CN102888630B - A kind of ionic liquid/additive system Low-temperature electro-deposition prepares the method for nano aluminum or nano aluminum coating - Google Patents
A kind of ionic liquid/additive system Low-temperature electro-deposition prepares the method for nano aluminum or nano aluminum coating Download PDFInfo
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Abstract
The present invention designs a kind of method adopting ionic liquid/additive system electrodeposited nanocrystalline aluminium or nano aluminum coating, it is characterized in that adopting ionic liquid and aluminum trichloride (anhydrous) to be mixed to form low-temperature electrolyte, add suitable additive and be prepared into ionic liquid/additive system.With the matrix processed for deposition cathode, adopt DC electrodeposition to prepare nano aluminum or nano aluminum coating, aluminum particulate size can adjust as required.This method avoid existing explained hereafter nano aluminum cost intensive, problem that output is little.The ionic liquid adopted is conventional ionic liquid, and wide material sources, cheap, specific conductivity is high, electrochemical window is wide, non-volatile, environmental friendliness.The use of suitable additive achieves and obtain the good nano aluminum of quality or nano aluminum coating in conventional ionic liquid system, and gained al deposition layer is fine and close, smooth, smooth.Ionic liquid/additive system can obtain nano material at a lower temperature, easy control of reaction system, energy consumption are little, the nano aluminum quality obtained is good, current efficiency is high, by the size regulating the consumption of additive and formula effectively can control nano aluminum, technique is simple, with low cost, application prospect is better.
Description
Technical field
The present invention relates to a kind of method adopting ionic liquid/additive system electrodeposited nanocrystalline aluminium or nano aluminum coating.Belong to nonferrous metallurgy field.
Background technology
The content of aluminium element in the earth's crust is only second to oxygen and silicon, and occupying the 3rd, is the metallic element that in the earth's crust, content is the abundantest.Aluminium is the second largest metallic substance being only second to iron and steel, occupy the half of non-ferrous metal ultimate production, have excellent physical and chemical performance, purposes is extremely extensive, with the relational degree of national economy up to 91%, be the requisite important foundation starting material of the national economic development and national defense construction.
In daily life, various aluminum products are used in a large number by people.Nano aluminum is as a kind of type material, and main application fields has three aspects, comprises the aluminium back surface field of rocket propellant, explosive additive and solar panel.These three aspects have very important significance for the situation of country and Economic development.But common aluminium powder and micron order aluminium powder are due to long ignition delay and slow combustion poweredly limit use.Become large " glomeration " at propellant combustion condense on surfaces, extend combustion time.Meanwhile, the defects such as incomplete combustion, increase infrared signal, the two phase flow loss of jet pipe and the gas discharge of formation plumage cigarette shape are likely produced.Compared with common aluminium powder, nanometer aluminium powder has the advantages that burning is faster, thermal discharge is larger, and compared with the common aluminium powder of same content, rate of combustion can improve 70%.The extensive Synthesis and applications research of nano aluminum is related to the development of China's national defense construction and the exploitation of high-tech product.The method preparing nano aluminum mainly contains using vaporization condensation process, line explosion method, mechanochemical reaction, pulse laser degrade method, arc discharge method and solution chemical method etc.Although nano aluminum has very important value in application aspect, but current preparation method's cost intensive, output are little, govern the development of nano aluminum in application aspect.Therefore, the low cost of Development of Novel, nano aluminum preparation method that output is large are extremely important.
Ionic liquid is a kind of class novel cpd be made up of organic cation and inorganic or organic anion completely, the excellent specific property such as have fusing point low (usually close to even lower than room temperature), not volatile, electrochemical window is wide, good conductivity, liquid state range are wide.Based on the physical and chemical performance of ionic liquid excellence, especially chemical property, in different kinds of ions liquid, achieve the galvanic deposit of aluminium.But be difficult to obtain nano level aluminum particulate in common ionic liquid, usual settled layer gained grain diameter is micron order, and settled layer is loose, coarse.In addition, although at some special ion liquid systems (such as: [BMP] NTf
2) in can obtain nano level settled layer, but this kind of ionic liquid usually expensive, preparation difficulty, significantly limit its application.Additive can selective adsorption on crystalline growth point, suppresses the growth of crystallization, promotes the formation of nucleus.Therefore, in conventional ionic liquid system, add the character that suitable additive can change settled layer, make settled layer fine and close, smooth, smooth, and finally obtain nano aluminum.Ionic liquid/additive system can obtain nano material at a lower temperature, easy control of reaction system, energy consumption are little, and without side reaction, the nano aluminum quality obtained is good, current efficiency is high, by the size regulating the consumption of additive and formula can control nano aluminum better, reduce costs, have a extensive future.
Summary of the invention
The object of the invention is to overcome the problem such as existing nano aluminum preparation method cost intensive, output is little, a kind of ionic liquid/additive system Low-temperature electro-deposition is provided to prepare the method for nano aluminum, this method temperature of reaction is low, energy consumption is little, the nano aluminum quality obtained is good, current efficiency is high, the size of nano aluminum can be controlled better, reduce costs.
The present invention adopts ionic liquid/additive system Low-temperature electro-deposition to prepare the method for nano aluminum, it is characterized in that said method comprising the steps of:
(1) ionic liquid is placed on and is equipped with in the vacuum drying oven of Vanadium Pentoxide in FLAKES, constant-temperature vacuum drying 24 ~ 48h;
(2) in glove box, under inert nitrogen gas or argon shield, under the stirring of magnetic stirring apparatus, slowly in ionic liquid, add aluminum chloride, be mixed to form low-temperature ionic liquids electrolytic solution according to a certain ratio, stir under constant temperature;
(3) select as required to add the additive that massfraction is 0.01% ~ 50%, stir;
(4) surface properties of cathode base material directly affects the combination degree of coating and substrate and the compactness of coating.Therefore need on pretreatment to carry out Pre-treatment before plating to matrix, method is as follows: sand papering → cleaning → electrochemical deoiling → washing → pickling → washing → acetone soaks → dry → dilution after concentrated hydrochloric acid and the vitriol oil nitration mixture in activation treatment → washed with de-ionized water → drying;
(5) anode adopts aluminium, graphite, pottery, vitreous carbon etc., and the distance between anode and negative electrode is 0.5 ~ 15cm;
(6) add appropriate electrolytic solution in a cell, under nitrogen or argon shield condition, constant electrolysis temperature is 20 DEG C ~ 300 DEG C, selects suitable voltage and stirring velocity, is 10 ~ 150A/m in current density
2condition under carry out DC electrodeposition and prepare nano aluminum settled layer.
(7) in electrodeposition process with under ultrasonic operational condition, nanometer aluminium powder can be obtained in electrolyzer.By acetonitrile, acetone and other organic solvent, nanometer aluminium powder is cleaned in glove box, put into oil bath after drying and preserve.
Described ionic liquid cation is quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazolium ion, pyridinium salt ion etc., and negatively charged ion has halide-ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions or other inorganic acid ion etc.Ionic liquid can be divided into imidazole salt, pyridine salt, quaternary ammonium salt and season phosphonium salt class etc., such as: one or more the mixing liquid in the two trifluoromethanesulfonimide salt of chlorination 1-butyl-3-Methylimidazole, 1-ethyl-3-methyllimidazolium bromide, 1-ethyl-3-methylimidazole a tetrafluoro borate, 1-ethyl-3-methylimidazole trifluoromethyl acetate, 1-ethyl-3-methylimidazole, chlorination 1-ethylpyridine, ethyl-butyl pyrroles two trifluoromethanesulfonimide salt, trimethyl ammonium chlorides etc.
The mol ratio of described aluminum trichloride (anhydrous) and ionic liquid is 0.5 ~ 5: 1.
Described body material is steel (such as soft steel, stainless steel etc.), metal species (iron, aluminium, copper, nickel etc.), alloy type (aluminium alloy, magnesium alloy), carbon element class, graphite, resin etc.
Described additive selects organic additive (such as benzene, toluene, dimethylbenzene, hexanaphthene, ammonium chloride, methyl alcohol, ethanol, formaldehyde, Glycerose, aubepine, choline chloride 60, glucose, niacin etc.), inorganic additives (such as Lanthanum trichloride, sodium-chlor, Repone K, lithium chloride, magnesium chloride, Manganous chloride tetrahydrate, Cerium II Chloride, Neodymium trichloride etc.), tensio-active agent (such as Span-80, Tween-20, Span-85, Span-40, Tween-20, CTAB etc.), one or more mixtures in high polymer (PVPK-30 etc.).
During plating, the stirring velocity of electrolyzer intermediate ion liquid electrolyte is 0 ~ 1000r/min.
Described inert nitrogen gas or the purity of argon gas are greater than 99.99%.
The present invention uses ionic liquid/additive system as ionogen, and electrolysis temperature is low, current efficiency is high, energy consumption is low, overcomes that existing process costs costliness, complex process, cost are high, particle size is difficult to the problems such as control.The material requirement of electrolyzer is anticorrosion, cost is low, usually adopts glass, quartz, tetrafluoroethylene etc.Nano aluminum size can be controlled by changing the kind of additive, addition and formula, obtain purity higher than 99.9% nano aluminum.Present invention process is simple, clean green, requires low, ionic liquid and additive wide material sources to the material of equipment, pollution-free, with low cost.
Accompanying drawing explanation
Fig. 1 is the pattern that ionic liquid/additive system Low-temperature electro-deposition prepares nano aluminum.
Embodiment
The present invention is illustrated by following instance, but the present invention be not only confined to following instance, all meet before and after the implementing method of described aim all in technical scope of the present invention.
Embodiment 1
By the vacuum-drying 24 hours at 50 DEG C of ionic liquid chlorination 1-butyl-3-Methylimidazole; in glove box; under the protection of rare gas element argon gas; chlorination 1-butyl-3-Methylimidazole will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism; in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition; until aluminum chloride and chlorination 1-butyl-3-Methylimidazole mol ratio are 2: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Add that massfraction is ionic liquid 0.1%, and mol ratio is Lanthanum trichloride and the hexanaphthene of 1: 1, continues to stir to ensure that electrolytic solution mixes, and obtains ionic liquid/additive electrolyte system.By base electrode copper sheet with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts sanding and polishing, ultrasonic cleaning, dried aluminium flake.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 1cm, keeps temperature of reaction to be 50 DEG C.Take aluminium flake as anode, copper sheet is negative electrode, and control current density is 10A/m
2, electrodeposition process stirring velocity is 200r/min, takes out test specimen after galvanic deposit 30min.Acetone, ethanol, deionized water rinsing is adopted successively after taking out test specimen, dry, obtain nano aluminum coating.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that settled layer aluminum particulate median size is 69.6nm, current efficiency is greater than 96%.
Embodiment 2
By the vacuum-drying 24 hours at 50 DEG C of ionic liquid chlorination 1-ethyl-3-methylimidazole; in glove box; under the protection of rare gas element argon gas; chlorination 1-ethyl-3-methylimidazole will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism; in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition; until aluminum chloride and chlorination 1-ethyl-3-methylimidazole mol ratio are 1.1: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Add the lithium chloride that massfraction is ionic liquid 0.01%, continue to stir to ensure that electrolytic solution mixes, obtain ionic liquid/additive electrolyte system.By base electrode stainless steel with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts sanding and polishing, ultrasonic cleaning, dried aluminium flake.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 0.5cm, keeps temperature of reaction to be 80 DEG C.Take aluminium flake as anode, stainless steel is negative electrode, and control current density is 50A/m
2, electrodeposition process stirring velocity is 300r/min, takes out test specimen after galvanic deposit 30min.Acetone, ethanol, deionized water rinsing is adopted successively after taking out test specimen, dry, obtain nano aluminum coating.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that settled layer aluminum particulate median size is 33.4nm, current efficiency is greater than 98%.
Embodiment 3
By the vacuum-drying 24 hours at 50 DEG C of ionic liquid chlorination 1-propyl group-3-Methylimidazole; in glove box; under the protection of rare gas element argon gas; chlorination 1-propyl group-3-Methylimidazole will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism; in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition; until aluminum chloride and chlorination 1-propyl group-3-Methylimidazole mol ratio are 3: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Add the benzene that massfraction is ionic liquid 10%, continue to stir to ensure that electrolytic solution mixes, obtain ionic liquid/additive electrolyte system.By base electrode soft steel with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts sanding and polishing, ultrasonic cleaning, dried aluminium flake.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 1.5cm, keeps temperature of reaction to be 50 DEG C.Take aluminium flake as anode, soft steel is negative electrode, and control current density is 100A/m
2, electrodeposition process stirring velocity is 500r/min, takes out test specimen after galvanic deposit 30min.Acetone, ethanol, deionized water rinsing is adopted successively after taking out test specimen, dry, obtain nano aluminum coating.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that settled layer aluminum particulate median size is 74.5nm, current efficiency is greater than 95%.
Embodiment 4
By the vacuum-drying 24 hours at 50 DEG C of ionic liquid 1-ethyl-3-methylimidazole a tetrafluoro borate; in glove box; under the protection of rare gas element argon gas; 1-ethyl-3-methylimidazole a tetrafluoro borate will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism; in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition; until aluminum chloride and 1-ethyl-3-methylimidazole a tetrafluoro borate mol ratio are 4: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Adding massfraction is ionic liquid 0.5%, and mol ratio is choline chloride 60 and the ammonium chloride of 1: 1, continues to stir to ensure that electrolytic solution mixes, and obtains ionic liquid/additive electrolyte system.By base electrode zinc metal sheet with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts sanding and polishing, ultrasonic cleaning, dried aluminium flake.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 1cm, keeps temperature of reaction to be 50 DEG C.Take aluminium flake as anode, zinc metal sheet is negative electrode, and control current density is 80A/m
2, electrodeposition process stirring velocity is 1000r/min, with under ultrasonic operational condition, obtains nanometer aluminium powder after galvanic deposit 30min in electrolyzer.With acetonitrile, nanometer aluminium powder is cleaned in glove box, put into oil tank after drying and preserve.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that settled layer aluminum particulate median size is 63.3nm, current efficiency is greater than 98.5%.
Embodiment 5
By the vacuum-drying 48 hours at 50 DEG C of ionic liquid 1-ethyl-3-methyllimidazolium bromide; in glove box; under the protection of rare gas element argon gas; 1-ethyl-3-methyllimidazolium bromide will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism; in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition; until aluminum chloride and 1-ethyl-3-methyllimidazolium bromide mol ratio are 0.5: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Adding massfraction is ionic liquid 5%, and mol ratio is Repone K and the divinyl of 1: 4, continues to stir to ensure that electrolytic solution mixes, and obtains ionic liquid/additive electrolyte system.By base electrode nickel sheet with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts sanding and polishing, ultrasonic cleaning, dried aluminium flake.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 1cm, keeps temperature of reaction to be 50 DEG C.Take aluminium flake as anode, nickel sheet is negative electrode, and control current density is 30A/m
2, with under ultrasonic operational condition, after galvanic deposit 30min, in electrolyzer, obtain nanometer aluminium powder.With acetonitrile, nanometer aluminium powder is cleaned in glove box, put into oil tank after drying and preserve.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that aluminum particulate median size is 66.3nm, current efficiency is greater than 92%.
Embodiment 6
By the vacuum-drying 48 hours at 50 DEG C of ionic liquid 1-ethyl-3-methylimidazole trifluoromethyl acetate; in glove box; under the protection of rare gas element argon gas; 1-ethyl-3-methylimidazole trifluoromethyl acetate will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism; in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition; until aluminum chloride and 1-ethyl-3-methylimidazole trifluoromethyl acetate mol ratio are 2: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Add the Span-85 that massfraction is ionic liquid 0.8%, continue to stir to ensure that electrolytic solution mixes, obtain ionic liquid/additive electrolyte system.By base electrode aluminium-zinc alloy with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts sanding and polishing, ultrasonic cleaning, dried aluminium flake.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 3cm, keeps temperature of reaction to be 50 DEG C.Take aluminium flake as anode, aluminium-zinc alloy is negative electrode, and control current density is 150A/m
2, with under ultrasonic operational condition, after galvanic deposit 30min, in electrolyzer, obtain nanometer aluminium powder.With acetonitrile, nanometer aluminium powder is cleaned in glove box, put into oil tank after drying and preserve.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that aluminum particulate median size is 29.9nm, current efficiency is greater than 93%.
Embodiment 7
By the vacuum-drying 48 hours at 50 DEG C of two for ionic liquid 1-ethyl-3-methylimidazole trifluoromethanesulfonimide salt, in glove box, under the protection of rare gas element argon gas, the two trifluoromethanesulfonimide salt of 1-ethyl-3-methylimidazole will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus, keep homo(io)thermism, in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition, until aluminum chloride and the two trifluoromethanesulfonimide salt mol ratio of 1-ethyl-3-methylimidazole are 1.5: 1, after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Adding massfraction is ionic liquid 0.2%, and mol ratio is magnesium chloride and the TX-100 of 1: 1, continues to stir to ensure that electrolytic solution mixes, and obtains ionic liquid/additive electrolyte system.After sand paper polishing grinding used for magnesium alloy for base electrode, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts sanding and polishing, ultrasonic cleaning, dried aluminium flake.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 0.8cm, keeps temperature of reaction to be 50 DEG C.Take aluminium flake as anode, magnesium alloy is negative electrode, and control current density is 60A/m
2, with under ultrasonic operational condition, after galvanic deposit 30min, in electrolyzer, obtain nanometer aluminium powder.With acetonitrile, nanometer aluminium powder is cleaned in glove box, put into oil tank after drying and preserve.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that aluminum particulate median size is 40.9nm, current efficiency is greater than 96%.
Embodiment 8
By the vacuum-drying 48 hours at 50 DEG C of ionic liquid 1-ethyl-3-methyllimidazolium bromide; in glove box; under the protection of rare gas element argon gas; 1-ethyl-3-methyllimidazolium bromide will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism; in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition; until aluminum chloride and 1-ethyl-3-methyllimidazolium bromide mol ratio are 2.5: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Adding massfraction is ionic liquid 5%, and mol ratio is Cerium II Chloride and the methyl alcohol of 1: 10, continues to stir to ensure that electrolytic solution mixes, and obtains ionic liquid/additive electrolyte system.By base electrode nickel sheet with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts sanding and polishing, ultrasonic cleaning, dried aluminium flake.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 1cm, keeps temperature of reaction to be 20 DEG C.Take aluminium flake as anode, nickel sheet is negative electrode, and control current density is 30A/m
2, with under ultrasonic operational condition, after galvanic deposit 30min, in electrolyzer, obtain nanometer aluminium powder.With acetonitrile, nanometer aluminium powder is cleaned in glove box, put into oil tank after drying and preserve.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that aluminum particulate median size is 66.3nm, current efficiency is greater than 84%.
Embodiment 9
By the vacuum-drying 48 hours at 50 DEG C of ionic liquid chlorination 1-ethylpyridine; in glove box; under the protection of rare gas element argon gas; chlorination 1-ethylpyridine will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism, in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition, until aluminum chloride and chlorination 1-ethylpyridine mol ratio are 5: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Add the toluene that massfraction is ionic liquid 50%, continue to stir to ensure that electrolytic solution mixes, obtain ionic liquid/additive electrolyte system.By base electrode copper sheet with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts vitreous carbon.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 1cm, keeps temperature of reaction to be 200 DEG C.Take vitreous carbon as anode, copper sheet is negative electrode, and control current density is 600A/m
2, with under ultrasonic operational condition, after galvanic deposit 30min, in electrolyzer, obtain nanometer aluminium powder.With acetonitrile, nanometer aluminium powder is cleaned in glove box, put into oil tank after drying and preserve.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that aluminum particulate median size is 72.6nm, current efficiency is greater than 99%.
Embodiment 10
By the vacuum-drying 48 hours at 50 DEG C of ionic liquid trimethyl ammonium chloride; in glove box; under the protection of rare gas element argon gas; trimethyl ammonium chloride will be filled and the chuck electrolyzer having installed thermometer is placed on magnetic stirring apparatus; keep homo(io)thermism, in electrolytic solution, successively add aluminum trichloride (anhydrous) change system composition, until aluminum chloride and trimethyl ammonium chloride mol ratio are 4: 1; after reaching thermal equilibrium and mixing, stir 2 ~ 3 hours under 50 DEG C of conditions.Adding massfraction is ionic liquid 1%, and mol ratio is Lanthanum trichloride, ammonium chloride, the hexanaphthene of 1: 1: 5, continues to stir to ensure that electrolytic solution mixes, and obtains ionic liquid/additive electrolyte system.By base electrode stainless steel with after sand paper polishing grinding, successively through oil removing, acid bubble, washing, acetone ultrasonic cleaning, after drying as deposition cathode; Anode adopts the graphite after ultrasonic cleaning.Added by ionic liquid in electrolyzer, the distance controlling of anode and negative electrode, at 1cm, keeps temperature of reaction to be 150 DEG C.Take graphite as anode, stainless steel is negative electrode, and control current density is 500A/m
2, with under ultrasonic operational condition, after galvanic deposit 30min, in electrolyzer, obtain nanometer aluminium powder.With acetonitrile, nanometer aluminium powder is cleaned in glove box, put into oil tank after drying and preserve.By disperseing (SEM/EDX) to analyze base in conjunction with scanning electron microscopy and X-ray, determine that aluminum particulate median size is 50.1nm, current efficiency is greater than 98%.
Claims (9)
1. adopt a method for ionic liquid/additive system electrodeposited nanocrystalline aluminium or nano aluminum coating, it is characterized in that described method comprises following steps:
(1) ionic liquid is placed on and is equipped with in the vacuum drying oven of Vanadium Pentoxide in FLAKES, constant-temperature vacuum drying 24 ~ 48h;
(2) in glove box, under inert nitrogen gas or argon shield, under the stirring of magnetic stirring apparatus, slowly in ionic liquid, add aluminum trichloride (anhydrous), be mixed to form low-temperature ionic liquids electrolytic solution, stir under constant temperature;
(3) add the additive that massfraction is 0.01% ~ 50%, stir;
(4) anticathode matrix carries out Pre-treatment before plating, and method is as follows: sand papering → cleaning → electrochemical deoiling → washing → pickling → washing → acetone soaks → dry → dilution after concentrated hydrochloric acid and the vitriol oil nitration mixture in activation treatment → washed with de-ionized water → drying;
(5) anode adopts aluminium, graphite, pottery, vitreous carbon, and the distance between anode and negative electrode is 0.5 ~ 15cm;
(6) add appropriate electrolytic solution in a cell, under nitrogen or argon shield condition, constant electrolysis temperature is 20 DEG C ~ 300 DEG C, is 10 ~ 150A/m in current density
2condition under carry out DC electrodeposition and prepare nano aluminum;
(7) in electrodeposition process with under ultrasonic operational condition, in electrolyzer, obtain nanometer aluminium powder after galvanic deposit 30min; With acetonitrile, nanometer aluminium powder is cleaned in glove box, put into oil bath after drying and preserve.
2. method according to claim 1, it is characterized in that described ionic liquid cation is quaternary ammonium salt ion, quaternary alkylphosphonium salt ion, imidazolium ion or pyridinium salt ion, negatively charged ion is halide-ions, tetrafluoroborate ion, hexafluorophosphoricacid acid ions or other inorganic acid ion.
3. method according to claim 1, is characterized in that described ionic liquid is one or more the mixing liquid in chlorination 1-butyl-3-Methylimidazole, 1-ethyl-3-methyllimidazolium bromide, 1-ethyl-3-methylimidazole a tetrafluoro borate, 1-ethyl-3-methylimidazole trifluoromethyl acetate, the two trifluoromethanesulfonimide salt of 1-ethyl-3-methylimidazole, chlorination 1-ethylpyridine, the two trifluoromethanesulfonimide salt of ethyl-butyl pyrroles, trimethyl ammonium chloride.
4. method according to claim 1, is characterized in that the mol ratio of described aluminum trichloride (anhydrous) and ionic liquid is 0.5 ~ 5:1.
5. method according to claim 1, is characterized in that described body material is metal species, alloy type, carbon element class, resin.
6. method according to claim 1, is characterized in that described body material is soft steel, stainless steel, iron, aluminium, copper, nickel, aluminium alloy, magnesium alloy, carbon element, graphite, vitreous carbon, pottery.
7. method according to claim 1, is characterized in that described additive selects one or more mixtures in organic additive, inorganic additives, tensio-active agent, high polymer.
8. method according to claim 1, is characterized in that described additive is benzene,toluene,xylene, hexanaphthene, divinyl, vinylbenzene, quadrol, ammonium chloride, methyl alcohol, ethanol, formaldehyde, Glycerose, aubepine, choline chloride 60, glucose, niacin, sodium-chlor, Repone K, lithium chloride, Manganous chloride tetrahydrate, magnesium chloride, Lanthanum trichloride, Cerium II Chloride, Neodymium trichloride, Span-80, Span-85, Span-40, Tween-20, CTAB, PVPK-30.
9. method according to claim 1, when it is characterized in that described plating, the stirring velocity of electrolyzer intermediate ion liquid electrolyte is 0 ~ 1000r/min.
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