CN101074479A - Method for treating magnesium-alloy workpiece, workpiece therefrom and composition therewith - Google Patents

Method for treating magnesium-alloy workpiece, workpiece therefrom and composition therewith Download PDF

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Publication number
CN101074479A
CN101074479A CNA2006100810216A CN200610081021A CN101074479A CN 101074479 A CN101074479 A CN 101074479A CN A2006100810216 A CNA2006100810216 A CN A2006100810216A CN 200610081021 A CN200610081021 A CN 200610081021A CN 101074479 A CN101074479 A CN 101074479A
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magnesium alloy
ion
surface treatment
nickel
constituent
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何靖
李威德
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JINMEIRUI SCIENCE AND TECHNOLOGY CO.,LTD.
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何靖
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Abstract

A method for treating magnesium-alloy work-piece surface, its work piece, its degrease surface treatment and non-electroplating nickel composition are disclosed. The process is carried out by forming displacing and activating layer containing nickel and metal M crystal seed on surface layer exposed with magnesium-alloy solid melt and heat treating. It has strong adhesion and long-period anti-corrosive function.

Description

The surface treatment method of magnesium alloy workpiece, handle the workpiece of gained and be used for each constituent of this method
Technical field
The present invention relates to a kind of method that is used for surface treatment one magnesium alloy workpiece, particularly relate to a kind of the utilization in regular turn at the exposed enterprising line replacement activation of upper layer (conversion activation), electroless plating (electroless plating) and the heat treated surface treatment method that the sosoloid (solid solution) of close-packed hexagonal body crystal formation is arranged, and through this method handle and the magnesium alloy workpiece of tool firm engagement transition layer, required each constituent during with this method of enforcement.
Background technology
Known magnesium alloy (Magnesium alloy) light weight, structural strength height, inexpensive, originally on Industrial materials, should play an important role, but because its surface-treated degree of difficulty height, so far magnesium alloy can't effectively commercialization volume production, study carefully its because of mainly contain following some: (1) magnesium is quite active metallic element, it can be corroded by most negatively charged ion in atmosphere or pH value are environment below 10, and the oxide film that magnesiaization forms is loosely organized and can't effectively cover substrate surface, so the slushing oil of magnesium alloy is very poor; (2) low (16～40HRE), in easily by the application scenario of scratch, workpiece surface subjects to destroy and therefore easier being corroded magnesium alloy hardness.And highlighted the problem of corrosion stability difference; (3) crystalline structure of magnesium metal is close-packed hexagonal body (hexagonal closed-packed, be called for short hcp), therefore, except lithium (Li), aluminium (Al), zinc (Zn), zirconium (Zr), the several elements of thorium (Th), be difficult to form solid fusion gold, that is the covering sticking power of magnesium alloy work-piece surface is very poor with other metallic elements, therefore the upper layer that is difficult to formation adequate thickness on magnesium alloy workpiece improves the problem of aforementioned corrosion-vulnerable, or magnesium alloy workpiece is firmly engaged with other workpiece.
In view of this, United States Patent (USP) the 4th, 551,211,4,770,946,5,683,522,6,645,339B1,6,669,997 B2,6,787,192 B2 and 6,755, propose the mode of solution respectively 918 B2 numbers, wish to make it have the essence applicability, be described as follows one by one now by magnesium alloy workpiece being bestowed surface treatment:
United States Patent (USP) the 4th; 551; disclose for No. 211, in alkaline medium, use compound such as aluminium hydroxide that magnesium alloy is carried out the method for anodizing, though can reach effect against corrosion; but the anonite membrane that gets because of anodizing can't with the Mg alloy surface tight joint; for avoiding thicker the causing easily of thickness of coating to come off, thus only can be formed with the coating of limiting thickness, moreover; the toughness of anonite membrane and intensity are all not enough, so can't reach long-term anticorrosion protection.
United States Patent (USP) the 4th; 770; disclose for No. 946; in alkaline medium, use in regular turn compound such as potassium permanganate to magnesium alloy carry out anodizing, thereon the coated heat thermosetting resin, impose that the electricity slurry is handled and the method for evaporation; similar aforementioned; anodizing and anonite membrane can't with the workpiece surface tight joint, and because of the thermal expansivity of thermosetting resin easily produces the crack much larger than magnesium alloy, so can't reach long-term anticorrosion protection equally.
United States Patent (USP) the 5th; 683; then disclose for No. 522; utilize that degreasing, alkaline aqueous solution are cleaned, deoxidation, and make magnesium alloy workpiece impregnated in a solution that contains phosphoric acid salt, fluorion and sodium bifluoride then, handle Mg alloy surface is carried out coating; similarly; because of connectivity is not enough, only can be formed with the upper layer of limiting thickness, so can't reach long-term anticorrosion protection.
United States Patent (USP) the 6th; 787; disclose a kind of method for preparing treated magnesium and magnesium alloy assembly 192 B2 numbers; it comprises one and has the step (A) of the first layer of difficulty soluble salt in order to formation; and one utilize one to be selected from alkanolamine; the pretreating agent of materials such as aliphatic amine comes the step (B) of the first layer of treatment step (A) gained; yet; because of this first layer contains crystal water usually and the problem of ion-transfer (migration) is easily arranged; therefore can't with the magnesium alloy tight joint; add that second tunic is made of more unsettled organic class material, so can't reach long-term anticorrosion protection.
United States Patent (USP) the 6th, 755, the invention that discloses for 918 B2 numbers then are to be displacer with vanadium and cerium; magnesium alloy workpiece is carried out surface treatment; because of the coating that forms can't closely engage with magnesium alloy workpiece, adequate thickness can't be provided equally, also long-term anticorrosion protection can't be reached.
United States Patent (USP) the 6th; 669; then disclose for 997 B2 numbers; down auxiliary at ultrasound; plate a bottom on the surface of magnesium alloy; on bottom, form the top layer in various mode afterwards; wherein underlying metal is that to adopt than the top layer be the metal of inertia (noble); though this method can obtain the coating of the temporary transient effect against corrosion of tool; but by than inert metal, for example (,) the formed bottom of copper equally can't tight joint in magnesium alloy, moreover; the inert metal of bottom can produce the internal cell effect and cause the rapid decline of corrosion strength with magnesium alloy, also can't reach long-term anticorrosion protection.
United States Patent (USP) the 6th, 645, disclose for 339 B1 numbers, preparation one earlier contains the constituent of at least one polymerizability silicone (silicone), at least one amino-contained silane and at least one filler, then utilize this constituent as between magnesium alloy workpiece or the tackiness agent of magnesium alloy workpiece and other base materials, but because of the hardness deficiency of this constituent after sclerosis, easily produce and break and engage also not good with Mg alloy surface, engage or make magnesium alloy workpiece to be engaged to the purpose of other workpiece between magnesium alloy workpiece so can't reach to make, also can't avoid magnesium alloy to be corroded simultaneously.
From the above, all trials are so far carried out surface treatment to magnesium alloy workpiece, and make magnesium alloy work-piece surface firmly engage the method for a coating by this, and deficiency and problem that can't practical commercialization are all arranged.
This shows that above-mentioned existing magnesium alloy work-piece surface is handled in method and used, and obviously still has inconvenience and defective, and demands urgently further being improved.Handle the problem that exists in order to solve magnesium alloy work-piece surface, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable design finished by development, and common product does not have appropriate structure to address the above problem, and this obviously is the problem that the anxious desire of relevant dealer solves.Therefore how to found a kind of new method for the treatment of magnesium alloy work-piece surface, just become the current industry utmost point to need improved target.
Because above-mentioned existing magnesium alloy work-piece surface is handled the defective that exists, the inventor is based on being engaged in this type of product design manufacturing abundant for many years practical experience and expertise, and the utilization of cooperation scientific principle, actively studied innovation, in the hope of founding a kind of new magnesium alloy work-piece surface processing scheme, can improve general existing magnesium alloy work-piece surface treatment technology, make it have more practicality.Through constantly research, design, and after studying sample and improvement repeatedly, create the present invention who has practical value finally.
Summary of the invention
Difficulty in view of magnesium alloy work-piece surface processing for a long time, this case contriver thinks to reach, aforementioned the whole bag of tricks not enough or can't business-like main cause be: the sticking power between these surface treatment gained tectums and Mg alloy surface is too poor, institute thinks and avoids causing easy obscission because of coating gravity, all can't plate adequate thickness in design and reach long-term effect against corrosion.Except can't problem effectively against corrosion, because of these tectums can't firmly be engaged on the magnesium alloy, thus make magnesium alloy work firmly to be bonded on the various workpiece easily, and then purposes is urgently restricted so far to make inexpensive magnesium alloy.
This case contriver thinks to reach, the flaky main cause of two metal interlevels is that the difference of crystal formation is excessive, therefore through testing and be aided with the basis of scientific principle in many ways, trial addresses the above problem all sidedly by form a crystal formation can firmly engage and can form thereon various functional layer with magnesium alloy near magnesium alloy transition layer on magnesium alloy workpiece.
Moreover, if magnesium alloy work-piece surface has impurity or oxide film etc., certainly will hinder the tight joint of transition layer, therefore must make the solid solution physical efficiency that is close-packed hexagonal body crystal formation at Mg alloy surface place expose earlier, then directly form the close transition layer of crystal formation more thereon, can really effectively overcome the problem of joint.
Then, set out near notion that can tight joint with crystal formation, this transition layer the best is to be made of the crystal formation metal that is hcp identical with magnesium, such as zinc (Zn), cobalt (Co) and cadmium (Cd).Simultaneously, considering the practicality of magnesium alloy workpiece after treatment, and under the excellent rerum natura (weldability, glossiness, solidity to corrosion and attrition resistance) of present nickel and nickel alloy coating, this transition layer is preferably and is designed to contain the nickel metal simultaneously, is beneficial on this transition layer can constitutionally to form the nickel coating of tight joint again.
The objective of the invention is to, overcome the defective of the surface treatment method existence of existing magnesium alloy workpiece, and a kind of surface treatment method of new magnesium alloy workpiece is provided, technical problem to be solved is to make it can make the coating that forms firm engagement on the magnesium alloy workpiece, thereby is suitable for practicality more.
Another object of the present invention is to, overcome the defective that existing magnesium alloy workpiece exists, and a kind of new magnesium alloy workpiece is provided, technical problem to be solved is to make it have the transition layer of a firm engagement on magnesium alloy workpiece, thereby is suitable for practicality more.
A further object of the present invention is, a kind of degreasing constituent is provided, technical problem to be solved is to make its surface treatment method that is available for aforesaid magnesium alloy workpiece, has the upper layer of most exposed sosoloid to produce one, thereby is suitable for practicality more.
An also purpose of the present invention is that a kind of surface treatment constituent is provided, and technical problem to be solved is to make it in the surface treatment method of aforesaid magnesium alloy workpiece, forms crystal seed as displacement activation constituent, thereby is suitable for practicality more.
An also purpose of the present invention is that a kind of electroless nickel plating constituent is provided, and technical problem to be solved is to make its surface treatment method that can be used for aforementioned magnesium alloy workpiece, thereby is suitable for practicality more.
The object of the invention to solve the technical problems realizes by the following technical solutions.A kind of method that is used for surface treatment one magnesium alloy workpiece according to the present invention proposes is characterized in that it comprises following steps:
(a) make one to have most the workpiece that magnesium alloy constituted that are the sosoloid of close-packed hexagonal body crystal formation by one and forms one and exposed most individual upper layers that are the sosoloid of close-packed hexagonal body crystal formation are arranged;
(b) make and form a displacement active layer that comprises most nickel crystal seeds and most metal M crystal seed on the upper layer of this workpiece, this metal M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance;
(c) on this displacement active layer, deposit one in the electroless plating mode and comprise one based on metallic nickel and metal M and be doped with the first plated state electroless nickel layer of the amorphous structure of phosphorus; And
(d) this workpiece is bestowed a thermal treatment, so that should with this displacement active layer place of the vicinity of this upper layer and the first plated state electroless nickel layer solid solution take place respectively by displacement active layer, and form a transition layer, and obtain one and have a magnesium alloy layer that constitutes by this magnesium alloy, the workpiece of one transition layer and one first electroless nickel layer, this transition layer has most the sosoloid that are close-packed hexagonal body crystal formation that contain magnesium and M, and it is at least one by M, at least the intermetallic compound of the two formation in nickel and the phosphorus, and first electroless nickel layer comprises one based on metallic nickel and M and be doped with the amorphous structure of phosphorus.
The object of the invention to solve the technical problems also adopts following technical measures further to realize.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, magnesium alloy in the wherein said step (a) also comprise most between described sosoloid any the two and contain the intergranular of at least one intermetallic compound, and this upper layer has more most slits and is to form by following mode: the end face contact one that makes this workpiece bestowed a ultrasound and with the reactivity of this intermetallic compound degreasing constituent greater than described sosoloid, so that the top layer of the sosoloid of at least a portion at contiguous this end face place and the intermetallic compound at least one part intergranular and the reaction of this constituent, and form a residue, then remove this residue is molten, so that most close-packed hexagonal body sosoloid expose out, and form most by the slit of this end face to lower recess.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said degreasing constituent comprise an organic acid, a teepol and a high polar organic solvent.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said organic acid are to be selected from lactic acid, formic acid, oxalic acid, succsinic acid, hexanodioic acid, citric acid, oxysuccinic acid, or the combination of above-mentioned substance.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said organic acid are that lactic acid and this residue comprise magnesium lactate.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said teepol are sodium laurylsulfonate and/or 1, the 2-alkyl phosphate.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said high polar organic solvent is the combination that is selected from methyl alcohol, ethanol, propyl alcohol, Virahol or above-mentioned substance.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said organic acid and the teepol concentration in this degreasing constituent respectively is 0.1-2M and 0.001-0.01M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said organic acid and the teepol concentration in this degreasing constituent respectively is 0.4-0.7M and 0.002-0.04M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the ultrasound in the wherein said step (a) has a frequency between 300-360KHz, or has one and can produce a frequency between the 300-360KHz frequency by simple harmonic quantity concussion.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, molten the removing of wherein said residue is by making water or the alcohols below the C4 clean this workpiece and reaching.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, molten the removing of wherein said residue is to reach by making water clean this workpiece.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, molten the removing of wherein said residue is to be undertaken by simultaneously this workpiece is bestowed a ultrasound when cleaning.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said ultrasound have a frequency between 300-360KHz, or have one and can produce a frequency between the 300-360KHz frequency by simple harmonic quantity concussion.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the metal M in the wherein said step (b) is a zinc.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said step (b) are to react by the displacement activation constituent that makes this upper layer and comprise water, fluorion, ammonium ion, M ion and nickel ion to reach.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said displacement activation constituent is bestowed a ultrasound.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said ultrasound have a frequency between 300-360KHz, or have one and can produce a frequency between the 300-360KHz frequency by simple harmonic quantity concussion.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said M is a zinc.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the displacement activation constituent that uses in the wherein said step (b) is to be maintained at one between 0-85 ℃ temperature, and has a pH value between between 0.1-2, fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, and 0.05-2M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the displacement activation constituent that uses in the wherein said step (b) is to be maintained at one between 15-30 ℃ temperature, and has a pH value between between 0.2-1.5, fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.7-1.4M, 0.5-0.9M, 0.12-0.25M, and 0.2-0.25M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, formed displacement active layer comprises most nickel crystal seeds, most metal M crystal seed in the wherein said step (b), and magnesium fluoride.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the electroless plating of wherein said step (c) is to be undertaken by making this displacement active layer contact one first electroless nickel plating constituent, and this first electroless nickel plating constituent comprises the C2-C8 organic acid ion that water, fluorion, ammonium ion, M ion, nickel ion, hypophosphite ion and are made for buffer reagent.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, M ion in the first electroless nickel plating constituent that uses in the wherein said step (c) is a zine ion, and this constituent is to be maintained at one between 70-100 ℃ temperature, and have a pH value between between 2-6.5, the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.1-5M, 0.1-5M, 0.02-2M, 0.02-2M, 0.05-1M and 0.02-2M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the first electroless nickel plating constituent that uses in the wherein said step (c) is to be maintained at one between 80-97 ℃ temperature, and have a pH value between between 3-4.5, the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.35-0.53M, 0.35-0.53M, 0.06-0.09M, 0.127-0.155M, 0.1-0.2M and 0.07-0.1M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the thickness of the formed first plated state electroless nickel layer of wherein said step (c) are controlled does not fill up the formed slit of this step (a).
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the heat treated temperature of wherein said step (d) are between 140 ℃ to 250 ℃.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the heat treated temperature of wherein said step (d) are between 170 ℃ to 190 ℃.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, it also comprises a step (c-1) between between step (c) and step (d), this step (c-1) is to contact by the second electroless nickel plating constituent that makes this first plated state electroless nickel layer and one contain nickel ion and Hypophosporous Acid, 50 root, and on this first plated state electroless nickel plating plated state layer, deposit one whereby and contain nickel and the armorphous nickel that is the face-centered cubic crystal formation, and be doped with the second plated state electroless nickel layer of phosphorus in intergranular and the armorphous nickel.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the second electroless nickel plating constituent in the wherein said step (c-1) comprises the C2-C8 organic acid ion that water, fluorion, ammonium ion, nickel ion, hypophosphite ion, a misfit agent and are made for buffer reagent, this misfit agent is to be selected from diethylenetriamine, quadrol, triethylene tetramine, or the combination of above-mentioned substance.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said organic acid ion is a citrate ion.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the wherein said second electroless nickel plating constituent is to be maintained at one between 70-100 ℃ temperature, and have a pH value between between 2-6.5, fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, 0.05-1M, 0.001-0.1M and 0.02-2M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the wherein said second electroless nickel plating constituent is to be maintained at one between 80-97 ℃ temperature, and have a pH value between between 3-5, fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.35-0.53M, 0.35-0.53M, 0.13-0.15M, 0.1-0.2M, 0.005-0.01M and 0.07-0.1M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, the thickness of the formed first plated state electroless nickel layer of wherein said step (c) is controlled and does not fill up this step (a) slit that forms, and the thickness of this second plated state electroless nickel layer is controlled and fills up the formed slit of this step (a).
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, it also comprises a step (c-2) between between step (c-1) and step (d), this step (c-2) is one to push up the step of plating on this second plated state electroless nickel layer, and be by plating, electroless plating, pen plating, electrostatic coating, or the combination of above-mentioned substance is carried out.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said step (c-2) are to deposit one by plating on this second plated state electroless nickel layer to contain the electrolytic coating that is face-centered cubic crystal formation nickel.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, plating in the wherein said step (c-2) is to utilize an electroplating composition to carry out, and this electroplating composition comprises the C2-C8 organic acid ion that fluorion, ammonium ion, nickel ion and are made for buffer reagent.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said organic acid ion is a citrate ion.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said electroplating composition is to be maintained at one between 25-70 ℃ temperature, and have a pH value between between 0.5-5.0, fluorion, ammonium ion, nickel ion and this organic acid ionic concentration respectively are 0.1-5M, 0.1-5M, 0.1-2M and 0.02-2M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, wherein said electroplating composition is to be maintained at one between 40-60 ℃ temperature, and have a pH value between between 1.5-3, fluorion, ammonium ion, nickel ion and this organic acid ionic concentration respectively are 1.75-2.1M, 1.75-2.1M, 1-1.3M and 0.48-0.72M.
The aforesaid method that is used for surface treatment one magnesium alloy workpiece, it further comprises the chemical rightenning step between step (a) and step (b), and after this chemical rightenning step, repeatedly implement again once just to carry out step (b) after this step (a),, this chemical rightenning step is to react by the acidic solution that makes this upper layer and contain fluorion, ammonium ion and nitrate ion to carry out.
The object of the invention to solve the technical problems also realizes by the following technical solutions.According to a kind of surface treated magnesium alloy workpiece that the present invention proposes, it comprises: a magnesium alloy layer, constituted by a magnesium alloy, and this magnesium alloy has most the sosoloid that are close-packed hexagonal body crystal formation; One transition layer, be formed on this magnesium alloy layer, have most the sosoloid that are close-packed hexagonal body crystal formation that contain magnesium and M, and at least one by the two intermetallic compound that constitutes at least in M, nickel and the phosphorus, metal M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance; And one first electroless nickel layer, be formed on this transition layer, comprise one based on metallic nickel and metal M and be doped with the amorphous structure of phosphorus.
The object of the invention to solve the technical problems also adopts following technical measures further to realize.
Aforesaid surface treated magnesium alloy workpiece, wherein said magnesium alloy have more most between described sosoloid any the two and contain the intergranular of at least one intermetallic compound, and the surface of this magnesium alloy layer depression has most slits.
Aforesaid surface treated magnesium alloy workpiece, the M/ nickel content ratio in the wherein said transition layer along a direction by extremely close this first electroless nickel layer side of close this magnesium alloy layer side, successively decreases.
Aforesaid surface treated magnesium alloy workpiece, the metal M in the wherein said transition layer is a zinc.
Aforesaid surface treated magnesium alloy workpiece, close this first electroless nickel layer side of wherein said transition layer contains the Ni that is close-packed hexagonal body crystal formation 5Zn 21
Aforesaid surface treated magnesium alloy workpiece, wherein said transition layer have a thickness that is not less than 20nm.
Aforesaid surface treated magnesium alloy workpiece, it further comprises second electroless nickel layer that is positioned on this first electroless nickel layer, this second electroless nickel layer contains the nickel that is the face-centered cubic crystal formation, the nickel-phosphorus alloy that is the body-centered teteragonal crystal formation, armorphous nickel, and is doped with phosphorus in intergranular and the armorphous nickel.
Aforesaid surface treated magnesium alloy workpiece, it is to fill up described slit that the surface depression of wherein said first electroless nickel layer has most slits and position second electroless nickel layer thereon.
Aforesaid surface treated magnesium alloy workpiece, it further comprises an electrolytic coating that is positioned on this second electroless nickel layer, and this electrolytic coating comprises the nickel that is the face-centered cubic crystal formation.
Aforesaid surface treated magnesium alloy workpiece, wherein said transition layer further comprise most the crystallites that are the M of close-packed hexagonal body crystal formation.
The object of the invention to solve the technical problems also further realizes by the following technical solutions.According to a kind of degreasing constituent that the present invention proposes, it comprises: an organic acid is to be selected from lactic acid, formic acid, oxalic acid, succsinic acid, hexanodioic acid, citric acid, oxysuccinic acid, or the combination of above-mentioned substance; One teepol; An and high polar organic solvent.
The object of the invention to solve the technical problems also adopts following technical measures further to realize.
Aforesaid degreasing constituent, wherein said organic acid is a lactic acid.
Aforesaid degreasing constituent, wherein said teepol are sodium laurylsulfonate and/or 1, the 2-alkyl phosphate.
Aforesaid degreasing constituent, wherein said high polar solvent is to be selected from methyl alcohol, ethanol, propyl alcohol, Virahol, or the combination of above-mentioned substance.
Aforesaid degreasing constituent, wherein said organic acid and the teepol concentration in this degreasing constituent respectively is 0.1-2M and 0.001-0.01M.
Aforesaid degreasing constituent, wherein said organic acid and the teepol concentration in this degreasing constituent respectively is 0.4-0.7M and 0.002-0.004M.
The object of the invention to solve the technical problems also further realizes by the following technical solutions.According to a kind of surface treatment constituent that the present invention proposes, it comprises water, fluorion, ammonium ion, metal M ion and nickel ion, and M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance.
The object of the invention to solve the technical problems also adopts following technical measures further to realize.
Aforesaid surface treatment constituent, wherein said M is a zinc.
Aforesaid surface treatment constituent, it has a pH value between between 0.1-2, and fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, and 0.05-2M.
Aforesaid surface treatment constituent has a pH value between between 0.2-1.5, and fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.7-1.4M, 0.5-0.9M, 0.12-0.25M, and 0.2-0.25M.
Aforesaid surface treatment constituent, it further comprises the C2-C8 organic acid ion that Hypophosporous Acid, 50 root and is made for buffer reagent, and this surface treatment constituent can be used for electroless nickel plating.
Aforesaid surface treatment constituent, wherein said organic acid ion is a citrate ion.
Aforesaid surface treatment constituent, have a pH value between between 2-6.5, the M ion is that the concentration of zine ion and fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.1-5M, 0.1-5M, 0.02-2M, 0.02-2M, 0.05-1M and 0.02-2M.
Aforesaid surface treatment constituent, have a pH value between between 3-4.5, the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.35-0.53M, 0.35-0.53M, 0.06-0.09M, 0.127-0.155M, 0.1-0.2M and 0.07-0.1M.
Aforesaid surface treatment constituent, it comprises: water, fluorion, ammonium ion, nickel ion, Hypophosporous Acid, 50 root, a misfit agent and are made for the C2-C8 organic acid ion of buffer reagent, this misfit agent is to be selected from diethylenetriamine, quadrol, triethylene tetramine, or the combination of above-mentioned substance.
Aforesaid surface treatment constituent, have a pH value between between 2-6.5, fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, 0.05-1M, 0.001-0.1M and 0.02-2M.
The present invention compared with prior art has tangible advantage and beneficial effect.By above technical scheme as can be known, major technique of the present invention thes contents are as follows:
The invention provides a kind of surface treatment method that forms the coating of firm engagement on the magnesium alloy workpiece that makes.The present invention's the method that is used for surface treatment one magnesium alloy workpiece comprises following steps:
(a) make one to have most the workpiece that magnesium alloy constituted that are the sosoloid of close-packed hexagonal body crystal formation by one and forms one and exposed most individual upper layers that are the sosoloid of close-packed hexagonal body crystal formation are arranged;
(b) make and form a displacement active layer that comprises most nickel crystal seeds and most metal M crystal seed on the upper layer of this workpiece, wherein this metal M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance;
(c) on this displacement active layer, deposit one in the electroless plating mode and comprise one based on metallic nickel and metal M and be doped with the first plated state electroless nickel layer of armorphous (amorphous) structure of phosphorus; And
(d) this workpiece is bestowed a thermal treatment, so that should with this displacement active layer place of the vicinity of this upper layer and the first plated state electroless nickel layer solid solution take place respectively by displacement active layer, and form a transition layer, and obtain one and have a magnesium alloy layer that constitutes by this magnesium alloy, the workpiece of one transition layer and one first electroless nickel layer, wherein, this transition layer has most the sosoloid that are close-packed hexagonal body crystal formation that contain magnesium and M, and it is at least one by M, at least the intermetallic compound of the two formation (intermetalliccompound) in nickel and the phosphorus, and first electroless nickel layer comprises one based on metallic nickel and M and be doped with the amorphous structure of phosphorus.Through step (a)-(d) handle and workpiece itself be nickel-zinc, nickel-cobalt or the nickel-cadmium electroless plating that is doped with phosphorus because of the top layer nickel coating, so also have and can weld or function such as against corrosion.
Be to promote the surface property of magnesium alloy workpiece, such as solidity to corrosion, hardness etc., through aforementioned this case method handle and workpiece can continue to plate thicker and can be against corrosion for a long time or the coating of other functions of tool.Therefore preferably, the inventive method more comprises a step (c-1) between between step (c) and step (d), and this step (c-1) is by making this first plated state electroless nickel layer and one contain nickel ion (Ni 2+) and Hypophosporous Acid, 50 root (H 2PO 2 -) second electroless nickel plating constituent contact, and on this first plated state electroless nickel plating plated state layer, deposit one by this and contain and be face-centered cubic (face-centered cubic, be called for short fcc) nickel and the armorphous nickel of crystal formation, and be doped with the second plated state electroless nickel layer of phosphorus in intergranular (grain boundary zone) and the armorphous nickel.This second plated state electroless nickel layer can be better than first electroless nickel layer in the structure intensity of after heat treatment signing an undertaking, and therefore, makes magnesium alloy workpiece can be provided as functional inner member.
In order to achieve the above object, the invention provides and a kind ofly handle and get, and have the magnesium alloy workpiece of the novelty of the transition layer of a firm engagement on this magnesium alloy workpiece through aforementioned surface treatment method of the present invention.Surface treated magnesium alloy workpiece of the present invention comprises: a magnesium alloy layer, constituted by a magnesium alloy, and this magnesium alloy has most the sosoloid that are close-packed hexagonal body crystal formation; One transition layer, be formed on this magnesium alloy layer, have most the sosoloid that are close-packed hexagonal body crystal formation that contain magnesium and M, and at least one by the two intermetallic compound that constitutes at least in M, nickel and the phosphorus, wherein metal M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance; And one first electroless nickel layer, be formed on this transition layer, comprise one based on metallic nickel and metal M and be doped with the amorphous structure of phosphorus.
Again, in order to achieve the above object, the present invention also provides a kind of degreasing constituent, it is available for the step (a) of aforementioned the inventive method, to produce a upper layer with most exposed sosoloid, this constituent comprises an organic acid, one teepol and a high polar organic solvent, wherein this organic acid is to be selected from lactic acid (lactic acid), formic acid (formic acid), oxalic acid (oxalicacid), succsinic acid (succinic acid), hexanodioic acid (adipic acid), citric acid (citricacid), oxysuccinic acid (malic acid), or the combination of above-mentioned substance.
Moreover in order to achieve the above object, the present invention also provides a kind of surface treatment constituent, and it comprises water, fluorion, ammonium ion, metal M ion and nickel ion, and wherein M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance.This surface treatment constituent itself can be used as a displacement activation constituent that is used for forming crystal seed in the step (b), and further comprises the C that hypophosphite ion and is made for buffer reagent when it 2-C 8During the organic acid ion, can be provided as the one first electroless nickel plating constituent (electroless plating plating bath just (electroless plating bath)) that step (c) electroless plating is used.
In addition, in order to achieve the above object, the present invention also provides a kind of electroless nickel plating constituent for aforementioned the inventive method step (c-1) use, and it comprises water, fluorion (F -), ammonium ion (NH 4 +), nickel ion, Hypophosporous Acid, 50 root, a misfit agent and be made for the C2-C8 organic acid ion of buffer reagent, wherein this misfit agent is to be selected from diethylenetriamine (diethylene triamine), quadrol (ethylenediamine), triethylene tetramine (triethylene tetraamine), or the combination of above-mentioned substance.
By technique scheme, the surface treatment method of magnesium alloy workpiece of the present invention, handle the workpiece of gained and be used for each constituent of this method, have following advantage at least:
1, the surface treatment method of magnesium alloy workpiece of the present invention, it can make the coating that forms firm engagement on the magnesium alloy workpiece, thereby is suitable for practicality more.
2, the degreasing constituent, surface treatment constituent and the electroless nickel plating constituent that propose of the present invention can be used for the surface treatment method of aforementioned magnesium alloy workpiece, helps to form the coating of firm engagement on magnesium alloy workpiece, thereby is suitable for practicality more.
3, the magnesium alloy workpiece of the present invention's proposition, it has powerful sticking power through above-mentioned surface treatment between its tectum and Mg alloy surface, have long-term effect against corrosion, makes magnesium alloy workpiece firmly to be bonded on the various workpiece.
In sum, the surface treatment method of the magnesium alloy workpiece that the present invention is special, handle the workpiece of gained and be used for each constituent of this method, it has above-mentioned many advantages and practical value, and in like product and method, do not see to have and similarly publish or use and really genus innovation, it is had large improvement technically, and has produced handy and practical effect, thereby is suitable for practicality more, and have the extensive utility value of industry, really be a new and innovative, progressive, practical new design.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 is a diagrammatic cross-section, illustrates to have the intergranular magnesium alloy workpiece.
Fig. 2 is a diagrammatic cross-section, illustrate that this magnesium alloy workpiece 1 contacts with a degreasing constituent and sosoloid top layer and intergranular in compound and constituent reaction form the situation of a residue.
Fig. 3 is a diagrammatic cross-section, illustrate that this residue is eliminated after, this workpiece surface exposes hcp sosoloid and forms one has most by the upper layer of this end face to the slit of lower recess.
Fig. 4 is a diagrammatic cross-section, illustrates that this surface exposure has to form a displacement active layer that contains Ni, M crystal seed and magnesium fluoride on the workpiece of sosoloid.
Fig. 5 is a diagrammatic cross-section, illustrates when carrying out electroless plating with one first electroless plating constituent on this displacement active layer that magnesium fluoride peels off automatically and the first plated state electroless nickel layer prolongs the sosoloid surface and grows up.
Fig. 6 is a diagrammatic cross-section, illustrates when bestowing thermal treatment, and displacement active layer and upper layer and the first plated state electroless nickel layer by this displacement active layer place solid solution take place.
Fig. 7 is a diagrammatic cross-section, illustrates after heat treatment, the surface treated workpiece with a magnesium alloy layer, transition layer and first electroless nickel layer that is obtained.
Fig. 8 is a diagrammatic cross-section, description of step (c) and (d) between when further comprising step (c-1), the surface treated workpiece that has more one second electroless nickel layer that is obtained.
Fig. 9 is a diagrammatic cross-section, description of step (c) and (d) between further comprise step (c-1) and (c-2) time, the surface treated workpiece that has more one second electroless nickel layer and electroless nickel layer that is obtained.
Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, the surface treatment method of the magnesium alloy workpiece that foundation the present invention is proposed, handle the workpiece of gained and be used for each constituent of this method, its embodiment, step, feature and effect thereof, describe in detail as after.
The present invention is described in detail below in conjunction with drawings and Examples:
Being applicable to the magnesium alloy workpiece of handling by this case method, is that these have most the workpiece that magnesium alloy constituted that are the sosoloid of close-packed hexagonal body crystal formation by one.
Optionally, as shown in Figure 1, when this workpiece 1 is to have most the sosoloid 11 that are close-packed hexagonal body crystal formation by one, and when having more most any the two and the magnesium alloy that contain the intergranular 12 of at least one intermetallic compound and constituting between these sosoloid 11, because of intergranular 12 structures comparatively loose, therefore, if before on magnesium alloy, forming transition layer, make the higher intermetallic compound of surface energy that more easily causes joint defect and accelerated corrosion in the intergranular 12 be removed and produce most slits to small part earlier, just replace activation and electroless plating afterwards and form an electroless plating, to strengthen the conjugation grade of coating and workpiece greatly by the increase of contact area as on workpiece, nailing on one deck with as the coating of a plurality of rivets.
Therefore, when the magnesium alloy in the magnesium alloy workpiece that the institute desire is handled is when having most intergranulars, preferably, make that this upper layer is exposed to be had outside most the sosoloid, more be formed with most slits.With reference to Fig. 2 and Fig. 3, this upper layer with most slits can form by following mode: an end face 13 contacts one that make this workpiece 1 bestowed a ultrasound and with the reactivity of this intermetallic compound degreasing constituent greater than these sosoloid, so that the top layer of the sosoloid 11 of at least a portion at contiguous these end face 13 places and the intermetallic compound at least one part intergranular 12 and the reaction of this constituent, and form a residue (residue) 2, then with these residue 2 molten removing, so that most close-packed hexagonal body sosoloid 11 expose out, and form most by the slit 14 of this end face 13 to lower recess.
The known suitable intergranular magnesium alloy of handling with this case method that has comprises, but be not limited to these by Al, Zn, Zr, Li, Th and/or Mn and Mg through solid solution and stabilization and magnesium alloy workpiece, commercially available AZ31B, AZ61A, ZK60A, LA141A, HM21A, HK31a and EZ33A specification for example.And it is the above magnesium alloy workpiece of 83wt% that method of the present invention is specially adapted to handle Mg content.
Preferably, the degreasing constituent that uses in this step (a) is aforementioned degreasing constituent provided by the present invention, and is to comprise an organic acid, a teepol and a high polar organic solvent.
This organic acid mainly is the intermetallic compound that is used for corroding intergranular.Preferably, this organic acid is to be selected from lactic acid, formic acid, oxalic acid, succsinic acid, hexanodioic acid, citric acid, oxysuccinic acid, or the combination of above-mentioned substance.More preferably, this organic acid is that lactic acid and this residue comprise magnesium lactate, and with the newborn acidulants of the metal of magnesium solid solution.
The effect of this teepol is to make the oiliness macromole that is attached to workpiece surface to become than wetting ability, in order to removing.The teepol that is applicable to this case comprises lauryl alcohol sodium sulfovinate (sodium lauryl sulfate), secondary alkylsurfuric acid is received (sodium iso-alkyl sulfate), lauryl alcohol polyvinyl ether sodium sulfate (sodium lauryl polyvinylether sulfate), glyceryl monolaurate two sodium sulfate (sodium glycerol mono laurate sulfate), sulfation natrium ricinoleicum (Polyglycerol Esters of Interesterified Ricinoleic Acidsodium salt), sodium laurylsulfonate (Sodium luaryl sulfonate) and 1,2-alkyl phosphate (1,2-Alkyl phosphate) etc.Preferably, this teepol is sodium laurylsulfonate and/or 1, the 2-alkyl phosphate.
Preferably, this high polar organic solvent is the not high person of solubleness who selects for use this residue, so that residue by molten remove preceding rest in the intergranular to small part and use this organic acid of control corrode intergranular degree of depth in 5-10 μ m, so preferably, this organic solvent is the combination that is selected from methyl alcohol, ethanol, propyl alcohol, Virahol or above-mentioned substance.In a specific example of the present invention, processed magnesium alloy is the ultracrystallite that contains the looser Mg17Al12 of structure in magnalium and the intergranular, when using a degreasing constituent that contains lactic acid, Virahol and teepol to corrode Mg alloy surface, formed residue comprises magnesium lactate and Aluctyl.
Preferably, this organic acid and the teepol concentration in this degreasing constituent respectively is 0.1-2M and 0.001-0.01M, preferably respectively be 0.4-0.7M and 0.002-0.04M, more preferably respectively be 0.5-0.6M and 0.0025-0.0035M, corrode the degree on intergranular and sosoloid surface in suitable scope with control.
Preferably, be used in this step (a) and the ultrasound that is applied to the degreasing constituent has a frequency between 300-360KHz, or have one and can shake (harmonic oscillation) by simple harmonic quantity and produce a frequency between the 300-360KHz frequency.Preferably, this ultrasound has a frequency between 300-360KHz, 150-180KHz or 20-45KHz.
Relevant aforementioned notion of corroding compound in the intergranular with the degreasing constituent that contains lactic acid, also can be spreaded to the oiliness macromole that removes magnesium alloy work-piece surface earlier with a solution that contains this teepol and this organic solvent, be corroded compound in the intergranular with a solution that contains organic acid and this organic solvent more then.
Preferably, molten the removing of this residue is by making water or the alcohols below the C4 clean this workpiece and reach, more preferably, being to use the molten removal of residue of water.Again more preferably, when cleaning and molten removal of residue, be simultaneously this workpiece to be bestowed one to have the ultrasound of frequency as described above.
When making thermal treatment, except metal M and magnesium solid solution, further for promoting the structural strength of transition layer, preferably, metal M is to select for use atomic size near the nickel person, and therefore, preferably, the metal M in this step (b) is a zinc.
Catalyst layer when formed displacement active layer is intended for step (c) electroless plating in this step (b), so thickness do not need too thick and do not have particular restriction, generally is to get final product between between 20-200nm, is preferably between 30-100nm, better is 40-60nm.
Preferably, this step (b) is to react by the displacement activation constituent that makes this upper layer and comprise water, fluorion, ammonium ion, M ion and nickel ion to reach, and this displacement activation constituent can be provided by aforementioned surface treatment constituent of the present invention.Preferably, this displacement activation constituent is bestowed a ultrasound, with guarantee formed crystal seed be firm engagement on the upper layer of sosoloid, and preferably, this supersonic frequency is used with degreasing in the aforementioned step (a).
When the M in the step (b) is zinc, preferably, this displacement activation constituent is to be maintained at one between 0-85 ℃ temperature, and has a pH value between between 0.1-2, wherein fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, and 0.05-2M.More preferably, this displacement activation constituent is to be maintained at one between 15-30 ℃ temperature, and have a pH value between between 0.2-1.5, wherein fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.7-1.4M, 0.5-0.9M, 0.12-0.25M, and 0.2-0.25M.Best, this displacement activation constituent is to be maintained at one between 20-25 ℃ temperature, and have a pH value between between 0.5-1, wherein fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.9-1.2M, 0.65-0.75M, 0.16-0.2M, and 0.22-0.24M.
With reference to Fig. 4 and Fig. 5, when the M in the step (b) is zinc and when being to use the displacement activation constituent of aforementioned fluoride ion, formed displacement active layer 3 comprises most nickel crystal seeds 31, most metal M crystal seed 32 on the workpiece 1, and magnesium fluoride 33.And the first plated state electroless nickel layer 4 was peeled off automatically along naked brilliant surface 15 growth of magnesium alloy when magnesium fluoride 33 can carry out electroless plating because of step (c).
Preferably, the thickness of the formed first plated state electroless nickel layer of this step (c) is controlled and does not fill up the formed slit of this step (a).Therefore preferably, the win thickness of plated state electroless nickel layer of the electroless plating of this step (c) is between 2-10 μ m, and better is between 3-8 μ m, and the best is between 4-6 μ m.
Preferably, step (c) is to be undertaken by making this displacement active layer contact one first electroless nickel plating constituent, and this first electroless nickel plating constituent comprises the C2-C8 organic acid ion that water, fluorion, ammonium ion, M ion, nickel ion, hypophosphite ion and are made for buffer reagent.This first electroless nickel plating constituent is to get by further add hypophosphite ion and this C2-C8 organic acid ion in aforementioned surface treatment constituent of the present invention.
Preferably, in step (c), M ion in this first electroless nickel plating constituent is a zine ion, and this constituent is to be maintained at one between 70-100 ℃ temperature, and have a pH value between between 2-6.5, wherein the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.1-5M, 0.1-5M, 0.02-2M, 0.02-2M, 0.05-1M and 0.02-2M.More preferably, this first electroless nickel plating constituent is to be maintained at one between 80-97 ℃ temperature, and have a pH value between between 3-4.5, wherein the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.35-0.53M, 0.35-0.53M, 0.06-0.09M, 0.127-0.155M, 0.1-0.2M and 0.07-0.1M.Best, this first electroless nickel plating constituent is to be maintained at one between 90-95 ℃ temperature, and have a pH value between between 3.5-4.0, wherein the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.4-0.5M, 0.4-0.5M, 0.07-0.08M, 0.135-0.145M, 0.14-0.16M and 0.08-0.09M.
Preferably, the heat treated temperature of this step (d) is between 140 ℃ to 250 ℃.More preferably, be between 170 ℃ to 190 ℃.Best, this thermal treatment is by heating to about 180 ℃ with a heat-up rate that is about 150 ℃/hr in 60min, be maintained at 170-190 ℃ then in the 60min that continues, in the 60min more afterwards, rising again to room temperature with the cooling rate of-150 ℃/hr.
Consult Fig. 6, after this workpiece 1 is bestowed thermal treatment, because of displacement active layer 3 by the nickel crystal seed 31 of magnesium alloy layer side and M crystal seed 32 to infiltration and solid solution 100 in the magnesium alloy workpiece (as among Fig. 6 with shown in the dotted line), and solid solution 100 also takes place by the metal M of the first plated state electroless nickel layer, 4 sides and nickel and the first plated state electroless nickel layer 4, so can obtain the surface treated magnesium alloy workpiece 5 as the novelty of Fig. 7 signal, it has magnesium alloy layer 51, transition layer 52 and one first electroless nickel layer 53 that is referred in the aforementioned summary of the invention.
When magnesium alloy workpiece 5 is constituted by having the intergranular magnesium alloy, and when the gold compound of part metals at least in the intergranular is removed, the surface of the magnesium alloy layer 51 in the workpiece 5 that gets through step (a)-(d) processing can be that depression has most slits 511 as shown in Figure 7.
Preferably, each ionic concn in this displacement activation constituent and the first electroless plating constituent is suitably regulated and control, so that this case M/ nickel content ratio in the transition layer in the magnesium alloy workpiece of surface treatment method gained, along a direction by extremely close this first electroless nickel layer side of close this magnesium alloy layer side, successively decrease.And for reaching the purpose of tight joint, formed this transition layer is preferably has a thickness that is not less than 20nm.
In a specific example of the present invention, treated and workpiece in transition layer in metal M be zinc, and this transition layer contain the Ni that is close-packed hexagonal body crystal formation near this first electroless nickel layer side 5Zn 21
Preferably, this step (b) and the displacement activation constituent of (c) middle use and each ionic concn in the first electroless nickel plating constituent, and the thermal treatment temp of step (d) is suitably regulated and control, so that this case is in the magnesium alloy workpiece of surface treatment method gained, this transition layer further comprises most the crystallites (ultrafine crystal) that are the M of close-packed hexagonal body crystal formation, with the generation that prevents that difference row from sliding.
When metal M is zinc in the inventive method, handle and the top layer of magnesium alloy workpiece, promptly first electroless nickel layer is to mix to dye the armorphous nickel zinc alloy that phosphorus is arranged, and itself can be used as scolder, so this kind magnesium alloy workpiece can firmly be engaged on other workpiece by welding.When this metal M was cobalt, first electroless nickel layer of workpiece surface was to mix to dye the armorphous nickel cobalt (alloy) that phosphorus is arranged, and it is low to have excellent hardness and internal stress, therefore also can reach purpose against corrosion.Similarly, when this metal M was cadmium, first electroless nickel layer of workpiece surface was assorted to dye the armorphous nickel-cadmium that phosphorus is arranged, and can be the material of welding and also tool function against corrosion.
For solidity to corrosion and the hardness that makes workpiece surface more promotes, preferably, surface treatment method of the present invention more comprises a step (c-1) between between step (c) and step (d), this step (c-1) is to contact by the second electroless nickel plating constituent that makes this first plated state electroless nickel layer and one contain nickel ion and Hypophosporous Acid, 50 root, and on this first plated state electroless nickel plating plated state layer, deposit one whereby and contain nickel and the armorphous nickel that is the face-centered cubic crystal formation, and be doped with the second plated state electroless nickel layer of phosphorus in intergranular and the armorphous nickel.Preferably, the thickness of this step (c-1) gained second plated state electroless plating is between 2-20 μ m, and better is between 7-15 μ m, and the best is between 8-12 μ m.
After step (c-1) is finished and is bestowed thermal treatment again, can obtain surface treated magnesium alloy workpiece 6 just like the novelty of Fig. 8 signal, it has the magnesium alloy layer 61 that is referred in the aforementioned summary of the invention, the transition layer of firmly following 62, one first electroless nickel layer 63, and one second electroless nickel layer 64, and this second electroless nickel layer 64 contains the nickel that is the face-centered cubic crystal formation, the nickel-phosphorus alloy that is the body-centered teteragonal crystal formation, armorphous nickel, and is doped with phosphorus in intergranular and the armorphous nickel.
Preferably, the second electroless nickel plating constituent in this step (c-1) is to be provided by aforementioned electroless nickel plating constituent of the present invention, and comprise the C2-C8 organic acid ion that water, fluorion, ammonium ion, nickel ion, hypophosphite ion, a misfit agent and are made for buffer reagent, wherein this misfit agent is to be selected from diethylenetriamine, quadrol, triethylene tetramine, or the combination of above-mentioned substance.Preferably, this organic acid ion is a citrate ion.
Preferably, this second electroless nickel plating constituent is to be maintained at one between 70-100 ℃ temperature, and have a pH value between between 2-6.5, wherein fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, 0.05-1M, 0.001-0.1M and 0.02-2M.More preferably, this second electroless nickel plating constituent is to be maintained at one between 80-97 ℃ temperature, and have a pH value between between 3-5, wherein fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.35-0.53M, 0.35-0.53M, 0.13-0.15M, 0.1-0.2M, 0.005-0.01M and 0.07-0.1M.Best, this second electroless nickel plating constituent is to be maintained at one between 90-95 ℃ temperature, and have a pH value between between 3.2-4.0, wherein fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.4-0.5M, 0.4-0.5M, 0.135-0.145M, 0.14-0.16M, 0.006-0.008M and 0.08-0.09M.
Especially, when the second electroless nickel plating constituent that uses aforementioned optimal selection carries out step (c-1), because of the pH value lower, make that the phosphorus content in the second plated state electroless nickel layer is higher, phospha dyes and can reduce the assorted space of dying of hydroperoxyl radical in the nickel metal, and hydroperoxyl radical discharges and produce the chance of stress under compression when also having reduced subsequent heat treatment in nickel dam.And because of magnesium alloy workpiece through behind electroless nickel, the crystal seed on surface is extremely many, makes that workpiece surface has higher reaction power when carrying out step (c-1) electroless plating for the second time, and advances to produce the crowded coating that tension stress is arranged.Moreover, because in second time during electroless nickel plating, the surface of workpiece discharges electronics because of the reaction of Hypophosporous Acid, 50 root, make workpiece have electronegative, and in the second electroless nickel plating constituent because of containing micromolecular electropositivity amine misfit agent, can and nickel ion misfit and the stronger electropositivity of band because the relation of electric field, nickel ion is diffused into the speed on surface of workpiece from constituent faster than general electroless nickel plating, and this also helps to form a coating of type internal stress.
The benefit that produces tension stress coating is that the few and magnesium alloy thermal expansivity of hole is about 25～30 μ m/ (m* ℃), thermal expansivity much larger than electroless nickel layer between 10～15 μ m/ (m* ℃), therefore in a specific example of the present invention, use the prescription of aforementioned optimal selection to make the second plated state electroless nickel layer keep suitable tension stress, not peeling when this can guarantee thermal treatment.
Preferably, the slit that is produced in the step (a) is filled up by the electroless plating of step (c-1), because the textural property and the intensity of second electroless nickel layer that step (c-1) is produced are better than first electroless nickel layer, therefore, with the gauge control of first electroless nickel layer in the degree of not filling up the slit fully, and make second electroless nickel layer possess the rivet effect, be comparatively ideal design when desiring plated with nickel phosphorus alloy upper layer.
Therefore, preferably, as shown in Figure 6, when after step (c) being will continue when carrying out step (c-1), the thickness of the formed first plated state electroless nickel layer 4 of this step (c) is controlled and does not fill up this step (a) slit that forms 14, and the thickness of this second plated state electroless nickel layer is controlled and fills up the formed slit 14 of this step (a).In this case, as shown in Figure 8, in the magnesium alloy workpiece 6 of subsequent heat treatment gained, it is to fill up these slits 631 (also filling up former slit 14 simultaneously) that the surface of this first electroless nickel layer 63 depression has most slits 631 and position second electroless nickel layer 64 thereon.
For making workpiece surface become more smooth and glossiness, solidity to corrosion and hardness being promoted again, the inventive method can more comprise a step (c-2) between between step (c-1) and step (d), this step (c-2) is a step of pushing up plating (topcoat) on this second plated state electroless nickel layer, and be by plating, electroless plating, pen plating (brush coat), electrostatic coating (powder coat), or the combination of above-mentioned substance is carried out.
Preferably, this step (c-2) is to deposit one by plating on this second plated state electroless nickel layer to contain the electrolytic coating that is face-centered cubic crystal formation nickel, and can obtain the surface treated magnesium alloy workpiece 7 just like the novelty of Fig. 9 signal after step (d) thermal treatment, it has the magnesium alloy layer 71 that referred in the aforementioned summary of the invention, transition layer 72, one first electroless nickel layer 73, one second electroless nickel layer 74 and an electrolytic coating 75 as the aforementioned.
Preferably, the plating in this step (c-2) is to utilize an electroplating composition to carry out, and this electroplating composition comprises the C2-C8 organic acid ion that fluorion, ammonium ion, nickel ion and are made for buffer reagent.Preferably, this organic acid ion is a citrate ion.Preferably, this electroplating composition is to be maintained at one between 25-70 ℃ temperature, and have a pH value between between 0.5-5.0, wherein fluorion, ammonium ion, nickel ion and this organic acid ionic concentration respectively are 0.1-5M, 0.1-5M, 0.1-2M and 0.02-2M.More preferably, this electroplating composition is to be maintained at one between 40-60 ℃ temperature, and have a pH value between between 1.5-3, wherein fluorion, ammonium ion, nickel ion and this organic acid ionic concentration respectively are 1.75-2.1M, 1.75-2.1M, 1-1.3M and 0.48-0.72M.Best, this electroplating composition is to be maintained at one between 45-55 ℃ temperature, and have a pH value between between 2-3, wherein fluorion, ammonium ion, nickel ion and this organic acid ionic concentration respectively are 1.8-2M, 1.8-2M, 1.1-1.2M and 0.56-0.64M.
Preferably, the plating in this step (c-2) is between 1-10A/dm with one 2Current density carry out, more preferably be 1-5A/dm 2, be 2-3A/dm best 2
Known to this case applicant, never the someone uses fluorion to be used as the conductive ion of electroplating composition (plating bath).The electroplating composition that aforementioned the inventive method step (c-2) is used is to serve as the anionic task of conduction with fluorion, have do not corrode magnesium alloy, ion is little and have high electronegative and movability and the strong advantage of conduction power.And preferably, contain the not gloss-imparting agent of sulfur-bearing in this electroplating composition, such as 1,4-butynediol and tonka bean camphor (coumarin) produce the insufficient problem of corrosion stability to avoid the coating sulfur-bearing.Moreover this electroplating composition uses the misfit agent of ammonium ion as nickel ion, with the puzzlement of avoiding nickelous fluoride solubility product deficiency to be produced.
Because when carrying out degreasing, allow sometimes pore exposes out in the magnesium alloy workpiece, at this moment, can further comprise a chemical rightenning (chemical polishing) step between step (a) and step (b) when implementing this case method, and after this chemical rightenning step, repeatedly implement again once just to carry out step (b) after this step (a), wherein, this chemical rightenning step is to react by the acidic solution that makes this upper layer and contain fluorion, ammonium ion and nitrate ion to carry out.Wherein fluorine ion source can be fluoric acid, Neutral ammonium fluoride, Sodium Fluoride and/or Potassium monofluoride, and the nitrate ion source can be nitric acid, ammonium nitrate, SODIUMNITRATE and/or saltpetre, and the source of ammonium ion can be Neutral ammonium fluoride and/or ammonium nitrate.And preferably, this chemical polishing soln is to comprise fluoric acid, Neutral ammonium fluoride and nitric acid, and concentration respectively is 50-70cc/L, 30-50g/L and 30-5-g/L.Be to execute son one simultaneously to have the ultrasound of range of frequency as described above when more preferably, carrying out chemical rightenning.
In a specific example of the present invention, this surface treatment method is to carry out according to following sequence of steps: step (a) → chemical rightenning → (a) → (b) → (c) → (c-1) → (c-2) → (d), and employed constituent in each step, comprise chemical rightenning, degreasing, the displacement activation, first electroless nickel plating, second electroless nickel plating and electronickelling constituent, all be the fluoride ion and the close system of filling a prescription, therefore come molten except that this residue except needing in the step (a) with water, in the time of fully need be as the electroless plating of carrying out multiple tracks or plating step in the past, need in per two road processing procedures with the water cleaning workpiece, to remove down in one step unwanted ion and to avoid collapsing groove (crack down) or un-desired reaction takes place, the simplification of this processing procedure has great help for the surface-treated volume production, and the most important thing is, experience according to general industry, can wash between each step, this kind practice may cause negative influence for the joint of the active magnesium alloy workpiece coating of voltinism on the contrary.Therefore, preferably when implementing this case method, except residue remove can water clean, the neither step of bestowing any with the water cleaning workpiece between all the other steps.
Be applicable to that the present invention is to comprise villiaumites such as fluoric acid, ammonium fluoride, Sodium Fluoride, Potassium monofluoride, zinc fluoride and/or nickelous fluoride as the fluorine ion source in all constituents.The ammonium ion source comprises Neutral ammonium fluoride and/or ammonium hypophosphite.The zine ion source comprises zinc carbonate, zinc hydroxide, zinc fluoride and/or zinc hypophosphite.The nickel ion source comprises nickel hydroxide, nickelous fluoride, citric acid nickel, nickelous hypophosphite.The source of Hypophosporous Acid, 50 root comprises Hypophosporous Acid, 50, potassium hypophosphite sodium, potassium hypophosphite and/or ammonium hypophosphite.The organic acid ion source of C2-C8 comprises oxalic acid, succsinic acid, oxysuccinic acid, hexanodioic acid and/or lactic acid.
Be noted that especially, when selecting above-mentioned various ion source, avoid making in the specific composition thing other ions that have the content that is enough to influence this constituent effect, for example in displacement activation constituent, to avoid the existence of Hypophosporous Acid, 50 root, promptly avoid using zinc hypophosphite and nickelous hypophosphite, to prevent to collapse groove; Because do not need the M ion, such as zine ion is so in the selection of fluorine ion source, should avoid zinc fluoride in the second electroless nickel plating constituent and electroplating composition.
In addition, relevant aforementioned supersonic applying, can be undertaken by any mode in the past, for example these containers of desiring to be bestowed supersonic constituent are bestowed ultrasound, insert a sound wave probe (sonicating probe) in constituents to splendid attire, or are loaded with one and desire to be bestowed supersonic constituent and be socketed on the ultrasonic vibrations device.
Below will further specify the present invention with embodiment, these embodiment of thought are the usefulness for illustrating only, but not in order to restriction the present invention.
Chemical and workpiece
1. diethylenetriamine: 100% liquid, available from Aldrich.
2. nickelous carbonate: nickel content 27wt%, available from difficult to understand wild in Japan.
3. sodium laurylsulfonate: available from Fluka.
4. tonka bean camphor: available from Merck.
5. the composition of employed each magnesium alloy workpiece and state are as follows among the embodiment:
Test specimen Mg content % The main metal % that refers and synthesizes The inferior metal % that refers and synthesizes Work status
AZ31B 94.7％ Aluminium 3% Zinc 1% T7, solid solution+stabilization
AZ61A 91.0％ Aluminium 6% Zinc 1% T7, solid solution+stabilization
ZK60A 93.6％ Zinc 6% Zirconium 0.4% T7, solid solution+stabilization
LA141A 83.3％ Lithium 14% Aluminium 1% T7, solid solution+stabilization
HM21A 96.4％ Thorium 2% Manganese 1% T7, solid solution+stabilization
HK31a 95％ Thorium 3% Zirconium 1% T7, solid solution+stabilization
EZ33A 92.1％ Thorium 3% Zinc 3% T7, solid solution+stabilization
＜embodiment 1 〉
Below utilize the inventive method that the magnesium alloy plate (work status T7) that 7 U.S.s that are numbered 1-7 advise LA141A is carried out surface treatment, step is as follows:
(i) at room temperature, preparation one contains concentration and respectively is the aqueous isopropanol (degreasing constituent) of the lactic acid of 50g/L, 0.5g/L and sodium laurylsulfonate, this solution is inserted a ultrasound oscillator, and these 7 workpiece are put into this oscillator, and the ultrasound frequency is decided to be about 330kHz, after lasting about 5min, clean these workpiece with water then.
(ii) at room temperature, preparation one contains concentration and respectively is 60cc/L, the fluoric acid of 40g/L and 40g/L, the chemical polishing soln of Neutral ammonium fluoride and nitric acid, this chemical polishing soln is inserted a ultrasound oscillator, and with step (i) be cleaned 7 workpiece put into this oscillator, and the ultrasound frequency is decided to be about 330kHz, after lasting about 0.5min, all workpiece are put back again in the oscillator of step (i), and last 5min, then clean these workpiece with water, this moment, this magnesium alloy workpiece was etched out most the degree of depth between the slit of 5-10m, and surface exposure goes out the crystal grain of a plurality of hcp crystal formations.
(iii) at room temperature, will be through cleaning and 7 workpiece insert and last about 5min in the displacement activation solution, so that these workpiece surface form the displacement active layer that a thickness is about 5-10nm and contains zinc crystal seed, nickel crystal seed and magnesium fluoride, this displacement activation solution, and is had one and is about 0.5 pH value and comprises the fluoric acid of water, 15cc/L, the Neutral ammonium fluoride of 40g/L, the zinc oxide of 15g/L and the nickelous carbonate of 45g/L in a frequency is decided to be the ultrasound oscillator of about 330kHz by splendid attire.
(iv) will through step (iii) and 7 workpiece in this displacement activation solution, shift out, and insert a temperature and be about in 95 ℃ the first electroless nickel plating plating bath and last about 5min, and accompany by lasting pneumatic blending, so that these workpiece surface form the first plated state electroless nickel layer (observing aforementioned magnesium fluoride can peel off) that a thickness is about 2-3 μ m, this first electroless nickel plating plating bath has one and is about 3.5 pH value and comprises the Neutral ammonium fluoride of water, 25g/L, the zinc oxide of 6g/L, the nickelous carbonate of 30g/L, the citric acid of 20g/L and the sodium hypophosphite of 20g/L.
(v) will through step (iv) and 7 workpiece in this first electroless nickel plating plating bath, shift out, and insert a temperature and be about in 95 ℃ the second electroless nickel plating plating bath and last about 15min, and accompany by lasting pneumatic blending, so that these workpiece surface form the second plated state electroless nickel layer that a thickness is about 5～7 μ m, this second electroless nickel plating plating bath has one and is about 3.2 pH value and comprises the Neutral ammonium fluoride of water, 25g/L, the diethylenetriamine of 1.0g/L, the nickelous carbonate of 30g/L, the citric acid of 20g/L and the sodium hypophosphite of 20g/L.
(vi) will through step (v) and 7 workpiece in this second electroless nickel plating plating bath, shift out, and insert a temperature and be about in 50 ℃ the electronickelling plating bath and last about 30min, and accompany by lasting pneumatic blending, so that these workpiece surface form a plated state electroless nickel layer, this electronickelling plating bath have one be about 2.5 pH value and comprise nickelous carbonate, the 150g/L of Neutral ammonium fluoride, the 250g/L of water, 120g/L citric acid, 10g/L 1, the tonka bean camphor of 4-butynediol and 2g/L, wherein this plating bath is bestowed a current density that is about 2.5A/dm2.
(vii) these 7 workpiece are shifted out plating bath, then in 60min with a heat-up rate that is about 150 ℃/hr, these 7 workpiece are heated to about 180 ℃, then in the 60min that continues, be maintained at 170-190 ℃, in the 60min more afterwards, rise again to room temperature with the cooling rate of-150 ℃/hr, obtain 7 surface treated magnesium alloy workpieces whereby, and the thickness average out to 36.5m of the plated film that forms by each coating on these workpiece, and the microscopic cross section of whole work-piece is as schematically shown in Figure 9, and wherein each of magnesium alloy laminar surface stems from the intergranular slit and sealed by second electroless nickel layer.The coating structure of workpiece after plated state and the thermal treatment
Identify as can be known that through XRD before not bestowing thermal treatment, in each workpiece of numbering 1-7, the zinc of the surface of this displacement active layer: nickel content is about 10: 1; The zinc of the surface of first electroless nickel layer: nickel content is about 1: 9, and XRD does not observe this two plated states layer and have the absorption peak of any crystal formation (because the crystal seed that the displacement activation produces is minimum crystallite); The second plated state electroless nickel layer comprises fcc crystal formation Ni and armorphous Ni, and wherein P dyes kenel and is present in fcc intergranular or the amorphous structure with assorted; Then comprise the nickel and the armorphous nickel that are the fcc crystal formation in the second plated state electroless nickel layer, and be doped with phosphorus in intergranular and the armorphous nickel; The Ni crystal that then comprises the fcc crystal formation in the plated state electroless nickel layer.
After bestowing the aforementioned hot processing, because of displacement active layer and the workpiece surface and the first plated state electroless nickel layer joint generation solid solution, zinc in the displacement active layer permeates in magnesium alloy, have most the individual crystallites that are the zinc of hcp crystal formation of the sosoloid that is the hcp crystal formation, majority that contain magnesium and zinc and form one, and at least one by the transition layer of the two intermetallic compound that constitutes at least in zinc, nickel and the phosphorus, wherein the bottom of transition layer has and observes the Zn that is the hcp crystal formation 9Ni 1Crystal, surperficial then observe the Ni that is hcp type δ phase 5Zn 21, this is MARTENSITIC TRANSFORMATION behavior, and the bonding force of coating and magnesium alloy is had considerable benefit; Have one based on metallic nickel and metal M and be doped with the amorphous structure of phosphorus as for first electroless nickel layer of gained after the thermal treatment; And second electroless nickel layer contains the nickel that is the fcc crystal formation, the nickel-phosphorus alloy that is the bct crystal formation, armorphous nickel, and is doped with phosphorus in intergranular and the armorphous nickel; The structure of the electrolytic coating after the thermal treatment (composition) is with the structure of aforementioned plated state.
Get the physical property measurement of workpiece 1-7 through surface treatment
To the test specimen of after heat treatment numbering 1-7 carry out in regular turn that bending is adhered to, DPH, internal stress and solidity to corrosion test, the theing contents are as follows of the method for various tests:
(1) crooked sticking power test (ASTM D3359): test piece is forced crooked 90 °, whether observation has plated film to separate or peels off, test result about sticking power is as shown in table 1, can find out in the table 1, through embodiment 1 surface treatment and 7 workpiece do not peel off, represent that each coating is that firm engagement is on magnesium alloy.
(2) DPH of nickel plated film test (CNS 7094 Z8017): use the diamond probe to be pressed into plated film with loading 100g, the shallow more person's hardness of the degree of depth is high more, is representation unit with Hv, and test result is as shown in table 1.
(3) internal stress of plated film test: the test of internal stress does not have standard method so far, just known to the applicant, the pertinent literature report of plated film internal stress test is not arranged yet.This case applicant utilize plated film because of the required externally applied forces of the deformation recovery that internal stress produced (with kgf/mm 2Be unit) be used as testing standard.When wherein testing institute's value and being negative value, represent tension stress, on the occasion of representing stress under compression, test result is as shown in table 1, as seen from Table 1, through embodiment 1 surface treatment and 7 workpiece in, the plated film that is formed by each coating all is in the tension stress state, plated film was not peeled off when this can be avoided magnesium alloy to expand with heat and contract with cold.
(4) anti-corrosion salt mist experiment: according to ASTM B368-61T method, these 7 workpiece are carried out the salt mist experiment of different time, be divided into 10 etc. according to Durbin ' s Standard afterwards, high anti-corrosion is good more more Deng number, micropore quantity is low more, and corrosion proof test result is as shown in table 1, as seen from Table 1, through embodiment 1 surface treatment and 7 workpiece, harsh salt mist experiment that can anti-at least 160hr.
Table 1
The workpiece numbering Salt mist experiment time hr Salt mist experiment is grade as a result Test result is adhered in bending Prestige formula hardness test result The internal stress test result
1 5 10 Do not peel off 281 -16.2
2 10 10 Do not peel off 305 -13.5
3 20 10 Do not peel off 293 -14.5
4 40 10 Do not peel off 317 -11.8
5 80 10 Do not peel off 302 -17.2
6 160 10 Do not peel off 308 -15.6
7 240 8 Do not peel off 296 -14.7
＜embodiment 2 〉
The magnesium alloy plate (work status T7) that 10 U.S.s that are numbered 8-17 are advised LA141A is carried out surface treatment with embodiment 1 identical step, the place that is different from embodiment 1 is: (plating vi) is that Yu Yifen has in the Kazakhstan formula groove (Hull cell) in high and low current district and carries out to step, wherein the current density of high Current Zone is 5A/dm2, and the current density in low current district is 1A/dm2.
Get thickness and the outward appearance of workpiece 8-17 through surface treatment
The height of 10 workpiece that embodiment 2 processing are got and the thickness that the low current district carries out plated film (forming by each coating is stacked on the magnesium alloy) respectively measure and the observation of gloss appearance degree.Wherein the thickness measuring of plated film is to use INOX caliper gage caliper gage made in Germany to measure, and the result is as shown in table 2.Gloss appearance degree as for the nickel plated film does not still have standard measurement mode at present, so with after the visual inspection, the result is as shown in table 2.
As shown in Table 2, the surface of plated film all is the brilliant metallic look on each magnesium alloy workpiece that gets through embodiment 2 processing, has reached requirement attractive in appearance under the thickness range of about 20-40 μ m.Moreover each workpiece represents that the used electronickelling plating bath of embodiment is fine because of the conduction power of fluorion, so splendid for the covering power in low current district in the coating film thickness lower than all quite (1.4-2.2) in high Current Zone and low current district.
Table 2
The test specimen numbering High Current Zone thickness average value μ m High Current Zone outward appearance Low current district thickness average value μ m Low current district outward appearance The thickness ratio
8 40.0 The brilliant metallic look 17.8 The brilliant metallic look 2.2
9 42.3 The brilliant metallic look 30.2 The brilliant metallic look 1.4
10 37.0 The brilliant metallic look 24.7 The brilliant metallic look 1.5
11 37.6 The brilliant metallic look 20.9 The brilliant metallic look 1.8
12 38.4 The brilliant metallic look 20.2 The brilliant metallic look 1.9
13 43.5 The brilliant metallic look 25.6 The brilliant metallic look 1.7
14 35.1 The brilliant metallic look 20.6 The brilliant metallic look 1.7
15 38.3 The brilliant metallic look 24.0 The brilliant metallic look 1.6
16 43.8 The brilliant metallic look 27.4 The brilliant metallic look 1.6
17 41.2 The brilliant metallic look 27.4 The brilliant metallic look 1.5
＜embodiment 3-8 〉
With the step identical with embodiment 1, the magnesium alloy plate of different size in the following table 3 is carried out surface treatment, test solidity to corrosion and crooked tack according to aforementioned identical mode, and carry out amount of thickness and survey.
Table 3
Embodiment Workpiece/Mg content % Thickness of coating μ m Salt mist experiment is grade as a result Experimental result is adhered in bending
3 AZ31B/94.7％ 37.5 10 Do not peel off
4 AZ61A/91.0％ 39.0 10 Do not peel off
5 ZK60A/93.6％ 39.5 10 Do not peel off
6 HM21A/96.4％ 37.0 10 Do not peel off
7 HK31a/95％ 36.5 10 Do not peel off
8 EZ33A/92.1％ 38.0 10 Do not peel off
The result:
As shown in Table 3, the magnesium alloy workpiece of each heterogeneity and content is after handling through this case method, plated film and magnesium alloy layer all have splendid then property, especially by removing the intergranular material, the displacement activation, step such as electroless plating and thermal treatment, the beyond thought effect that transition layer caused that is obtained, be to engage also in the identical mode of crystal formation because of transition layer itself and magnesium alloy layer, therefore, aforementioned each workpiece can be coated with the plated film of about 40 μ m, and do not see that any one peels off adhering to experiment through harsh bending yet, also because of firm engagement like this and the certain thickness plated film of tool, make the workpiece of embodiment 3-8 can reach best solidity to corrosion (grade is 10), it is too late far away that these effects are all any in the past surface treatment method of Mg alloy institute.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the method that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent embodiment of equivalent variations, but every content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.

Claims (67)

1. method that is used for surface treatment one magnesium alloy workpiece is characterized in that: comprise following steps:
(a) make one to have most the workpiece that magnesium alloy constituted that are the sosoloid of close-packed hexagonal body crystal formation by one and forms one and exposed most individual upper layers that are the sosoloid of close-packed hexagonal body crystal formation are arranged;
(b) make and form a displacement active layer that comprises most nickel crystal seeds and most metal M crystal seed on the upper layer of this workpiece, this metal M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance;
(c) on this displacement active layer, deposit one in the electroless plating mode and comprise one based on metallic nickel and metal M and be doped with the first plated state electroless nickel layer of the amorphous structure of phosphorus; And
(d) this workpiece is bestowed a thermal treatment, so that should with this displacement active layer place of the vicinity of this upper layer and the first plated state electroless nickel layer solid solution take place respectively by displacement active layer, and form a transition layer, and obtain one and have a magnesium alloy layer that constitutes by this magnesium alloy, the workpiece of one transition layer and one first electroless nickel layer, this transition layer has most the sosoloid that are close-packed hexagonal body crystal formation that contain magnesium and M, and it is at least one by M, at least the intermetallic compound of the two formation in nickel and the phosphorus, and first electroless nickel layer comprises one based on metallic nickel and M and be doped with the amorphous structure of phosphorus.
2. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 1, it is characterized in that: the magnesium alloy in this step (a) also comprise most between described sosoloid any the two and contain the intergranular of at least one intermetallic compound, and this upper layer has more most slits and is to form by following mode: the end face contact one that makes this workpiece bestowed a ultrasound and with the reactivity of this intermetallic compound degreasing constituent greater than described sosoloid, so that the top layer of the sosoloid of at least a portion at contiguous this end face place and the intermetallic compound at least one part intergranular and the reaction of this constituent, and form a residue, then remove this residue is molten, so that most close-packed hexagonal body sosoloid expose out, and form most by the slit of this end face to lower recess.
3. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 2 is characterized in that: this degreasing constituent comprises an organic acid, a teepol and a high polar organic solvent.
4. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 3 is characterized in that: this organic acid is to be selected from lactic acid, formic acid, oxalic acid, succsinic acid, hexanodioic acid, citric acid, oxysuccinic acid, or the combination of above-mentioned substance.
5. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 4 is characterized in that: this organic acid is that lactic acid and this residue comprise magnesium lactate.
6. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 3 is characterized in that: this teepol is sodium laurylsulfonate and/or 1, the 2-alkyl phosphate.
7. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 3 is characterized in that: this high polar organic solvent is the combination that is selected from methyl alcohol, ethanol, propyl alcohol, Virahol or above-mentioned substance.
8. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 3 is characterized in that: this organic acid and the teepol concentration in this degreasing constituent respectively is 0.1-2M and 0.001-0.01M.
9. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 8 is characterized in that: this organic acid and the teepol concentration in this degreasing constituent respectively is 0.4-0.7M and 0.002-0.04M.
10. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 2, it is characterized in that: the ultrasound in this step (a) has a frequency between 300-360KHz, or has one and can produce a frequency between the 300-360KHz frequency by simple harmonic quantity concussion.
11. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 2 is characterized in that: molten the removing of this residue is by making water or the alcohols below the C4 clean this workpiece and reaching.
12. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 11 is characterized in that: molten the removing of this residue is to reach by making water clean this workpiece.
13. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 11 is characterized in that: molten the removing of this residue is to be undertaken by simultaneously this workpiece is bestowed a ultrasound when cleaning.
14. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 13 is characterized in that: this ultrasound has a frequency between 300-360KHz, or has one and can produce a frequency between the 300-360KHz frequency by simple harmonic quantity concussion.
15. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 1 is characterized in that: the metal M in this step (b) is a zinc.
16. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 1 is characterized in that: this step (b) is to react by the displacement activation constituent that makes this upper layer and comprise water, fluorion, ammonium ion, M ion and nickel ion to reach.
17. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 16 is characterized in that: this displacement activation constituent is bestowed a ultrasound.
18. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 17 is characterized in that: this ultrasound has a frequency between 300-360KHz, or has one and can produce a frequency between the 300-360KHz frequency by simple harmonic quantity concussion.
19. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 16 is characterized in that: this M is a zinc.
20. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 19, it is characterized in that: the displacement activation constituent that uses in this step (b) is to be maintained at one between 0-85 ℃ temperature, and has a pH value between between 0.1-2, fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, and 0.05-2M.
21. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 20, it is characterized in that: the displacement activation constituent that uses in this step (b) is to be maintained at one between 15-30 ℃ temperature, and has a pH value between between 0.2-1.5, fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.7-1.4M, 0.5-0.9M, 0.12-0.25M, and 0.2-0.25M.
22. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 16 is characterized in that: formed displacement active layer comprises most nickel crystal seeds, most metal M crystal seed in this step (b), and magnesium fluoride.
23. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 1, it is characterized in that: the electroless plating of this step (c) is to be undertaken by making this displacement active layer contact one first electroless nickel plating constituent, and this first electroless nickel plating constituent comprises the C2-C8 organic acid ion that water, fluorion, ammonium ion, M ion, nickel ion, hypophosphite ion and are made for buffer reagent.
24. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 23, it is characterized in that: the M ion in the first electroless nickel plating constituent that uses in this step (c) is a zine ion, and this constituent is to be maintained at one between 70-100 ℃ temperature, and have a pH value between between 2-6.5, the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.1-5M, 0.1-5M, 0.02-2M, 0.02-2M, 0.05-1M and 0.02-2M.
25. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 24, it is characterized in that: the first electroless nickel plating constituent that uses in this step (c) is to be maintained at one between 80-97 ℃ temperature, and have a pH value between between 3-4.5, the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.35-0.53M, 0.35-0.53M, 0.06-0.09M, 0.127-0.155M, 0.1-0.2M and 0.07-0.1M.
26. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 2 is characterized in that: the thickness of the formed first plated state electroless nickel layer of this step (c) is controlled and does not fill up the formed slit of this step (a).
27. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 1 is characterized in that: the heat treated temperature of this step (d) is between 140 ℃ to 250 ℃.
28. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 27 is characterized in that: the heat treated temperature of this step (d) is between 170 ℃ to 190 ℃.
29. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 1, it is characterized in that: also comprise a step (c-1) between between step (c) and step (d), this step (c-1) is to contact by the second electroless nickel plating constituent that makes this first plated state electroless nickel layer and one contain nickel ion and Hypophosporous Acid, 50 root, and on this first plated state electroless nickel plating plated state layer, deposit one whereby and contain nickel and the armorphous nickel that is the face-centered cubic crystal formation, and be doped with the second plated state electroless nickel layer of phosphorus in intergranular and the armorphous nickel.
30. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 29, it is characterized in that: the second electroless nickel plating constituent in this step (c-1) comprises the C2-C8 organic acid ion that water, fluorion, ammonium ion, nickel ion, hypophosphite ion, a misfit agent and are made for buffer reagent, this misfit agent is to be selected from diethylenetriamine, quadrol, triethylene tetramine, or the combination of above-mentioned substance.
31. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 30 is characterized in that: this organic acid ion is a citrate ion.
32. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 30, it is characterized in that: this second electroless nickel plating constituent is to be maintained at one between 70-100 ℃ temperature, and have a pH value between between 2-6.5, fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, 0.05-1M, 0.001-0.1M and 0.02-2M.
33. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 32, it is characterized in that: this second electroless nickel plating constituent is to be maintained at one between 80-97 ℃ temperature, and have a pH value between between 3-5, fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.35-0.53M, 0.35-0.53M, 0.13-0.15M, 0.1-0.2M, 0.005-0.01M and 0.07-0.1M.
34. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 29, it is characterized in that: the thickness of the formed first plated state electroless nickel layer of this step (c) is controlled and does not fill up this step (a) slit that forms, and the thickness of this second plated state electroless nickel layer is controlled and fills up the formed slit of this step (a).
35. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 29, it is characterized in that: also comprise a step (c-2) between between step (c-1) and step (d), this step (c-2) is one to push up the step of plating on this second plated state electroless nickel layer, and be by plating, electroless plating, pen plating, electrostatic coating, or the combination of above-mentioned substance is carried out.
36. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 35 is characterized in that: this step (c-2) is to deposit one by plating on this second plated state electroless nickel layer to contain the electrolytic coating that is face-centered cubic crystal formation nickel.
37. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 36, it is characterized in that: the plating in this step (c-2) is to utilize an electroplating composition to carry out, and this electroplating composition comprises the C2-C8 organic acid ion that fluorion, ammonium ion, nickel ion and are made for buffer reagent.
38. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 37 is characterized in that: this organic acid ion is a citrate ion.
39. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 37, it is characterized in that: this electroplating composition is to be maintained at one between 25-70 ℃ temperature, and have a pH value between between 0.5-5.0, fluorion, ammonium ion, nickel ion and this organic acid ionic concentration respectively are 0.1-5M, 0.1-5M, 0.1-2M and 0.02-2M.
40. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 39, it is characterized in that: this electroplating composition is to be maintained at one between 40-60 ℃ temperature, and have a pH value between between 1.5-3, fluorion, ammonium ion, nickel ion and this organic acid ionic concentration respectively are 1.75-2.1M, 1.75-2.1M, 1-1.3M and 0.48-0.72M.
41. the method that is used for surface treatment one magnesium alloy workpiece as claimed in claim 1, it is characterized in that: further comprise the chemical rightenning step between step (a) and step (b), and after this chemical rightenning step, repeatedly implement again once just to carry out step (b) after this step (a),, this chemical rightenning step is to react by the acidic solution that makes this upper layer and contain fluorion, ammonium ion and nitrate ion to carry out.
42. a surface treated magnesium alloy workpiece is characterized in that it comprises:
One magnesium alloy layer is made of a magnesium alloy, and this magnesium alloy has most the sosoloid that are close-packed hexagonal body crystal formation;
One transition layer, be formed on this magnesium alloy layer, have most the sosoloid that are close-packed hexagonal body crystal formation that contain magnesium and M, and at least one by the two intermetallic compound that constitutes at least in M, nickel and the phosphorus, metal M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance; And
One first electroless nickel layer is formed on this transition layer, comprises one based on metallic nickel and metal M and be doped with the amorphous structure of phosphorus.
43. surface treated magnesium alloy workpiece as claimed in claim 42, it is characterized in that: this magnesium alloy have more most between described sosoloid any the two and contain the intergranular of at least one intermetallic compound, and the surface of this magnesium alloy layer depression has most slits.
44. surface treated magnesium alloy workpiece as claimed in claim 42 is characterized in that: the M/ nickel content ratio in this transition layer, along a direction by extremely close this first electroless nickel layer side of close this magnesium alloy layer side, successively decrease.
45. surface treated magnesium alloy workpiece as claimed in claim 42 is characterized in that: the metal M in this transition layer is a zinc.
46. surface treated magnesium alloy workpiece as claimed in claim 45 is characterized in that: close this first electroless nickel layer side of this transition layer contains the Ni5Zn21 that is close-packed hexagonal body crystal formation.
47. surface treated magnesium alloy workpiece as claimed in claim 42 is characterized in that: this transition layer has a thickness that is not less than 20nm.
48. surface treated magnesium alloy workpiece as claimed in claim 42, it is characterized in that: further comprise second electroless nickel layer that is positioned on this first electroless nickel layer, this second electroless nickel layer contains the nickel that is the face-centered cubic crystal formation, the nickel-phosphorus alloy that is the body-centered teteragonal crystal formation, armorphous nickel, and is doped with phosphorus in intergranular and the armorphous nickel.
49. surface treated magnesium alloy workpiece as claimed in claim 48 is characterized in that: it is to fill up described slit that the surface depression of this first electroless nickel layer has most slits and position second electroless nickel layer thereon.
50. surface treated magnesium alloy workpiece as claimed in claim 48 is characterized in that: further comprise an electrolytic coating that is positioned on this second electroless nickel layer, this electrolytic coating comprises the nickel that is the face-centered cubic crystal formation.
51. surface treated magnesium alloy workpiece as claimed in claim 42 is characterized in that: this transition layer further comprises most the crystallites that are the M of close-packed hexagonal body crystal formation.
52. a degreasing constituent is characterized in that it comprises:
One organic acid is to be selected from lactic acid, formic acid, oxalic acid, succsinic acid, hexanodioic acid, citric acid, oxysuccinic acid, or the combination of above-mentioned substance;
One teepol; And
One high polar organic solvent.
53. degreasing constituent as claimed in claim 52 is characterized in that: this organic acid is a lactic acid.
54. degreasing constituent as claimed in claim 52 is characterized in that: this teepol is sodium laurylsulfonate and/or 1, the 2-alkyl phosphate.
55. degreasing constituent as claimed in claim 52 is characterized in that: this high polar solvent is to be selected from methyl alcohol, ethanol, propyl alcohol, Virahol, or the combination of above-mentioned substance.
56. degreasing constituent as claimed in claim 52 is characterized in that: this organic acid and the teepol concentration in this degreasing constituent respectively is 0.1-2M and 0.001-0.01M.
57. degreasing constituent as claimed in claim 56 is characterized in that: this organic acid and the teepol concentration in this degreasing constituent respectively is 0.4-0.7M and 0.002-0.004M.
58. a surface treatment constituent is characterized in that: comprise water, fluorion, ammonium ion, metal M ion and nickel ion, M is the combination that is selected from zinc, cobalt, cadmium or above-mentioned substance.
59. surface treatment constituent as claimed in claim 58 is characterized in that: M is a zinc.
60. surface treatment constituent as claimed in claim 59 is characterized in that: have a pH value between between 0.1-2, fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, and 0.05-2M.
61. surface treatment constituent as claimed in claim 60 is characterized in that: have a pH value between between 0.2-1.5, fluorion, ammonium ion, zine ion and nickel concentration respectively are 0.7-1.4M, 0.5-0.9M, 0.12-0.25M, and 0.2-0.25M.
62. surface treatment constituent as claimed in claim 58 is characterized in that: further comprise the C2-C8 organic acid ion that Hypophosporous Acid, 50 root and is made for buffer reagent, this surface treatment constituent can be used for electroless nickel plating.
63. surface treatment constituent as claimed in claim 62 is characterized in that: this organic acid ion is a citrate ion.
64. surface treatment constituent as claimed in claim 62, it is characterized in that: have a pH value between between 2-6.5, the M ion is that the concentration of zine ion and fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.1-5M, 0.1-5M, 0.02-2M, 0.02-2M, 0.05-1M and 0.02-2M.
65. as the described surface treatment constituent of claim 64, it is characterized in that: have a pH value between between 3-4.5, the concentration of fluorion, ammonium ion, zine ion, nickel ion, hypophosphite ion and this organic acid ion respectively is 0.35-0.53M, 0.35-0.53M, 0.06-0.09M, 0.127-0.155M, 0.1-0.2M and 0.07-0.1M.
66. electroless nickel plating constituent, it is characterized in that: comprise: water, fluorion, ammonium ion, nickel ion, Hypophosporous Acid, 50 root, a misfit agent and are made for the C2-C8 organic acid ion of buffer reagent, this misfit agent is to be selected from diethylenetriamine, quadrol, triethylene tetramine, or the combination of above-mentioned substance.
67. as the described electroless nickel plating constituent of claim 66, it is characterized in that: have a pH value between between 2-6.5, fluorion, ammonium ion, nickel ion, hypophosphite ion, this misfit agent concentration and organic acid ionic concentration respectively are 0.1-5M, 0.1-5M, 0.02-2M, 0.05-1M, 0.001-0.1M and 0.02-2M.
CNA2006100810216A 2006-05-19 2006-05-19 Method for treating magnesium-alloy workpiece, workpiece therefrom and composition therewith Pending CN101074479A (en)

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CN103820801B (en) * 2014-03-18 2016-05-04 天津市澳路浦润滑科技股份有限公司 Water-based response type aluminium special-purpose metal detergent and preparation method thereof
CN105839083A (en) * 2016-05-23 2016-08-10 深圳市瑞世兴科技有限公司 Magnesium alloy nickel plating method
WO2018098665A1 (en) * 2016-11-30 2018-06-07 Aramco Services Company Scaling and corrosion resistant fluid conduit
CN111359969A (en) * 2020-04-21 2020-07-03 程太军 Oxidation cleaning treatment integrated equipment for magnesium alloy surface modification
CN111359969B (en) * 2020-04-21 2021-05-11 江苏中科亚美新材料股份有限公司 Oxidation cleaning treatment integrated equipment for magnesium alloy surface modification
CN114214611A (en) * 2021-12-30 2022-03-22 河北中瓷电子科技股份有限公司 Low-temperature replacement gold plating process for packaging shell

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