CN101831641B - Acid zinc dipping solution of magnesium-lithium alloy and zinc dipping method - Google Patents
Acid zinc dipping solution of magnesium-lithium alloy and zinc dipping method Download PDFInfo
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- CN101831641B CN101831641B CN201010173022XA CN201010173022A CN101831641B CN 101831641 B CN101831641 B CN 101831641B CN 201010173022X A CN201010173022X A CN 201010173022XA CN 201010173022 A CN201010173022 A CN 201010173022A CN 101831641 B CN101831641 B CN 101831641B
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Abstract
The invention provides acid zinc dipping solution and a zinc dipping method of magnesium-lithium alloy. The acid zinc dipping solution of the magnesium-lithium alloy is prepared by taking zinc chloride as main salt, malic acid as main coordination agent and acidity regulator, lactic acid as auxiliary coordination agent, sodium fluoride as additive and ammonia water as PH regulator. A thin, flat and smooth acid zinc dipping layer can be obtained by adopting the acid zinc dipping solution of the magnesium-lithium alloy of the invention to carry out zinc dipping for once, and the zinc particles of the acid zinc dipping layer are spherical, have uniform size and are tiny and compact, and the coverage degree of the zinc dipping layer on a basal body is rather high. After the acid zinc dipping, the plating layer obtained by either electroplating or chemical plating has excellent performance. The method has the advantages of low preparation cost, less preparation steps, simple operation, wild reaction conditions, capability of alleviating strong corrosion of strong basic zinc dipping solution to the basal body of the magnesium-lithium alloy, environment friendliness, energy saving, less conditions which need to be controlled and can be easily realized and great possibility of being applied to mass production.
Description
Technical field
What the present invention relates to is a kind of surface treatment liquid of alloy material.Specifically a kind of casting magnesium lithium alloy is electroplated and the preceding pretreated acidic zinc dipping solution of electroless plating.The invention still further relates to a kind of cast magnesium lithium alloy soak the zinc method.Belong to inorganic metal material field.
Background technology
Magnesium lithium alloy is a lightest present structural metallic materials, have the high-strength characteristics of ultralight, and having advantages such as good electromagnetic shielding ability and shock resistance, good toughness, bending strength are big, easy deformation processing, is a preferred class formation material in the fields such as aerospace, weapons, automobile, electronics, military affairs.The research of magnesium lithium alloy at present both at home and abroad mainly concentrates on aspects such as the preparation of high performance alloys and performance.Research direction mainly concentrates on founding, preparation technology and mechanics, mechanical property etc.When being added in of the elemental lithium in the alloy improves plasticity, improves ductility and reduce alloy density, also significantly reduced its etch resistant properties.The solidity to corrosion difference of magnesium lithium alloy is its key in application factor of restriction, and therefore, the surface treatment method that research improves alloy corrosion resistance has important practical significance.The method that improves general corrosion stability of magnesium alloy has a lot as chemical conversion, plating or electroless plating, anodic oxidation, vapour deposition, differential arc oxidation, ion implantation etc. mainly concentrate on chemical conversion, plating, electroless plating and anodic oxidation etc. and improve the corrosion proof method of magnesium lithium alloy at present.Casting magnesium lithium alloy, the i.e. magnesium lithium alloy used of foundry goods and die casting.To carrying out special pre-treatment before the casting magnesium lithium alloy electroplating surface, its method mainly contains soaks zinc method and chemically coated nickel method.To also carrying out special pre-treatment before the casting magnesium lithium alloy surface chemical plating, its method mainly contains soaks zinc method and direct chemical plating.The general usefulness of the zinc method of soaking of magnesium lithium alloy be that alkalescence is soaked the zinc method, its main component is: zinc sulfate 30g/L, trisodium phosphate 120g/L, Sodium Fluoride or lithium fluoride 3-5g/L, yellow soda ash 5g/L, pH 10.2-10.4, temperature 70-80 ℃, time 3-10min.This method needs, and to soak the zinc temperature higher, and need secondary soaking zinc could obtain good displacement zinc layer.Because the zinc dipping solution of alkalescence makes the magnesium lithium alloy matrix be subjected to serious corrosion, can't satisfy the accurate requirement to accessory size, therefore alkaline dip galvanizing technique more and more has not been suitable for magnesium lithium alloy.Along with the fast development of 3C electronic product, also more and more surging to the demand of acidic zinc dipping, the research of acidic zinc dipping solution is significant.
Summary of the invention
The object of the present invention is to provide a kind of easy and simple to handle, mild condition, the magnesium lithium alloy acidic zinc dipping solution energy-conservation, that toxic is little and with low cost.The present invention also aims to provide a kind of and soak the zinc method based on magnesium lithium alloy acidic zinc dipping solution of the present invention
The object of the present invention is achieved like this:
The mixed solution that magnesium lithium alloy acidic zinc dipping solution of the present invention is as follows to be obtained:
(1) zinc chloride 70-75g fully dissolves with distilled water, obtains liquor zinci chloridi;
(2) oxysuccinic acid 8-10g fully dissolves with distilled water, obtains malic acid solution;
(3) Sodium Fluoride 4-5g/L fully dissolves with distilled water, obtains Fluorinse;
(4) 2ml lactic acid is added in the malic acid solution, fully stir, obtain mixed liquor A;
(5) liquor zinci chloridi is added in the mixed liquor A under constantly stirring, make the abundant complexing of zine ion, obtain mixed liquid B;
(6) Fluorinse is under agitation poured in the mixed liquid B, and fully stirred;
(7) adding distil water is diluted to 1 liter volume;
(8) regulate pH to 4.0 with ammoniacal liquor;
(9) obtain acidic zinc dipping solution with filter paper filtering.
The zinc method of soaking based on magnesium lithium alloy acidic zinc dipping solution of the present invention is:
(1) magnesium lithium alloy is polished, adopting then with chromic anhydride, iron nitrate, Potassium monofluoride is that the etching solution of main component carries out etch, and temperature is a room temperature, time 1.5min;
(2) magnesium lithium alloy behind over etching is cleaned with cold water, clean with flowing water again;
(3) will put into phosphoric acid through the magnesium lithium alloy that cleans, ammonium hydrogen fluoride solution activates, temperature is a room temperature, time 1.5min;
(4) magnesium lithium alloy behind overactivation is cleaned with flowing water;
(5) slowly acidic zinc dipping solution is warming up to 40 ℃;
(6) handle soaking zinc in the magnesium lithium alloy immersion acidic zinc dipping solution of handling well, in soaking the zinc process, constantly shake sample, make the hydrogen desorption that is adsorbed on specimen surface, galvanizing time is 120s;
(7) the magnesium lithium alloy sample that will soak behind the zinc takes out, and fully washes oven dry with flowing water;
The mixed solution that described acidic zinc dipping solution is as follows to be obtained:
1) zinc chloride 70-75g fully dissolves with distilled water, obtains liquor zinci chloridi;
2) oxysuccinic acid 8-10g fully dissolves with distilled water, obtains malic acid solution;
3) Sodium Fluoride 4-5g/L fully dissolves with distilled water, obtains Fluorinse;
4) 2ml lactic acid is added in the malic acid solution, fully stir, obtain mixed liquor A;
5) liquor zinci chloridi is added in the mixed liquor A under constantly stirring, make the abundant complexing of zine ion, obtain mixed liquid B;
6) Fluorinse is under agitation poured in the mixed liquid B, and fully stirred;
7) adding distil water is diluted to 1 liter volume;
8) regulate pH to 4.0 with ammoniacal liquor;
9) use filter paper filtering.
Described oxysuccinic acid is a L MALIC ACID.
The present invention adopts zinc chloride as main salt, and oxysuccinic acid is as main coordination agent and acidity regulator, and lactic acid is as auxiliary complexing agent, and Sodium Fluoride is as additive, and agent is mixed with acidic zinc dipping solution to ammoniacal liquor as pH regulator.The replacement(metathesis)reaction of acidic zinc dipping takes place that alkalescence carries out must be slowly, and the reduction rate of zinc slows down.Adopt this system once to soak zinc and just can obtain thinly and smooth smooth, the zinc particle presents spherical, and size is even, the acidic zinc dipping layer of tiny densification, and zinc-impregnating layer is very high to the level of coverage of matrix.No matter electroplate or electroless plating the coating performance excellence that obtains through behind the acidic zinc dipping.This method preparation cost is low, and preparation steps is few, and is simple to operate, the reaction conditions gentleness has been slowed down the strong corrosion that the strong basicity zinc dipping solution causes the magnesium lithium alloy matrix, environmental protection and energy saving, need the condition of control few and be easy to accomplish, get a good chance of being applied to scale operation.
Under the ammoniacal liquor adjusting condition, the zinc-impregnating layer particle presents slick fairly regular spherical, and zinc-impregnating layer is big to the magnesium lithium alloy surface coverage, and than even compact, improved the solidity to corrosion of matrix, the membrane resistance of acidic zinc dipping layer is up to 836.9 Ω, and steady potential is about-1.00V.
The acidic zinc dipping solution of casting magnesium lithium alloy uses oxysuccinic acid as acidity regulator, replacing hydrofluoric acid commonly used in the acidic zinc dipping solution is the technical breakthrough of acidic zinc dipping, the new prescription of the acidic zinc dipping solution that the present invention obtains, at first reduced the concentration of main salt, secondly the cooperation by Sodium Fluoride and oxysuccinic acid, lactic acid has improved the performance of acidic zinc dipping solution, minimizing has improved the safety coefficient of experiment to the corrosion of experimental installation.The present invention is simpler than other method technology, is easy to control, and with low cost, little to the degree of magnesium lithium alloy matrix corrosion, the form of zinc crystal grain, uniformity coefficient, density, coverage are all relatively good.Compare with traditional strong basicity zinc dipping solution, satisfy the requirement to the accessory size measure of precision, coordination agent does not contain prussiate, helps environment protection, helps health of operators, can realize green production.Magnesium lithium alloy soaks behind the zinc good with the subsequent plating layer bonding force.
Description of drawings
Fig. 1 a-Fig. 1 g is that magnesium lithium alloy utilizes acidic zinc dipping solution of the present invention to soak the SEM figure of gained acidic zinc dipping layer behind the zinc, and wherein Fig. 1 a is for amplifying 100 times, Fig. 1 b for amplifying 200 times, Fig. 1 c for amplifying 500 times, Fig. 1 d for amplifying 2000 times, Fig. 1 e for amplifying 5000 times, Fig. 1 f for amplifying 10000 times, Fig. 1 g for amplifying 30000 times.
Fig. 2 is the EIS spectrogram of magnesium lithium alloy matrix in 3.5%NaCl solution.
Fig. 3 is the EIS spectrogram of magnesium lithium alloy acidic zinc dipping layer in 3.5%NaCl solution.
Fig. 4 is the equivalent-circuit diagram of EIS, wherein R
eBe solution resistance, it is the Luggin kapillary mouth of pipe of reference electrode and the solution ohmage between the research electrode, C
fBe membrane capacitance, R
fBe membrane resistance; C
tBe research electrode/solution interface electric double layer capacitance, R
tElectrochemical reaction resistance for the research electrode.
Fig. 5 soaks the time-potential curve of zinc process for the magnesium lithium alloy matrix in the acidic zinc dipping solution of example.Current potential sharply increases in time when soaking zinc as seen from the figure and just having begun, and during the 200s left and right sides, the speed that current potential rises is in time slowed down, and during the 1000s left and right sides, current potential fluctuation up and down very by a small margin changes, but basicly stable about-1.00V.By analyzing as can be known, the reaction times of acidic zinc dipping is optimum about 2min.
The table 1 of Fig. 6 is the component value of equivalent electrical circuit.Magnesium lithium alloy acidic zinc dipping layer has improved the solidity to corrosion of matrix greatly as seen from table.
Embodiment
For example the present invention is done in more detail below and describes:
Present embodiment is a kind of easy and simple to handle, mild condition, energy-conservation, that toxic is little and with low cost a kind of novel method of casting the acidic zinc dipping solution that contains L MALIC ACID of magnesium lithium alloy.
A) magnesium lithium alloy sample polishing, adopting with chromic anhydride, iron nitrate, Potassium monofluoride then is the etch of main component, temperature is a room temperature, time 1.5min;
B) will be through A) sample after the etch cleans with cold water, cleans with flowing water;
C) will be through B) sample put into phosphoric acid, ammonium hydrogen fluoride solution activates, temperature is a room temperature, time 1.5min;
D) will be through C) sample after the activation cleans with flowing water;
E) will be through D) after sample put into acidic zinc dipping solution and soak zinc and handle.
The compound method of magnesium lithium alloy acidic zinc dipping solution and soak the technological specification of zinc following (experiment agents useful for same and distilled water are analytical pure)
1) getting zinc chloride 75g/L fully dissolves with distilled water;
2) getting oxysuccinic acid 10g/L fully dissolves with distilled water;
3) getting Sodium Fluoride 5g/L fully dissolves with distilled water;
4) get 2ml/L lactic acid and add step 2) malic acid solution in, fully stir;
5) with 1) under constantly stirring, add in the formed solution of step 4), make the abundant complexing of zine ion;
6) with 3) under agitation pour in the formed solution of step 5), and fully stir;
7) adding distil water is diluted to the volume of regulation;
8) regulate pH to 4.0 with ammoniacal liquor;
9) use the filter paper filtering acidic zinc dipping solution;
10) slowly acidic zinc dipping solution is warming up to 40 ℃;
11) handle soaking zinc in the magnesium lithium alloy sample immersion acidic zinc dipping solution of handling well, in soaking the zinc process, constantly shake sample, make the hydrogen desorption that is adsorbed on specimen surface.Galvanizing time is 120s;
12) the magnesium lithium alloy sample that will soak behind the zinc takes out, and fully washes oven dry with flowing water.
Claims (2)
1. magnesium lithium alloy acidic zinc dipping solution, the mixed solution that it is characterized in that as follows being obtained:
(1) zinc chloride 70-75g fully dissolves with distilled water, obtains liquor zinci chloridi;
(2) oxysuccinic acid 8-10g fully dissolves with distilled water, obtains malic acid solution;
(3) Sodium Fluoride 4-5g/L fully dissolves with distilled water, obtains Fluorinse;
(4) 2ml lactic acid is added in the malic acid solution, fully stir, obtain mixed liquor A;
(5) liquor zinci chloridi is added in the mixed liquor A under constantly stirring, make the abundant complexing of zine ion, obtain mixed liquid B;
(6) Fluorinse is under agitation poured in the mixed liquid B, and fully stirred;
(7) adding distil water is diluted to 1 liter volume;
(8) regulate pH to 4.0 with ammoniacal liquor;
(9) obtain acidic zinc dipping solution with filter paper filtering.
A magnesium lithium alloy acidic zinc dipping solution soak the zinc method, it is characterized in that:
(1) magnesium lithium alloy is polished, adopting then with chromic anhydride, iron nitrate, Potassium monofluoride is that the etching solution of main component carries out etch, and temperature is a room temperature, time 1.5min;
(2) magnesium lithium alloy behind over etching is cleaned with cold water, clean with flowing water again;
(3) will put into phosphoric acid through the magnesium lithium alloy that cleans, ammonium hydrogen fluoride solution activates, temperature is a room temperature, time 1.5min;
(4) magnesium lithium alloy behind overactivation is cleaned with flowing water;
(5) slowly acidic zinc dipping solution is warming up to 40 ℃;
(6) handle soaking zinc in the magnesium lithium alloy immersion acidic zinc dipping solution of handling well, in soaking the zinc process, constantly shake sample, make the hydrogen desorption that is adsorbed on specimen surface, galvanizing time is 120s;
(7) the magnesium lithium alloy sample that will soak behind the zinc takes out, and fully washes oven dry with flowing water;
The mixed solution that described acidic zinc dipping solution is as follows to be obtained:
1) zinc chloride 70-75g fully dissolves with distilled water, obtains liquor zinci chloridi;
2) oxysuccinic acid 8-10g fully dissolves with distilled water, obtains malic acid solution;
3) Sodium Fluoride 4-5g/L fully dissolves with distilled water, obtains Fluorinse;
4) 2ml lactic acid is added in the malic acid solution, fully stir, obtain mixed liquor A;
5) liquor zinci chloridi is added in the mixed liquor A under constantly stirring, make the abundant complexing of zine ion, obtain mixed liquid B;
6) Fluorinse is under agitation poured in the mixed liquid B, and fully stirred;
7) adding distil water is diluted to 1 liter volume;
8) regulate pH to 4.0 with ammoniacal liquor;
9) use filter paper filtering.
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