CN105209667A - Electrolytic generation of manganese (III) ions in strong sulfuric acid - Google Patents

Electrolytic generation of manganese (III) ions in strong sulfuric acid Download PDF

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CN105209667A
CN105209667A CN201480014056.0A CN201480014056A CN105209667A CN 105209667 A CN105209667 A CN 105209667A CN 201480014056 A CN201480014056 A CN 201480014056A CN 105209667 A CN105209667 A CN 105209667A
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manganese
methods
ion
acid
solution
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CN105209667B (en
Inventor
T·皮尔逊
T·克拉克
R·V·查帕内利
C·罗宾森
A·西斯洛普
A·辛
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MacDermid Acumen Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/21—Manganese oxides
    • 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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/22—Roughening, e.g. by etching
    • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Abstract

An electrolytic cell and a method of electrochemical oxidation of manganese(II) ions to manganese(III) ions in the electrolytic cell are described. The electrolytic cell comprises (1) an electrolyte solution of manganese(II) ions in a solution of at least one acid; (2) a cathode immersed in the electrolyte solution; and (3) an anode immersed in the electrolyte solution and spaced apart from the cathode. Various anode materials are described including vitreous carbon, reticulated vitreous carbon, woven carbon fibers, lead and lead alloy. Once the electrolyte is oxidized to form a metastable complex of manganese(III) ions, a platable plastic may be contacted with the metastable complex to etch the platable plastic. In addition, a pretreatment step may also be performed on the platable plastic prior to contacting the platable plastic with the metastable complex to condition the plastic surface.

Description

The electrolysis of manganese (III) ion in strength sulfuric acid generates
Cross reference related application
The application is the application number 13/677 at present still in examination submitted on November 15th, 2012, the part of 798 continues, this application is the application number 13/356 at present still in examination submitted on January 23rd, 2012, the part of 004 continues, and their respective themes are incorporated to herein with its entirety all by reference.
Technical field
The present invention relates to a kind of modification method of the plated plastics for etching such as ABS and ABS/PC in general.
Background technology
In this area known in order to multiple object with metal-plated non-conductive substrate (that is, plastics).Plastic shaping is produced relatively cheap, and metallized plastic are used to many application.Such as, metallized plastic are for decoration and for the manufacture of electronics.The example of decorative use comprises auto parts, such as automotive trim.The example of electronic applications comprises printed circuit board (PCB), wherein comprises the conductor of printed circuit board (PCB) with the metal of selectivity pattern plating, and for the metallized plastic of EMI shielding.ABS resin is for decorative purpose the most often by the plastics of plating, and phenol resins and epoxy resin are printed circuit board (PCB)s manufacture in the most often by the plastics of plating.
Plating on frosting is used to produce various article of consumption.The production of plastic shaping is relatively cheap, and platable material is used for many application, comprises automotive trim.The plating of plastics relates to many stages.First stage relates to etching plastics, and to provide the machinery of subsequent metal overlay film to stick together, and provide suitable surface for the absorption of palladium catalyst, this palladium catalyst is typically in order to the deposition of catalysis initial metal layer from autocatalytically nickel or copper-plating technique.Then, the settled layer of deposited copper, nickel and/or chromium can be executed.
The initial etch of plastic assembly is the integral part of whole operation.But, only there is the plastic assembly of certain type to be applicable to plating.The most common plastic type for electroplating is the adulterant (ABS/PC) of acrylonitrile/butadiene/styrene (ABS) or ABS and polycarbonate.ABS is by two phase composites.The relatively hard phase that first-phase is made up of vinyl cyanide/styrol copolymer, second-phase is softer polyhutadiene phase.
At present, this material is nearly all use the mixture of chromic acid and sulfuric acid to etch, and this is very effective etching reagent for ABS and ABS/PC.The polyhutadiene of these plastics is containing double bond in the backbone of polymkeric substance, and it is oxidized by chromic acid, thus causes fracture completely and the dissolving of the polyhutadiene phase being exposed to this frosting, reaches effective etching of this frosting.
A problem of traditional chromic acid etching step is that chromic acid is considered to carcinogens, and control is all the more strict, needs to replace chromic acid with safer surrogate as far as possible.The use of chromic acid etching reagent also has known critical defect, comprises the toxicity of chromium cpd, causes it to dispose difficulty, and the chromic acid residue stayed on polymer surfaces suppresses electroless deposition, and rinses chromic acid residue difficulty from this polymer surfaces after treatment.In addition, the sexavalent chrome sulphuric acid soln of heat has natural danger for worker.The worker Chang You of these chromium etching solutions of everyday exposure burns and upper respiratory tract hemorrhage.Therefore, the safer surrogate of development acidic chromium etching solution is expected very much.
In early days the surrogate using high manganese ion as chromic acid is focused on usually to the trial replacing etching plastics chromic acid.The United States Patent (USP) the 4th, 610 of the people such as Tubergen, describe permanganate in No. 895 and combinationally use with sour, it is incorporated herein by reference in full.Afterwards, U.S. Patent Application Publication No. 2005/0199587 suggestion permanganate of Bengston and ionic palladium activation stage combinationally used, and it is incorporated herein by reference in full.No. 2009/0092757th, the U.S. Patent Application Publication of Satou describes sour permanganate solution and high halide-ions (such as, perchlorate or periodate) combinationally uses, and it is incorporated herein by reference in full.Finally, No. WO2009/023628th, the International Publication of Enthone describes and does not use high manganese ion when having basic metal or alkaline earth metal cation, and it is incorporated herein by reference in full.
The United States Patent (USP) the 3rd, 625 of the people such as Stahl, No. 758 also illustrate permanganate solution, and it is incorporated herein by reference in full.Stahl suggested chromium and sulfuric acid bath or the permanganate solution suitability for the preparation of surface.In addition, the United States Patent (USP) the 4th, 948 of the people such as Courduvelis, No. 630 full text are incorporated herein by reference, and which depict a kind of Alkaline permanganate solutions of heat, and it is also containing a kind of material, such as clorox, its oxidizing potential is higher than the oxidizing potential of permanganate solution.United States Patent (USP) the 5th, 648, No. 125 full text of Cane are incorporated herein by reference, and which depict the Alkaline permanganate solutions using and comprise potassium permanganate and sodium hydroxide, wherein this permanganate solution is maintained at high temperature, i.e. about 165 ℉ to 200 ℉.
Visible, advise that many kinds of etching solutions replace in the technique of chromic acid for the preparation of metallization non-conductive substrate.But due to various economy, performance and/or environment, these techniques are all not yet proved to be gratifying, therefore these techniques not yet reach business success or are accepted to become the substitute of applicable chromic acid etching by industry.In addition, the stability of these etching solutions based on permanganate also may not be good, causes the formation of Manganse Dioxide mud.
Inventor's solution that have studied based on permanganate forms mud and the tendency of decompose themselves occurs.Under strong acidic environment, according to following reaction, high manganese ion can react with hydrogen ion, produces manganese (II) ion and water:
4MnO 4 -+12H +→4Mn 2++6H 2O+5O 2(1)
Then manganese (II) ion that this reaction is formed can react with high manganese ion further, according to following reaction, forms Manganse Dioxide mud:
2MnO 4 -+2H 2O+3Mn 2+→5MnO 2+4H +(2)
Therefore, be no matter the high manganese ion that the high manganese ion that added by an alkali metal salt of permanganate or electrochemical in-situ are produced, the formula based on strongly-acid permanganate solution is unstable in essence.Compared to the chromic acid etching used at present, the adverse chemical stability of acid permanganate makes it conscientiously useless for large-scale commercial applications application.Alkaline permanganate etching is more stable, and is widely used in printed circuit board industry, and for etching epoxy printed circuit board (PCB), but alkaline permanganate is not effective etching reagent for the plastics of such as ABS or ABS/PC.Therefore, manganese (VII) cannot as the etching reagent of these materials degree of gaining broad commercial acceptance.
Do not use chromic acid and the trial that etches ABS has comprised the silver (II) and cobalt (III) that use electrochemistry to produce.Some metal can be oxidized anodically the state of oxidation into high oxidation.Such as, cobalt can be oxidized to cobalt (III) from cobalt (II) and silver can from silver (I) be oxidized to silver (II).
But, be not applicable at present plastics the manganese based on permanganate (no matter for acid or alkali form) or other state of oxidation any or by using suitable business success etching reagent of other acid or oxygenant.
Therefore, this area still needs a kind of not containing chromic acid and be the etching reagent of the acceptable improvement of business, its plastic base used for the preparation of follow-up plating.
Summary of the invention
An object of the present invention is to provide a kind of etching reagent not containing chromic acid for plastic base.
Another object of the present invention is to provide the acceptable etching reagent of a kind of business for plastic base.
Another object of the present invention is to provide a kind of etching reagent based on mn ion for plastic base.
An also object of the present invention is to provide a kind of to be suitable in strong acid oxidization electrolysis matter but not by the electrode of this electrolyte degradation.
An also object of the present invention is to provide the acceptable electrode being suitable for producing manganese (III) ion in strength sulfuric acid of a kind of business.
An also object of the present invention is to provide a kind of pre-treatment step of the improvement for nursing one's health plastic base before etching.
In one embodiment, the present invention relates to a kind of electrolyzer in general, and it comprises:
Electrolyte solution, it comprises manganese (III) ion in the solution being in sulfuric acid and additional acid, and this additional acid is selected from the group be made up of methanesulfonic, methane-disulfonic acid and combination thereof;
Negative electrode, itself and this electrolyte solution contacts; And
Anode, itself and this electrolyte solution contacts.
In another embodiment, the present invention relates to a kind of electrolyzer in general, and it comprises:
Electrolyte solution, it comprises manganese (III) ion in the solution being at least one acid;
Negative electrode, itself and this electrolyte solution contacts; And
Anode, itself and this electrolyte solution contacts, wherein this anode comprises the material selected from the group be made up of vitreous carbon, reticulated vitreous carbon, weaving carbon fiber, lead, lead alloy and one or more combination aforementioned.
In another embodiment, the present invention relates to a kind of method preparing the solution that can etch plastic base in general, and the method comprises the following steps:
In electrolyzer, provide ionogen, this ionogen comprises the solution of manganese (II) ion in the solution being at least one acid, and wherein this electrolyzer comprises anode and negative electrode; And
Apply electric current to the anode of this electrolyzer and negative electrode; And
Be oxidized this ionogen to form manganese (III) ion, wherein this manganese (III) ion forms metastable state complex compound.
In another embodiment, the present invention relates to the electrode being suitable for manganese (II) ion electrochemical being oxidized to manganese (III) ion in strong acid solution in general.
In another embodiment, the present invention relates to a kind of method manganese (II) ion electrochemical being oxidized into manganese (III) ion in general, comprises the following steps:
Ionogen is provided in electrolyzer, this ionogen is included in the solution of manganese (II) ion in the solution of at least one acid, wherein this at least one acid comprises sulfuric acid and additional acid, this additional acid is selected from by methanesulfonic, methane-disulfonic acid and its group formed, and wherein this electrolyzer comprises anode and negative electrode;
Electric current is applied between this anode and this negative electrode; And
Be oxidized this ionogen to form manganese (III) ion, wherein this manganese (III) ion forms metastable state complex compound.
In an also embodiment, the present invention relates to a kind of method etching plastic components in general, the method comprise by this plastic components with comprise manganese (III) ion and contact with the solution of at least one acid.
Embodiment
The present inventor has been found that can in strong acid solution, and preferably in strength sulfuric acid solution, most preferably in the sulphuric acid soln of at least 8M, under low current density, electrolysis divalent manganesetion is easily to produce manganic.More particularly, the present inventor has been found that the Manganic ion solution in strongly acidic solution can etch ABS.
Manganic is unstable and have high oxidative (be 1.51 relative to the standard oxidationreduction potential of standard hydrogen electrode).In the solution, its via following reaction quickly disproportionation (disproportionate) be Manganse Dioxide and bivalent manganese:
2Mn 3++2H 2O→MnO 2+Mn 2++4H +(3)
But in strength sulfuric acid solution, Manganic ion becomes metastable (meta-stable), and forms the sulfate complex of cherry purple/red color.Contriver has been found that this sulfate complex is the medium being applicable to etching ABS, and has many advantages being better than the Chrome-free etching of prior art.
Therefore, in one embodiment, the present invention relates to a kind of method preparing the solution that can etch plastic base in general, and the method comprises the following steps:
In electrolyzer, provide ionogen, this ionogen comprises manganese (II) solion in the solution being at least one acid, and wherein this electrolyzer comprises anode and negative electrode; And
Apply electric current to this anode of this electrolyzer and this negative electrode; And
Be oxidized this ionogen to form manganese (III) ion, wherein this manganese (III) ion forms metastable state complex compound.
In a preferred embodiment, this plastic base comprises ABS or ABS/PC.
Although consider that phosphoric acid and sulfuric acid are all suitable for composition of the present invention, in a preferred embodiment, this acid is sulfuric acid.At room temperature, in 7M sulfuric acid, the transformation period of manganese (III) ion is about 2 years.Contrastingly the transformation period of manganese (III) ion of same concentrations is about 12 days in 7M phosphoric acid.Infer the higher stability of manganese (III) ion in sulfuric acid be due to define manganese-sulfate complex and in sulphuric acid soln obtainable hydrogen ion concentration higher.Another problem of use phosphoric acid is the limited solubleness of manganous phosphate (III).Therefore, although other mineral acid of such as phosphoric acid can be used in composition of the present invention, usually preferably sulfuric acid is used.
In use, the remarkable stability of manganese (III) ion in strength sulfuric acid provides following advantage:
1) because manganese (III) ion is formed under low current density, the electricity needs of this technique is usually very low.
2) because this anode operates under low-down current density, therefore, it is possible to use negative electrode little for annode area, to prevent the cathodic reduction of manganese (III) ion.This eliminate the demand separating pond, and make the engineering of etching reagent regenerated reactor simpler.
3) because this technique does not produce high manganese ion, permanganic anhydride (this is safety hazard thing, because it has explosivity) can not therefore be produced in this solution.
4) due to the high stability of manganese (III) ion in strength sulfuric acid, therefore this etching reagent can use in direct marketing.Aborning, this etching reagent only needs a little regenerated reactor in the side of groove, to maintain manganese (III) content of etching solution and to prevent the accumulation of manganese (II) ion.
5) because other etch process is based on permanganate, the result of the therefore reaction of permanganate and manganese (II) ion causes quick " mud " of Manganse Dioxide and this etching solution very short lifetime.This should not be problem (although along with time may produce some disproportionations) for the etching solution based on manganese (III).
6) according to the present invention, the electrolysis of manganese (III) generates and can not produce any poisonous gas.Although can produce some hydrogen at negative electrode, due to low current demand, this is less than the hydrogen that many electroplating technologies produce.
As described herein, in a preferred embodiment, this acid is sulfuric acid.The concentration of sulfuric acid is preferably at least 8 moles, is more preferably about 9 to about 15 moles.In the process, the concentration of sulfuric acid is important.Concentration is lower than about 9 moles, and etch-rate is slack-off, more than 14 moles, then and the solubleness step-down of mn ion in solution.In addition, very the sulfuric acid of high density tends to from absorption of air moisture, and has harm for operation.Therefore, in most preferred embodiments, the concentration of sulfuric acid is about 12 to 13 moles, and its enough rare adding with safety adds water to etching, and enough strong with the etch-rate optimizing plastics.Under the sulfuric acid of this concentration, be up to the manganous sulfate of about 0.08M in the preferred operations temperature solubilized of etching.In order to the etching of the best, in solution mn ion concentration should how high can reach many higher positions for it.
Although also can use manganese (II) ion in other similar source as known in the art in enforcement of the present invention, this manganese (II) ion is preferably selected from the group in being made up of manganous sulfate, manganous carbonate and manganous hydroxide.The concentration range of manganese (II) ion can be about 0.005 mole to saturated.In one embodiment, this ionogen also comprises colloidal silica manganese.This can to a certain extent in solution the natural result of manganese (III) disproportionation formed, maybe can specially be added.
Manganese (III) ion can be produced easily by the oxidation of manganese (II) ion by electrochemical appliance.In addition, preferably this ionogen does not comprise any high manganese ion usually.
As described herein, in order to obtain the fast etch rate for ABS plastic, need the acid using high density.Need the existence of sulfate radical or hydrogen sulfate ion, to form complex compound with mn ion, and at least need the sulfuric acid volumetric molar concentration of 8M to obtain the good stability etched.In order to the etching of good plastics, find that fast-etching needs the sulfuric acid concentration at least about 12M.This has the effect reducing manganese ion dissolution degree in bath, and in bathing at the operational, mn ion maxima solubility is about 0.08M.Because etch-rate depends on the concentration of manganese in solution (III) ion and the maximum conversion per-cent for maintaining stability is about 50%, expect to increase the manganese amount that may be dissolved in bath.
Contriver has been found that by the another kind of acid a part of sulfuric acid of displacement and increases the manganese amount that may be dissolved in bath, and wherein mn ion can have more solvability.
Suitable acid is selected limited.Such as, hydrochloric acid can produce chlorine at anode, and nitric acid can produce nitrogen protoxide at negative electrode.Perchloric acid and Periodic acid are expected and can produce high manganese ion, and it can resolve into Manganse Dioxide.Organic acid generally can by manganese (III) ion Quick Oxidation.Therefore, for oxygenizement, there is required stability and the acid of ability increasing manganese ion dissolution degree in bath is methanesulfonic and methane-disulfonic acid.Because solubleness ratio in methanesulfonic (with sulfuric acid) of manganese (II) is significantly better in methane-disulfonic acid, the former selection produces better properties.Therefore, methanesulfonic is preferred additional acid, and sulfuric acid is preferred main acid.
Based on more than, the present invention also relates to a kind of ionogen for etching ABS and ABS/PC plastics in general, comprise sulfuric acid, and combinationally use methanesulfonic or methane-disulfonic acid, to obtain better manganese ion dissolution degree in bath, wherein this ionogen contains the sulfuric acid of at least 8M and comprises about 0M to the methanesulfonic of about 6M or methane-disulfonic acid, the preferably methanesulfonic of about 1M to about 6M.
More particularly, the present invention relates to a kind of electrolyzer in general, comprises:
Electrolyte solution, comprise manganese (III) ion in the solution being in sulfuric acid and additional acid, this additional acid is selected from the group be made up of methanesulfonic, methane-disulfonic acid and combination thereof;
Negative electrode, itself and this electrolyte solution contacts; And
Anode, itself and this electrolyte solution contacts.
In addition, the present invention also relates to a kind of electrolyzer in general, comprises:
Electrolyte solution, comprises manganese (III) ion in the solution being at least one acid;
Negative electrode, itself and this electrolyte solution contacts; And
Anode, itself and this electrolyte solution contacts, wherein this anode comprises the material selected from the group be made up of vitreous carbon, reticulated vitreous carbon, weaving carbon fiber, lead, lead alloy and one or more combination aforementioned.
In addition, the present invention also relates to a kind of method manganese (II) ion electrochemical being oxidized to manganese (III) ion in general, comprises the following steps:
In electrolyzer, provide ionogen, wherein this ionogen comprises manganese (II) solion in the solution being at least one acid, and wherein this electrolyzer comprises anode and negative electrode;
Electric current is applied between this anode and this negative electrode; And
Be oxidized this ionogen to form manganese (III) ion, wherein this manganese (III) ion forms metastable state complex compound.
Once this ionogen is oxidized to form metastable state complex compound, this can be plated plastics and be immersed in for some time in this metastable state complex compound, to etch the surface that this can plate plastics, in one embodiment, at the temperature of 30 to 80 DEG C, this can plate plastics and be immersed in this metastable state complex compound.Etch-rate raises along with temperature and to increase and slow 50 DEG C below.
The upper limit of temperature is determined by the character of etched plastics.ABS starts distortion more than 70 DEG C, and therefore in a preferred embodiment, particularly when etching ABS material, electrolytical temperature is maintained at about 50 to about 70 DEG C.The plastics leaching time is in the electrolyte preferably about 10 to about 30 minutes.
The conventional pre-treatment for plated plastics can be used to carry out follow-up plating to the object etched in this way, or the surface of the etching of these plastics can be used to promote sticking together of coating, paint or other top coat.
The concentration of manganese (II) ion used in etching of the present invention is determined by volt-ampere circulation method.Oxygenizement is subject to diffusion control, therefore needs effectively to stir etching solution in this electrolytic acid cleaning oxydation process.
In electrolyzer described herein, spendable anode and negative electrode can comprise various material.Negative electrode can comprise the material selected from the group be made up of the coated titanium of platinum, platinized titanium, niobium, iridium oxide and lead.In one preferred embodiment, negative electrode comprises platinum or platinized titanium.Another preferred embodiment in, negative electrode comprises lead.Anode also can comprise platinized titanium, platinum, iridium/tantalum pentoxide, niobium, boron doped diamond or other suitable material any.
Contriver finds, although the combination of manganese (III) ion and strength sulfuric acid (that is, 8 ~ 15 moles) can etch ABS plastic, this etching reagent also very has aggressiveness to the necessary electrode of generation manganese (III) ion.Especially, the anode with titanium-base can by this etching reagent fast degradation.
Therefore, in the trial determining more suitable electrode materials, test other electrode materials various, comprise lead and graphite.Vitreous carbon and reticulated vitreous carbon are considered to firmer, and when applying to be preferably 0.1 ~ 0.4A/dm 2during the electric current of (amassing based on nominal surface), manganese (III) ion can be produced.In addition, because vitreous carbon in commercial applications and reticulated vitreous carbon do not have a cost effectiveness as electrode, therefore anode also can be manufactured by weaving carbon fiber and obtain.
Carbon fiber is fiber manufacture from polyacrylonitrile (PAN) and obtains.These fibers, at increased temperature through oxidizing process, then carry out carburising step in very high temperature under an inert atmosphere.This carbon fiber is then prepared for sheet, and it is combined with various resin system usually, produces high strength assembly.Carbon fiber sheet also has good electrical conductivity, and this fiber has random layer (turbostratic) (that is, nonsequential bed) structure usually.Do not want to be limited to theory, believe that this structure makes carbon fiber be effective as electrode.SP in lattice 2the carbon atom of hydridization provides good electrical conductivity, and SP 3carbon atom and the graphite linings of hydridization link together, and are fixed their position, thus provide good chemical resistant properties.
Comprise the carbon containing at least 95% for the preferred material in electrode of the present invention and do not flood the weaving carbon fiber of any resin.For the ease of process and weaving, carbon fiber is usually with epoxy resin starching (sizing), and this can occupy maximum 2% of fibre weight.With this low percentage, when as electrode, the etched high sulfuric acid content of epoxy starching removes fast.This can cause the initial mild variable color of etching solution, but can not affect performance.In this initial " break-in " after the stage, anode demonstrates can resist this ionogen, and the efficient oxidation manganese (II) ion becomes manganese (III).
By fixing this weaving carbon fiber material in suitable providing in the framework of electrical contact and construction anode.Also can carbon fibre material be used when producing manganese (III) ion as negative electrode, but use plumbous more convenient, if particularly negative electrode is significantly less than anode when pond is not separated in use.
The current density sections applied in this electrolyzer is limited to the oxygen overpotential on selected anode material.Such as, when platinized and titanized anode, current density is about 0.4A/dm 2on, anode potential is enough high with releasing oxygen.Now, the transformation efficiency that manganese (II) ion becomes manganese (III) ion declines, and thus wastes the current density of any further increase.Moreover, produce and tend to produce Manganse Dioxide but not manganese (III) ion at anode surface more exceeding potential operations anode more needed for high current density.
Find surprisingly, lead anode can be effectively used in electrolyzer described herein.Owing to forming sulfuric acid lead layer on surface, it has very limited solubleness in sulfuric acid, and therefore in strong acid, lead becomes passivation.This makes anode passivation, until reach very high overpotential (relative to standard hydrogen electrode more than 2V).At the current potential higher than this level, produce oxygen and the mixture of plumbic oxide.Although expect that this high operation current potential is conducive to oxygen and produces and high manganese ion but not the formation of manganese (III) ion, the experiment of lead anode is used only to produce manganese (III) ion and without permanganate.This confirms by dilute with water etching solution, and manganese (III) ion disproportionation produces brown Manganse Dioxide and manganese (II) ion.The filtration of this solution produces in fact colourless manganese (II) solion characteristic but not the high manganese ion of purple.
The present inventor has been found that because these anodes have very high efficiency for the oxidation of manganese (II) ion, therefore when using lead anode, needs the speed monitoring oxidation.Thus, if the speed of oxidation is monitored and control, then there is too a high proportion of manganese (II) ion oxidized, leave the manganese (II) of very lower concentration.When without manganese (II) ion, anode starts manganese oxide (III) ion and becomes manganese (IV), and it forms insoluble Manganse Dioxide fast.
Based on the above, be importantly no more than original concentration 50%, and be oxidized to manganese (III) ion preferably more than manganese (II) ion of 25%, to maintain this electrolytical stability.When lead anode, this relates to by the titration of this etching solution or uses redox electrode monitor the accumulation of manganese (III) ion and when manganese (III) content reaches desired amount, stop this electrolysis.When sulfuric acid concentration is 12.5M, needs manganese (III) ion of the concentration had more than 0.01M to be used for effectively etching and maximum stability, and be no more than 0.04M based on total Fe content 0.08M.
Anode can comprise plumbous or suitable lead alloy, and selected types of alloys can affect efficiency of conversion.Pure lead or the lead comprising small proportion tin effective especially, and the efficiency of conversion produced is about 70%.Also find, with the stirring of resonable degree, surprisingly can apply high current density and still maintain this switching rate.
After use lead anode carries out long-time electrolysis, find the final film forming Manganse Dioxide.Once the Manganse Dioxide of significant quantity concentrates at electrode surface, it tends to quickly thickening.But Manganse Dioxide can easily be reduced electrochemically as manganese (II) ion.Therefore, by the method periodically making electric current in pond reverse, alleviate or get rid of the accumulation of Manganse Dioxide.Repeatedly electric current oppositely between time cycle be not crucial, as long as apply enough coulomb electric charges so that the amount of the Manganse Dioxide being deposited on surface is reverted back manganese (II) ion in reversal phase.
Based on the above, when using lead to reach to produce manganese (III) ion in sulphuric acid soln the object etching ABS or ABS/PC with lead alloy, suitable working concentration has been reached at manganese (III) ion, when namely can be 0.01 to 0.04M based on this suitable working concentration of total Fe content 0.08M, now preferably interrupt electrolysis program, make manganese (II) ion leaving significant quantity in the solution, thus bath is stablized and can not be deposited excessive Manganse Dioxide.Preferred electrode materials comprises such as pure lead, the plumbous antimony containing 4% antimony of having an appointment, the lead-tin anode containing the most nearly 5% tin and lead/tin/calcium anode.Enforcement of the present invention also can use other suitable lead alloy.In addition, the use of periodically reverse electric current prevents at anode accumulation Manganse Dioxide film.This maintains the transformation efficiency of anode effectively, and minimizing or eliminating remove and the demand of clearing up anode from etching bath or regenerated reactor.
In addition, in order to effectively produce manganese (III) ion, usually need to use the annode area larger than cathode area.Preferably, the anticathode area ratio of anode is at least about 10:1.By this, negative electrode can directly be soaked in the electrolyte, and does not need to have separation pond.Although this technique can use separate pond configuration effort, this can bring unnecessary complicacy and expense.
Referring now to following non-limiting example, the present invention is described:
comparative example 1:
12.5 mol sulfuric acid (500 milliliters) solution of 0.08 mol sulfuric acid manganese (II) is heated to 70 DEG C, and the ABS that a slice can be plated grade is immersed in this solution.Even in this solution of immersion after 1 hour, this test panel does not have discernible etching yet, and after the washing, this surface " does not soak ", and can not support uncracked moisture film.
embodiment 1:
By immerse area be 1dm 2platinized and titanized anode and surface-area 0.01dm 2platinized titanium negative electrode in the solution of comparative example 1, apply the electric current 5 hours of 200mA, this solution of electrolysis.
In the electrolytic process, find that this solution colour changes to very dark purple/redness from almost colourless.Confirmation does not have high manganese ion.
Then this solution is heated to 70 DEG C, and the ABS that a slice can be plated grade is immersed in this solution.After immersion 10 minutes, this testing plate complete wetting, and uncracked moisture film can be supported after being flushed.After immersion 20 minutes, this sample cleans in water, dry and detect with sweep electron microscope (SEM).This testing plate of this detection display is etched by essence, and visible many etching recesses.
embodiment 2:
With current density 0.2A/dm 2use platinized and titanized anode, electrolysis contains the solution of 12.5M sulfuric acid and 0.08M manganous sulfate (II).Usable floor area is less than the platinized titanium negative electrode of 1% annode area, to prevent the cathodic reduction of manganese (III) ion produced at anode.Electrolysis carries out the long-time enough coulomb that transmission is enough being manganese (III) by all manganese (II) ionic oxide formations.The solution obtained is that dark cherry is purple/red.Do not produce high manganese ion in this step.This is also confirmed by visible spectrum, and this manganese (III) ion produces the absorption spectrum being different from permanganate solution completely.
embodiment 3:
Etching solution such as prepared by above-described embodiment 2 is heated to 65 ~ 70 DEG C on magnetic stirrer/hot-plate, and for some time of 20 ~ 30 minutes is immersed in the test piece of ABS in this solution.Detect some in these test pieces by SEM, and some test pieces process with normal electroplating plastic pre-treatment sequence (being plating to 25 ~ 30 microns with inner reduction, pre-soaking, activation, acceleration, electroless nickel, copper in M).Then these test pieces are annealed and use Instron machine to carry out peel strength test.
Plated test piece is carried out 30 minutes peel strength tests, shows that stripping strength is about changing between 1.5 and 4N/cm.
Use surface-area is 0.196cm 2platinum rotating disc electrode (RDE) in different rotating speeds, obtain a volt-ampere cycle diagram from the solution comprising 12.5M sulfuric acid and 0.08M manganous sulfate.Together with using, model 263A's determine potentiometer (potentiostat) and silver/silver chloride reference electrode with RDE.
In all cases, forward scan is presented at about 1.6V has a peak relative to Ag/AgCl, is then near plateau region to 1.75V, and after-current increases.Reverse scan produces similar at the slightly plateau region of low current and the peak near 1.52V.The dependency of these results to electrode rotary speed shows, mass transportation controls to be the Main Factors in this mechanism.This plateau region indicates potential range, and on this potential range, manganese (III) ion is formed by electrochemical oxidation process.
Carry out determining potentiometer scanning at 1.7V.Find that electric current lands at the beginning, increase over time, become.In the current density of this current potential 0.15 and 0.4A/dm 2between change.
After this experiment, with fixed current density 0.3A/dm 2carry out constant-current discharge (galvanostatic) and measure examination.At the beginning, reached the current density of applying by the current potential of about 1.5V, but carry out along with experiment, after about 2400 seconds, find that current potential is increased to about 1.75V.
After being etched more than 10 minutes, finding the surperficial complete wetting of this ABS test piece, and support uncracked moisture film after the washing.After for some time of 20 or 30 minutes, this plate is obviously etched.
embodiment 4:
Preparation comprises the solution of 10.5M sulfuric acid and 2M methanesulfonic.At temperature 68 ~ 70 DEG C, the manganous sulfate of 0.16M can be dissolved easily, however dissolve in 12.5M sulphuric acid soln manganous sulfate for comparing, only solubilized 0.08M.By the electrolysis of solutions of this preparation to produce manganese (III) ion that manganese (III) concentration is 0.015M, its etch-rate provided can compare favourably with the speed obtained from the 12.5M sulphuric acid soln with 0.015M manganese (III) concentration.
Continue the electrolysis in the bath of embodiment 4, until manganese (III) content reaches 0.04M and another plate is etched.The etch-rate (specific concentration 0.015M gained speed height about 25%) promoted is obtained under manganese (III) ion of this higher concentration.
comparative example 2:
To comprise graphite and nominal at the temperature of 65 DEG C, to measure surface-area be 1dm 2electrode immerse 500 milliliters in 12.5M sulfuric acid containing 0.08M manganous sulfate solution in.Negative electrode in this pond is nominal measurement surface-area is 0.1dm 2lead flake.The electric current applying 0.25 ampere, to this pond, obtains 0.25A/dm 2nominal anodic current density and 2.5A/dm 2nominal cathode current density.
Find in the electrolysis being less than 1 hour, graphite anode rapid disruption is also degraded.In addition, do not find that manganese (II) ionic oxide formation becomes manganese (III) ion.
comparative example 3:
To the titanium-base of the tantalum/iridium oxide coating (50% tantalum oxide, 50% iridium oxide) being coated with mixing be comprised at the temperature of 65 DEG C and nominal measure surface-area be 1dm 2electrode immerse 500 milliliters in 12.5M sulfuric acid containing 0.08M manganous sulfate solution in.Negative electrode in this pond is nominal measurement surface-area is 0.1dm 2lead flake.The electric current applying 0.25 ampere, to this pond, obtains 0.25A/dm 2nominal anodic current density and 2.5A/dm 2nominal cathode current density.
Find in this solution, to form manganese (III) fast, and gained solution can etch ABS plastic and the plastics that can be processed in follow-up plating time produce good sticking together.But, after the time of operation two weeks (this solution of electrolysis 8 hours/day), find that coat is wrinkling from titanium-base, and titanium-base itself dissolves in the solution.
comparative example 4:
To the titanium-base scribbling platinum be comprised at the temperature of 65 DEG C and nominal measure surface-area be 1dm 2electrode immerse 500 milliliters in 12.5M sulfuric acid containing 0.08M manganous sulfate solution in.Negative electrode in this pond is nominal measurement surface-area is 0.1dm 2lead flake.The electric current applying 0.25 ampere, to this pond, obtains 0.25A/dm 2nominal anodic current density and 2.5A/dm 2nominal cathode current density.
Find in this solution, to form manganese (III) fast, and gained solution can etch ABS plastic, and produce good sticking together during the plastics that can be processed in follow-up plating.But, after the time of operation two weeks (this solution of electrolysis 8 hours/day), find that coating is wrinkling from titanium-base, and titanium-base itself dissolves in the solution.
embodiment 5:
To vitreous carbon be comprised at the temperature of 65 DEG C and nominal measure surface-area be 0.125dm 2electrode immerse 100 milliliters in 12.5M sulfuric acid containing 0.08M manganous sulfate solution in.Negative electrode in this pond is nominal measurement surface-area is 0.0125dm 2platinum line sheet.The electric current applying 0.031 ampere, to this pond, obtains 0.25A/dm 2nominal anodic current density and 2.5A/dm 2nominal cathode current density.
Find in this solution, to form manganese (III) fast, and gained solution can etch ABS plastic, and produce good sticking together during the plastics that can be processed in follow-up plating.This electrode is not obviously subject to the impact that electrolysis time extends.
embodiment 6:
The electrode that will comprise weaving carbon fiber sheet (derive from Zoltek company, have the Panex3550KTow of 1.5% epoxy starching) is fixed on by the plastic frame of poly(vinylidene fluoride) (PVDF) construction.At the temperature of 65 DEG C, nominal is measured surface-area is 1dm 2electrode immerse 500 milliliters in 12.5M sulfuric acid containing 0.08M manganous sulfate solution in.Negative electrode in this pond is nominal measurement surface-area is 0.1dm 2lead flake.The electric current applying 0.25 ampere, to this pond, obtains 0.25A/dm 2nominal anodic current density and 2.5A/dm 2nominal cathode current density.
Find in this solution, to form manganese (III) fast, and gained solution can etch ABS plastic, and produce good sticking together during the plastics that can be processed in follow-up plating.This electrode is not obviously subject to the impact that electrolysis time extends.Use this electrode to carry out electrolysis more than two weeks, and detection does not find degraded.The low cost of this material and quick utilizability make it be suitable for many commercial applications.
embodiment 7:
At the temperature of 68 ~ 70 DEG C, will by having 0.4dm 2effective surface area (that is, not calculating electrode back) lead form anode immerse containing 2 liters in 12.5M sulfuric acid containing 0.08M manganous sulfate solution beaker in.Another electrode in this pond is made up of lead electrode, and this lead electrode has and is about 0.04dm 2surface-area.Magnetic stirrer is used to stir this solution, to obtain the stirring of appropriateness in this electrolytical surface.Apply 0.4A/dm 2current density to this anode, and determine the speed of manganese (III) relative to electrolysis time.The sample being diluted this bath by phosphoric acid determines that the amount of manganese (III) is to prevent manganese (III) disproportionation, and uses l ferrous ammonium sulfate solution titration, uses the pentanoic be dissolved in acid as indicator.
Use 0.8A/dm 2with 1.6A/dm 2current density repeat experiment.(that is, the moderate agitation of magnetic stirrer is used), due to efficiency of conversion and at 0.4A/dm under the fluid dynamics condition of experiment 2identical (70%) that obtained is obviously 1.6A/dm in current density 2, oxygenizement is not limited by mass transport.At 3.2A/dm 2further test, and find that efficiency of conversion is down to 42%, and the generation speed of manganese (III) is only than at 1.6A/dm 2what obtained is high by 10%.This shows, under the stirring condition used in this experiment, the overall Limited Current density produced for manganese is about 1.6A/dm 2.This be equivalent to switching rate for the switching rate about four times that can be reached by platinized and titanized anode so high.
The result explanation of these experiments, manganese (III) ion is produced by the electrolysis using manganese (II) ion and use platinum or platinized and titanized anode to operate under low current density in the sulfuric acid of rather high concentration, and by using other anode material various can improve the method further, this other anode material various comprises vitreous carbon, carbon fiber, lead and alloy lead anode.
Moreover compared to etching the etch-rate obtained from chromic acid, the slower etch-rate of the etching based on manganese of the present invention has illustrated and needed to provide pre-treatment step, in order to produce higher sticking together value and make it possible to carry out shorter etching period.
The object of this pre-treatment step is the situation on the surface adjusting plastics to be etched, makes it etch more fast and evenly, causes shorter etching period and better stick together.
The situation using the surface of solvent adjustment ABS plastic is known.But nearest specification is strictly limited in feasibility plate wire using volatile solvent, because they are usually flammable and have health and safety problem (many for genotoxicity and liver can be caused to injure).Therefore, the selection of solvent is limited.
Propylene carbonate is comparatively safe solvent, has good water-soluble, hypotoxicity and low combustible (flash-point is 135 DEG C), and is desirable from health and safety angle.Gamma-butyrolactone is also feasible, but has more toxicity, and is controlled substance in some countries due to its recreational use.
In the present invention, find when the organic hydroxy acids such as the use of propylene carbonate and such as lactic acid, oxyacetic acid or gluconic acid combine, better result can be obtained in conjunction with the described etching solution based on manganese of the application.Propylene carbonate is used alone or uses together with wetting agent provides good sticking together and the etching period shortened, but after etching, activation and follow-up plating, because ABS/PC adulterant has the tendency producing indenture, therefore bad order.In this pretreatment stage, propylene carbonate and these hydroxy acids are combinationally used and can effectively avoid this problem.
Usually, the concentration of propylene carbonate is about 100 to about 500mL/L, and this organic acid concentration is about 100 to about 500mL/L.In addition, service temperature is generally about 20 DEG C to 70 DEG C, and soak time is about 2 to about 10 minutes.
Therefore, the present invention also relates to a kind of pretreatment compositions for plating plastic base in general, comprises gamma-butyrolactone or propylene carbonate, combinationally uses with organic hydroxy acids such as such as lactic acid, oxyacetic acid or gluconic acids.
comparative example 5:
The test piece that formed by the ABS/PC adulterant be made up of 45% polycarbonate is immersed in the solution containing 150mL/L propylene carbonate, soak time and temperature as shown in table 1.After this, clean this plate, and etch in the solution containing 12.5M sulfuric acid and 0.08M manganese, wherein the mn ion of 0.015M has been manganese (III) by electrolytic oxidation.30 minutes are carried out under being etched in the temperature of 68 ~ 70 DEG C.Herein after reason, clean this plate, activate this plate at the upper use standard plating of plastics pre-treatment sequence (illustrating according to technical data, MacDermidD34 palladium activator, MacDermid accelerator and MacDermidJ64 electroless nickel), then electroplate in copper.Check the decorative appearance of this plate, and use Instron tensile testing machine to leave behind settled layer to carry out quantitative adhesion test from this substrate.Obtain to stick together value as shown in table 1.
Table 1. sticks together value
This value of sticking together is quite changeable, and finds stain and indenture in this plated part.Copper coating also has indenture.
embodiment 8:
Repeat the experiment carried out in comparative example 5, difference is to use the preconditioned agent of 88% lactic acid solution comprising 150mL/L propylene carbonate and 250mL/L.The result of these tests is as shown in table 2.
Table 2. sticks together value
Use this preconditioned agent comprising lactic acid, improve the consistence of sticking together.After plating, find that decorative appearance is splendid, and there is no stain and indenture.

Claims (52)

1. an electrolyzer, comprises:
Electrolyte solution, it comprises and is in manganese (III) ion in the solution comprising sulfuric acid and additional acid and manganese (II) ion, and described additional acid is selected from the group be made up of methanesulfonic, methane-disulfonic acid and combination thereof;
Negative electrode, itself and described electrolyte solution contacts; With
Anode, itself and described electrolyte solution contacts.
2. electrolyzer as claimed in claim 1, wherein said solution comprises the sulfuric acid of at least 8M.
3. electrolyzer as claimed in claim 2, wherein said solution comprises the sulfuric acid of at least 12M.
4. electrolyzer as claimed in claim 1, wherein said solution comprises methanesulfonic or the methane-disulfonic acid of about 1M to about 6M.
5. electrolyzer as claimed in claim 1, wherein said solution comprises the sulfuric acid of 9 to 15 moles, and the methanesulfonic of about 1M to about 6M.
6. electrolyzer as claimed in claim 1, wherein said anode comprises the material in the group being selected from and being made up of vitreous carbon, reticulated vitreous carbon, weaving carbon fiber, lead, lead alloy, platinized titanium, platinum, iridium/tantalum pentoxide, niobium, boron doped diamond and one or more combination aforementioned.
7. electrolyzer as claimed in claim 6, wherein said anode comprises lead or lead alloy.
8. electrolyzer as claimed in claim 1, wherein said negative electrode comprises the material in the group being selected from and being made up of platinum, platinized titanium, iridium/tantalum pentoxide, niobium and lead.
9. electrolyzer as claimed in claim 9, wherein said negative electrode comprises lead.
10. electrolyzer as claimed in claim 7, wherein said electrolyzer also comprises the device for monitoring manganese (II) ionic concn in described solution.
11. electrolyzers as claimed in claim 1, the area of wherein said anode is greater than the area of described negative electrode.
12. 1 kinds of electrolyzers, comprise:
Electrolyte solution, comprises manganese (III) ion in the solution being at least one acid and manganese (II) ion;
Negative electrode, itself and described electrolyte solution contacts; With
Anode, itself and described electrolyte solution contacts, wherein said anode comprises the material in the group being selected from and being made up of vitreous carbon, reticulated vitreous carbon, weaving carbon fiber, lead, lead alloy, platinized titanium, platinum, iridium/tantalum pentoxide, niobium, boron doped diamond and one or more combination aforementioned.
Manganese (II) ion electrochemical is oxidized to the method for manganese (III) ion, comprises the following steps by 13. 1 kinds:
Ionogen is provided in electrolyzer, it comprises manganese (II) solion in the solution being at least one acid and additional acid, described additional acid is selected from by methanesulfonic, methane-disulfonic acid and its group formed, and wherein said electrolyzer comprises anode and negative electrode;
Electric current is applied between described anode and described negative electrode; And
Be oxidized described ionogen to form manganese (III) ion, wherein said manganese (III) ion forms metastable state complex compound.
14. methods as claimed in claim 13, wherein said at least one acid comprises sulphuric acid soln.
15. methods as claimed in claim 14, wherein said at least one acid comprises the sulfuric acid that concentration is at least 8M.
16. methods as claimed in claim 15, wherein said ionogen comprises the methanesulfonic of the sulfuric acid of at least 8M and about 1M to about 6M.
17. methods as claimed in claim 13, wherein said anode comprises lead or lead alloy.
18. methods as claimed in claim 17, are included in described solution the step of the accumulation monitoring manganese (III) ion.
19. methods as claimed in claim 18, manganese (II) ion wherein no more than original concentration 50% is oxidized to manganese (III) ion.
20. methods as claimed in claim 19, manganese (II) ion wherein no more than original concentration 25% is oxidized to manganese (III) ion.
21. methods as claimed in claim 18, wherein use redox electrode to monitor the accumulation of described manganese (III) ion, wherein when described manganese (III) ion content reaches the amount of expectation, stop electrolysis.
22. methods as claimed in claim 18, wherein monitor the accumulation of described manganese (III) ion by etching solution described in titration, wherein when described manganese (III) ion content reaches the amount of expectation, stop electrolysis.
23. methods as claimed in claim 13, are included in described electrolyzer and periodically make electric current reverse, prevent Manganse Dioxide from accumulating on described anode thus.
24. methods as claimed in claim 13, also comprise and can plate plastics and described metastable state complex thereof for some time to etch the described step can plating plastics.
25. methods as claimed in claim 24, wherein described plate plastics and described metastable state complex thereof before, the described plastics that plate contact with pretreatment compositions to nurse one's health the described surface appearance can plating plastics, and described pretreatment compositions comprises the solvent selected from the group be made up of propylene carbonate, gamma-butyrolactone and combination thereof.
26. methods as claimed in claim 25, wherein said solvent comprises propylene carbonate.
27. methods as claimed in claim 25, wherein said preprocessing solution also comprises organic hydroxy acids.
28. methods as claimed in claim 27, wherein said organic hydroxy acids is selected from the group be made up of lactic acid, oxyacetic acid, gluconic acid and one or more combination aforementioned.
29. methods as claimed in claim 18, wherein said method also comprises the concentration monitoring manganese (II) ion in described solution.
30. methods as claimed in claim 27, under wherein said pretreatment compositions maintains the temperature of about 20 to about 70 DEG C, and the described plastics that plate contact about 2 to about 10 minutes with described pretreatment compositions.
31. methods as claimed in claim 13, wherein said manganese (II) ion is obtained from the compound selected from the group be made up of manganous sulfate, manganous carbonate and manganous hydroxide.
32. methods as claimed in claim 13, wherein said solution also comprises colloidal silica manganese.
33. methods as claimed in claim 13, the concentration of manganese described in wherein said ionogen (II) ion be about 0.005 mole to saturated.
34. methods as claimed in claim 13, wherein said negative electrode comprises the material selected from the group be made up of platinum, platinized titanium, iridium/tantalum pentoxide, niobium and lead.
35. methods as claimed in claim 34, wherein said negative electrode comprises lead.
36. methods as claimed in claim 34, wherein said negative electrode comprises platinized titanium or platinum.
37. methods as claimed in claim 13, the current density of wherein said anode is about 0.1 to about 0.4A/dm 2.
38. methods as claimed in claim 13, wherein said electrolytical temperature maintains about 30 DEG C to about 80 DEG C.
39. methods as claimed in claim 13, wherein said ionogen does not comprise any permanganate.
40. methods as claimed in claim 24, wherein said plastic packets of plating is containing acrylonitrile-butadiene-styrene (ABS) or acrylonitrile-butadiene-styrene (ABS)/polycarbonate.
41. 1 kinds of methods etching plastic components, described method comprise by described plastic components with comprise manganese (III) ion and contact with the solution of at least one acid.
42. methods as claimed in claim 41, wherein said at least one acid comprises sulfuric acid.
43. methods as claimed in claim 42, wherein said at least one acid also comprises methanesulfonic or methane-disulfonic acid.
44. methods as claimed in claim 43, wherein said acid solution comprises the methanesulfonic of the sulfuric acid of at least 8M and about 1M to about 6M.
45. methods as claimed in claim 41, wherein said plastic components comprises acrylonitrile/butadiene/styrene.
46. methods as claimed in claim 43, wherein said manganese (III) ion is produced in described solution by the electrolytic oxidation of manganese (II).
47. methods as claimed in claim 46, wherein said electrolytic oxidation occurs in the anode in described solution, and described anode comprises vitreous carbon, reticulated vitreous carbon, weaving carbon fiber, lead or lead alloy.
48. methods as claimed in claim 41, wherein described plastic components with comprise before manganese (III) ion contacts with the described solution of at least one acid, described plastic components contacts the surface appearance nursing one's health described plastic components with pretreatment compositions, described pretreatment compositions comprises the solvent selected from the group be made up of propylene carbonate, gamma-butyrolactone and combination thereof.
49. methods as claimed in claim 48, wherein said solvent comprises propylene carbonate.
50. methods as claimed in claim 48, wherein said preprocessing solution also comprises organic hydroxy acids.
51. methods as claimed in claim 50, wherein said organic hydroxy acids is selected from the group be made up of lactic acid, oxyacetic acid, gluconic acid and one or more combination aforementioned.
52. methods as claimed in claim 50, wherein said pretreatment compositions comprises the propylene carbonate of about 100 to 500mL/L and the described organic hydroxy acids of about 100 to 500mL/L.
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