratio non-aqueous eletrolyte specific conductivity 80 DEG C time of electrolytic solution 40 DEG C time of such as adding 6wt.% water is taller.Therefore, when adopting the electrolytic solution of the present invention's configuration to electroplate, not only quality of coating and performance improve, and energy-conserving and environment-protective more.
As shown in Figure 3, it be loose for not adding water and electroplating the nickel coating that obtains, and adds in the electrolytic solution that a certain amount of water configures and electroplate that to obtain plated layer compact even.
As shown in Figure 4, after adding a certain amount of water, the current efficiency of plating significantly improves, particularly when cold galvanising clearly, such as: when electroplating under 60 DEG C of conditions, the current efficiency of non-aqueous eletrolyte is less than 50%, and after adding the water of 6%, current efficiency is up to 98%.
Electronickelling coating on embodiment 2 Copper substrate
First, electrolytic solution is prepared:
(1) 1:2 takes 70g choline chloride 60 and 60g urea in molar ratio, both is mixed with glass stick; Be placed in by the mixture obtained in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 70 DEG C, until form colourless transparent liquid, obtains the degree of depth melt type ionic liquid altogether of 125mL;
(2) measure the water of 32.5mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 157.5mL mixed solution that formed of melt type ionic liquid and water that water-content is 20%;
(3) 7.49g Nickel dichloride hexahydrate and 13.7mg nicotinic acid is taken respectively, being joined the degree of depth (2) prepared is total in the mixed solution of melt type ionic liquid and water, constant temperature 50 DEG C is stirred to whole dissolving, forms the electrolytic solution containing 0.2M nickel ion and 0.01wt% nicotinic acid of green clarification.
Then, the electrolytic solution plating prepared is adopted:
(1) by Copper substrate at 65wt.%HNO
3clean 1 minute in the salpeter solution of (40%, V/V), then wash 1 minute, stand-by;
(2) pretreated Copper substrate is put into electrolytic solution to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 50 DEG C, and electroplating time is 30min, and current density is 0.5A/dm
2;
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Fig. 5 is shown in by the SEM photo of prepared nickel coating.Can see from macrograph, coating is made up of spheroidal particle, combines closely between particle; Partial enlargement can be seen, spheroidal particle is made up of very tiny small-particle, and coating is very fine and close.
The EDS analytical results of prepared nickel coating is shown in Fig. 6, and coating is pure nickel, does not have being mingled with of other electroplating bath components.Current efficiency according to weighting method calculating is 100%.
Embodiment 3 magnesium alloy substrate powers on galvanized coatings
First, electrolytic solution is prepared:
(1) 1:1.8 takes 70g choline chloride 60 and 55.8g ethylene glycol in molar ratio, choline chloride 60 is joined in ethylene glycol liquid, and be placed in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 60 DEG C, until formation colourless transparent liquid, obtain the degree of depth melt type ionic liquid altogether of 110mL;
(2) measure the water of 10mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 120mL mixed solution that formed of melt type ionic liquid and water that water-content is 8.33%;
(3) 4.09g Zinc Chloride Anhydrous and 1.30g citric acid is taken respectively, being joined the degree of depth (2) prepared is total in the mixed solution of melt type ionic liquid and water, constant temperature 60 DEG C is stirred to whole dissolving, forms the electrolytic solution containing 0.25M zine ion and 1wt.% citric acid of achromaticity and clarification.
Then, the electrolytic solution plating prepared is adopted:
(1) by AZ91D magnesium alloy after polishing, alkaline degreasing, pickling, activation, the process of leaching zinc, stand-by.
(2) pretreated AZ91D magnesium alloy substrate is put into electrolytic solution to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 60 DEG C, and electroplating time is 45min, and current density is 0.7A/dm
2.
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Fig. 7 is shown in by the SEM photo of prepared zinc coating.Can see from macrograph, coating is by block granulometric composition; Partial enlargement can be seen, particle surface is smooth, combines closely between particle.
The EDS analytical results of prepared zinc coating is shown in Fig. 8, and coating is pure zinc, does not have being mingled with of other electroplating bath components.Current efficiency according to weighting method calculating is 96%.
Embodiment 4 Copper substrate powers on galvanized coatings
First, electrolytic solution is prepared:
(1) 1:2.5 takes 70g choline chloride 60 and 56.25g methane amide in molar ratio, choline chloride 60 is joined in methane amide liquid, and be placed in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 80 DEG C, until formation colourless transparent liquid, obtain the degree of depth melt type ionic liquid altogether of 110mL;
(2) measure the water of 20mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 130mL mixed solution that formed of melt type ionic liquid and water that volume of water per-cent is 15.38%;
(3) 1.06g dry oxidation zinc, 11.2g Sodium Bromide and 11.2g Potassium Bromide is taken respectively, being joined the degree of depth (2) prepared is total in the mixed solution of melt type ionic liquid and water, constant temperature 80 DEG C is stirred to whole dissolving, forms the electrolytic solution of achromaticity and clarification containing 0.1M zine ion, 7.5wt% Sodium Bromide and 7.5wt% Potassium Bromide.
Then, the electrolytic solution plating prepared is adopted:
(1) by Copper substrate at 65wt.%HNO
3clean 1 minute in the salpeter solution of (40%, V/V), then wash 1 minute, stand-by;
(2) pretreated Copper substrate is put into electrolytic solution to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 80 DEG C, and electroplating time is 60min, and current density is 1A/dm
2;
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Fig. 9 is shown in by the SEM photo of prepared zinc coating.Can see from macrograph, coating is even; Partial enlargement can be seen, coating is made up of the lamella thing of well-crystallized, combines closely between lamella.Current efficiency according to weighting method calculating is 93%.
Nickel-zinc alloy layer on embodiment 5 Copper substrate
First, electrolytic solution is prepared:
(1) 1:3 takes 35g choline chloride 60 and 69.07g glycerine in molar ratio, joined in glycerol liquids by choline chloride 60, and be placed in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 40 DEG C, until formation colourless transparent liquid, obtain the degree of depth melt type ionic liquid altogether of 85mL;
(2) measure the water of 25mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 110mL mixed solution that formed of melt type ionic liquid and water that water-content is 22.72%;
(3) 12.65g Zinc Sulphate Heptahydrate and 2.89g nickel sulfate hexahydrate, 6.3g oxalic acid is taken respectively, being joined the degree of depth (2) prepared is total in the mixed solution of melt type ionic liquid and water, constant temperature 40 DEG C is stirred to whole dissolving, formed green clarification, containing the electrolytic solution of 0.4M zine ion, 0.1M nickel ion and 5wt% oxalic acid.
Then, the electrolytic solution plating prepared is adopted:
(1) by Copper substrate at 65wt.%HNO
3clean 1 minute in the salpeter solution of (40%, V/V), then wash 1 minute, stand-by;
(2) pretreated Copper substrate is put into electrolytic solution to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 40 DEG C, and electroplating time is 120min, and current density is 0.1A/dm
2;
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Figure 10 is shown in by the SEM photo of prepared nickel zinc coating.Can see from macrograph, coating is made up of spheroidal particle, combines closely between particle; Partial enlargement can be seen, spheroidal particle smooth surface, and coating is very fine and close.
The EDS analytical results of prepared nickel coating is shown in Figure 11, and coating is made up of nickel, zinc, oxygen element, and atomic ratio content is respectively Ni:69.47%; O:20.23%; Zn:10.30%, higher oxygen level illustrates that coating exists certain oxidation, but does not have being mingled with of other electroplating bath components.Current efficiency according to weighting method calculating is 98%.
Electro-coppering coating on embodiment 6 Ni substrate
First electrolytic solution is prepared:
(1) 1:0.5 takes 35g choline chloride 60 and 26g propanedioic acid in molar ratio, choline chloride 60 and propanedioic acid glass stick are mixed, and be placed in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 80 DEG C, until formation colourless transparent liquid, obtain the degree of depth melt type ionic liquid altogether of 52mL;
(2) measure the water of 50mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 102mL mixed solution that formed of melt type ionic liquid and water that water-content is 49%;
(3) 12.24g six brochantite and 2.27g oxysuccinic acid is taken respectively, being joined the degree of depth (2) prepared is total in the mixed solution of melt type ionic liquid and water, constant temperature 30 DEG C is stirred to whole dissolving, formed blue clarification, containing the electrolytic solution of 0.3M cupric ion and 3wt.% oxysuccinic acid.
Then the electrolytic solution plating prepared is adopted:
(1) by the H of Ni substrate at 75wt.%
3pO
4electrolytic cleaning 1 minute in (98%, V/V) solution, bath voltage is 2.5V, then washes 1 minute, stand-by;
(2) pretreated Ni substrate is put into electrolytic solution to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 30 DEG C, and electroplating time is 60min, and current density is 0.5A/dm
2.
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Figure 12 is shown in by the SEM photo of prepared copper coating.Can see from macrograph, coating surface becomes rock-like; Partial enlargement can be seen, coating is very fine and close.
The EDS analytical results of prepared nickel coating is shown in Figure 13, and coating is fine copper, does not have being mingled with of other electroplating bath components.Current efficiency according to weighting method calculating is 100%.
Embodiment 7 Copper substrate powers on nickel plated copper coating
First, electrolytic solution is prepared:
(1) 1:2 takes 35g choline chloride 60 and 85g p-methyl benzenesulfonic acid in molar ratio, choline chloride 60 and p-methyl benzenesulfonic acid glass stick are mixed, and be placed in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 80 DEG C, until formation colourless transparent liquid, obtain the degree of depth melt type ionic liquid altogether of 110mL;
(2) measure the water of 5mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 115mL mixed solution that formed of melt type ionic liquid and water that water-content is 4.34%;
(3) 0.2g copper chloride dihydrate, 3.34g six water nickelous nitrate and 1.25g lithium fluoride is taken respectively, being joined the degree of depth (2) prepared is total in the mixed solution of melt type ionic liquid and water, constant temperature 70 DEG C is stirred to whole dissolving, formed green clarification, containing the electrolytic solution of 0.01M cupric ion, 0.1M nickel ion and 1wt% lithium fluoride.
Then the electrolytic solution plating prepared is adopted:
(1) by Copper substrate at 65wt.%HNO
3clean 1 minute in the salpeter solution of (40%, V/V), then wash 1 minute, stand-by;
(2) pretreated Copper substrate is put into electrolytic solution to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 70 DEG C, and electroplating time is 10min, and current density is 5A/dm
2;
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Figure 14 is shown in by the SEM photo of prepared copper coating.Can see from macrograph, coating surface is even; Can see under high power, surface is made up of block, and combine closely between block, coating is very fine and close.
EDS analytical results Figure 15 of prepared nickel coating, coating is made up of nickel, copper, and atomic ratio content is respectively Ni:33.98%, Cu:66.01%, does not have being mingled with of other electroplating bath components.Current efficiency according to weighting method calculating is 100%.
Electrodeposited chromium coating on embodiment 8 stainless steel base
First, electrolytic solution is prepared:
(1) 1:4 takes 35g choline chloride 60 and 108g p-methyl phenol in molar ratio, choline chloride 60 and p-methyl phenol glass stick are mixed, and mixture is placed in constant temperature blender with magnetic force and carries out heated and stirred, temperature controls at 50 DEG C, until formation colourless transparent liquid, obtain the degree of depth melt type ionic liquid altogether of 125mL;
(2) measure the water of 1.26mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 126.26mL mixed solution that formed of melt type ionic liquid and water that water-content is 1%;
(3) 5.05g chromium chloride hexahydrate and 12.86g tartrate is taken respectively, being joined the degree of depth (2) prepared is total in the mixed solution of melt type ionic liquid and water, constant temperature 50 DEG C is stirred to whole dissolving, formed intense violet color, containing 0.15M trivalent chromic ion and the tartaric electrolytic solution of 8wt.%.
Then, the electrolytic solution plating prepared is adopted:
(1) by stainless steel alkaline degreasing-acid etching process, alkaline degreasing liquid consists of: the sodium sulfite aqueous solution of 2wt.% sodium hydroxide, 5wt.% sodium phosphate and 3wt.%, and temperature is 60 DEG C, and the treatment time is 15min; Acid etching liquid consists of: the aqueous solution of 60g/L hydrochloric acid, 250g/L nitric acid, 100g/L hydrofluoric acid, and temperature is room temperature state, and the time is 5min, stand-by;
(2) pretreated stainless steel base is put into electrolytic solution to electroplate, adopt the mode of pulse plating, the service temperature of plating is 50 DEG C, and electroplating time is 90min, and current density is 1.5A/dm
2=1s, 0A/dm
2=2s.
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Figure 16 is shown in by the SEM photo of prepared chromium coating, and can see from macrograph, coating surface is even; Partial enlargement can be seen, coating surface does not exist the such tiny crack of traditional aqueous electrodeposited chromium coating, and coating is finer and close.
The EDS analytical results of prepared chromium coating is shown in Figure 17, and coating is elementary composition primarily of chromium, and simultaneously containing certain oxygen, carbon and a small amount of chlorine element, atomic ratio content is respectively Cr:84.20%, O:17.35%, C:5.72%, Cl:1.73%; Higher oxygen level illustrates that coating exists certain oxidation, and carbon and chlorine element may be mingled with caused by a small amount of electrolytic solution for coating.Current efficiency according to weighting method calculating is 97%.
Eleetrotinplate coating on embodiment 9 Copper substrate
First, electrolytic solution is prepared:
(1) 1:2 takes 70g choline chloride 60 and 60g urea in molar ratio, both is mixed with glass stick; Be placed in by the mixture obtained in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 80 DEG C, until form colourless transparent liquid, obtains the degree of depth melt type ionic liquid altogether of 125mL;
(2) measure the water of 13.89mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 138.89mL mixed solution that formed of melt type ionic liquid and water that water-content is 10%;
(3) take 6.27g bis-hydrated stannous chloride, joined the degree of depth (2) prepared and be total in the mixed solution of melt type ionic liquid and water, constant temperature 80 DEG C is stirred to whole dissolving, forms the electrolytic solution containing 0.2M tin ion of achromaticity and clarification.
Then the electrolytic solution plating prepared is adopted:
(1) by Copper substrate at 65wt.%HNO
3clean 1 minute in the salpeter solution of (40%, V/V), then wash 1 minute, stand-by;
(2) pretreated Copper substrate is put into electrolytic solution to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 80 DEG C, and electroplating time is 30min, and current density is 2A/dm
2;
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Current efficiency according to weighting method calculating is 100%.
Eleetrotinplate zn alloy coating on embodiment 10 Copper substrate
First, electrolytic solution is prepared:
(1) 1:1.8 takes 70g choline chloride 60 and 77.5g ethylene glycol in molar ratio, choline chloride 60 is joined in ethylene glycol liquid, and be placed in constant temperature blender with magnetic force and carry out heated and stirred, temperature controls at 70 DEG C, until formation colourless transparent liquid, obtain the degree of depth melt type ionic liquid altogether of 130mL;
(2) measure the water of 10mL, it is slowly joined in the colourless transparent liquid above-mentioned (1) prepared under whipped state, obtain the degree of depth altogether 140mL mixed solution that formed of melt type ionic liquid and water that water-content is 7.14%;
(3) 1.33g anhydrous stannous chloride and 9.54g Zinc Chloride Anhydrous is taken respectively, being joined the degree of depth (2) prepared is total in the mixed solution of melt type ionic liquid and water, constant temperature 70 DEG C is stirred to whole dissolving, forms the electrolytic solution containing 0.5M zine ion and 0.05M tin ion of achromaticity and clarification.
Then, the electrolytic solution plating prepared is adopted:
(1) by Copper substrate at 65wt.%HNO
3clean 1 minute in the salpeter solution of (40%, V/V), then wash 1 minute, stand-by;
(2) pretreated Copper substrate is put into electrolytic solution to electroplate, adopt the mode of direct current electrode position, the service temperature of plating is 70 DEG C, and electroplating time is 60min, and current density is 0.1A/dm
2;
(3) taken out by sample after having electroplated, running water dries up, and obtains finished product.
Current efficiency according to weighting method calculating is 100%.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. an electrolytic solution, containing choline chloride 60, hydrogen bond donor, main salt, additive and water, the mol ratio of described choline chloride 60 and hydrogen bond donor is (1:4) ~ (1:0.5), the water of the additive of the main salt containing (0.01 ~ 1) mole in every 1000ml electrolytic solution, (0.1 ~ 150) gram and (1 ~ 500) gram.
2. electrolytic solution according to claim 1, it is characterized in that, described hydrogen bond donor be selected from urea, ethylene glycol, ethanamide, methane amide, glycerine, oxalic acid, propanedioic acid, toluylic acid, trichoroacetic acid(TCA), p-methyl benzenesulfonic acid, p-methyl phenol or m-methyl phenol one or more.
3. electrolytic solution according to claim 1, is characterized in that, described main salt be selected from nickel salt, zinc salt, mantoquita, chromic salts or pink salt one or more; One or more in described nickel salt preferential oxidation nickel, nickelous chloride, single nickel salt or nickel sulfamic acid; One or more in described zinc salt preferential oxidation zinc, zinc chloride or zinc sulfate; One or more in described mantoquita preferential oxidation copper, cupric chloride, copper sulfate or cupric nitrate; One or more in the preferred chromium chloride of described chromic salts or chromium nitrate; One or more in described pink salt preferential oxidation tin, tin protochloride or stannous sulfate.
4. electrolytic solution according to claim 1, is characterized in that, described additive be selected from nicotinic acid, EDTA, citric acid, oxalic acid, oxysuccinic acid, tartrate, asccharin, lithium chloride, lithium fluoride, Sodium Bromide, Potassium Bromide one or more.
5. the preparation method of the electrolytic solution according to the arbitrary claim of Claims 1 to 4, comprises the steps:
(1) by proportioning by choline chloride 60 and hydrogen bond donor, mixing, heating, obtain ionic liquid;
(2) in gained ionic liquid in step (1), add water by proportioning, obtain mixed solution;
(3) add in gained mixed solution in step (2) by proportioning and become owner of salt and additive, heating for dissolving, obtain electrolytic solution.
6. preparation method according to claim 5, is characterized in that, in step (1), the temperature of heating controls at 40-80 DEG C.
7. preparation method according to claim 5, is characterized in that, in step (3), the temperature of heating controls at 30-80 DEG C.The application of electrolytic solution according to the arbitrary claim of Claims 1 to 4 in field of electroplating, electropolishing field, chemical conversion film field.
8. an electro-plating method, comprises the steps:
(1) treatment before plating: by the pretreatment process process in body material conveniently electroplating technology;
(2) pretreated body material is put into electrolytic solution described in the arbitrary claim of Claims 1 to 4 to electroplate;
(3) take out sample, flushing dries up.
9. electro-plating method according to claim 8, is characterized in that, in step (2), adopts the mode of direct current electrode position or pulse plating to electroplate.
10. electro-plating method according to claim 8, is characterized in that, in step (2), the service temperature of plating is 30-80 DEG C, and electroplating time is 10-120min, and current density is 0.1-5A/dm
2.
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