CN1740401B - An energy enhanced process for treating a conductive surface and products formed thereby - Google Patents
An energy enhanced process for treating a conductive surface and products formed thereby Download PDFInfo
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- CN1740401B CN1740401B CN 200510090986 CN200510090986A CN1740401B CN 1740401 B CN1740401 B CN 1740401B CN 200510090986 CN200510090986 CN 200510090986 CN 200510090986 A CN200510090986 A CN 200510090986A CN 1740401 B CN1740401 B CN 1740401B
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Abstract
The disclosure relates to a process for forming a deposit on the surface of a metallic or conductive surface. The process employs an energy enhanced process to deposit a silicate containing coating or film upon a metallic or conductive surface.
Description
The subject requirement applying date of this paper is February 1 calendar year 2001, application number is 09/775, the rights and interests of 072 U.S. Patent application, this application is to be on March 22nd, 2000 applying date, application number is 09/532,982 part continues, and the latter is to be on August 6th, 1999 applying date, application number is 09/369,780 (present U.S. Patent number is U.S.6,153,080) part continues, 09/369, No. 780 application is to be on July 24th, 1998 applying date, application number is 09/122,002 part continuation, 09/122, No. 002 application is to be on January 30th, 1998 applying date, by people such as Robert L.Heimann propose exercise question for " being used to form the electrolysis process of mineral " 09/016,250 (present U.S. Patent number is 6,149,794) part continues, and whole openly texts of above-mentioned application are incorporated this paper into as a reference at this.That subject requirement of the present invention on January 31st, 1997 proposes, provisional application number is 60/036, rights and interests under the 35U.S.C.111 of 024 U.S. Patent application (a), 35 U.S.C.1198 (e) and the 35U.S.C.120 and on May 2nd, 1997 propose, exercise question is the rights and interests of 60/045, No. 446 application of " non-equilibrium enhanced mineral deposition method ".The open text of previously presented these provisional application is incorporated herein by reference at this.
Invention field
The application relates to a kind of sedimental processing method that forms on metallic surface or conductive surface.This processing method utilizes coating or the film that electrolysis process will for example contain mineral to deposit on the surface of metal, that contain metal or conduction.
Background of invention
In electric clean operation, utilized silicate to clean steel, tin in other surface already.The electricity cleaning is usually as the cleaning before the electroplating operations.Described " utilizing silicate as the sanitising agent in the sheet tin preparation " this piece article in the plating of publishing in February, 1966 by L.J.Brown, the document is incorporated herein by reference at this.
At United States Patent (USP) U.S.3,658,662 (Casson, people such as Jr.) and United Kingdom U.K.498 disclose in 485 by utilizing the anode process electrolysis to form the processing method of protective layer or film, and these two pieces of patents are incorporated herein by reference at this.
On October 4th, 1994 issue, exercise question is the United States Patent (USP) U.S.5 of the Riffe of " being used to avoid metal construction corroding method and device ", 352, described in 342 that electromotive force is applied on the zinc solvent that contains coating, this patent is incorporated herein by reference at this.
Summary of the invention
The present invention has solved the several problems relevant with conventional practice by being provided at the anode process that forms protective layer (for example protective layer is in the scope that approximately about 2,500 dusts of 100-are thick) in substrate metal or that contain metal.Usually can following enforcement anode process: the substrate contact (for example dipping) that will have conductive surface be to bath that contains silicate or medium in, and bath is interior and make substrate as negative electrode wherein electric current to be introduced (for example by).
Processing method of the present invention can form the layer mineral that comprises an amorphous matrix, and this matrix is surrounded or the suprabasil metal silicate crystal of fusion.The characteristic of layer mineral has been described in following common trial of listing and the common patent application of transferring the possession of in further detail.
The conductive surface that utilizes processing method of the present invention to handle (for example forming layer mineral) in other characteristic, can have higher erosion resistance, increased resistance, thermotolerance, flexible, anti-stress split corrodibility, to the adhesivity of finish paint.Surface treated has bigger erosion resistance (for example ASTM B-117) than conventional trivalent or hexavalent chromate system in other beneficial characteristics.Processing method of the present invention can provide the zine plate goods of the anti-red embroidery of the anti-white embroidery of about at least 72 hours (and usually greater than about 96 hours) with ASTM B-117 and about at least 168 hours (and usually greater than about 400 hours).Can provide erosion resistance by adopting rinsing and/or applying at least a finish paint.
Processing method of the present invention is owing to need not to form for example layer mineral of anti-corrosion layer with multiple solvent or the system that contains solvent, and has significant improvement than ordinary method.Compare with ordinary method, processing method of the present invention need not solvent basically.And " need not solvent basically " be meant, exists in electrolytic environments and be less than about 5wt%, is less than the volatile organic compounds (V.O.C.s) of about 1wt% usually.
Processing method of the present invention contains chromic salt and/or phosphatic compound (and for example waste treatment of the attached work of discharging, the worker of these compounds of use in other hostile environment influence factor are exposed to the sun) owing to reduced (if not eliminating), also has significant improvement than ordinary method.Though processing method of the present invention can be used to strengthen chromic acidization or phosphorylation surface, processing method of the present invention can be with more the useful surface of environment being replaced these surfaces.Therefore, processing method of the present invention " need not chromic salt " and " need not phosphoric acid salt basically " basically, thereby makes product also be substantially free of chromic salt (sexavalence and trivalent) and be substantially free of phosphoric acid salt.Processing method of the present invention also is substantially free of heavy metal for example chromium, lead, cadmium, cobalt, the palladium in other material.Basically the meaning that need not chromic salt, need not phosphoric acid salt and need not heavy metal basically basically is to have chromic salt, phosphoric acid salt and/or the heavy metal that is less than 5wt%, is typically about 0wt% in the processing method that is used for preparing product or the finished product.Except having exempted the technology that contains chromic salt, method of the present invention is compared with the chromic salt coating method of routine, has also formed the bigger thermotolerance, the flexible coating that have in other characteristic.This improved thermotolerance has been widened processing range, can after forming coating of the present invention, implement these technologies for example the thermofixation face in other technology be coated with method, stamping method/moulding method, riveting.
Compare with the electric cleaning procedure of routine, the present invention forms in substrate in the cathode technique of layer mineral and adopts silicate.Conventional electric cleaning procedure is managed to avoid to form and is contained the product of oxide compound (for example greenalite), and the present invention relates to a kind of method that is used to form the product that contains silicate (for example mineral).
The cross reference and the patent application of relevant patent
Theme of the present invention relates to common trial and common WO 98/33960, the non-interim U.S. Patent Application Serial of transferring the possession of 08/850,323 (present U.S. Patent number is 6,165,257); Respectively at 08/850 of on May 2nd, 1997 and proposition on January 30th, 1998,586 (present U.S. Patent number is 6,143,420) and 09/016,853 (unauthorizeds), and people such as Robert L.Heimann on January 31st, 1997 propose 08/791,337 (present U.S. Patent number is 5,938,976), 08/791, No. 337 application is people such as Robert L.Heimann, exercise question is 08/634 of " the corrosion-resistant Laemmli buffer system Laemmli that is used for metal product ", the part of 215 (applying date is on April 18th, 1996) number application continues, and 08/634, No. 215 application is again people such as Heimann, the part of the non-interim U.S. Patent Application Serial 08/476,271 (applying date be nineteen ninety-five June 7 day) corresponding with WO 96/12770 continues, 08/476, (applying date is on October 21st, 1994 to No. 271 interim U.S. Patent Application Serial 08/327,438 of application right and wrong, and present U.S. Patent number is 5,714,093) part continues.
It is that on January 30th, 1998, exercise question are the non-interim U.S. Patent Application Serial Number 09/016,849 (agent certificate EL004RH-1) of " corrosion protection coating " that theme of the present invention relates to the applying date.It is on January 30th, 1998 that theme of the present invention also relates to the applying date, (present U.S. Patent number is 6 to exercise question for " aqueous gelatinous composition and uses thereof ", 033,495) non-interim U.S. Patent Application Serial Number 09/016,462 (agent certificate EL005NM-1).Above-mentioned these patents, patent application and publication are incorporated herein by reference at this.
The accompanying drawing summary
Fig. 1 is circuit and the schematic representation of apparatus that is used to implement one aspect of the present invention.
Fig. 2 is the synoptic diagram that adopts a technology of electrolysis process of the present invention.
Detailed Description Of The Invention
The present invention relates to a kind of metal or conductive surface on deposition or form the processing method on the useful surface of one deck (coating or the film that for example contain mineral).This processing method adopt silicate medium (for example containing soluble mineral component or its precursor) and utilize electric Enhancement Method handle conductive surface (for example metal or conductive surface on obtain to contain the coating or the film of mineral)." coating that contains mineral ", " mineralising film " or the meaning of " mineral " are meant, quite thin coating or the film that forms on metal or conductive surface, wherein at least a portion coating or film comprise that at least a mineral that contain metal for example surround or the amorphous phase or the matrix of fusion crystal (comprising zinc silicate).Mineral and the mineral that contain limit in above-mentioned common trial and common patent of transferring the possession of and patent application to some extent, and are incorporated herein by reference at this.The meaning of " electrolysis " or " galvanic deposit " or " electricity strengthens " is meant that by electric current being flowed into or contacting the environment that produces with conductive substrates (perhaps having conductive surface) simultaneously by the medium that contains silicate, wherein substrate is as negative electrode.The meaning of " metal that contains ", " metal " or " metal " is meant, thin slice in other structure, formed article, fiber, rod, particle, continuous length (for example coil and metal wire), be coated with metallic surface, and these structures are with at least a metal and comprise that a kind of alloy of metal is a basal component, that included this metal has a natural generation or chemistry, machinery or heat modification surface.Usually will comprise a film or a thin layer in other structure on the surface of natural generation on the metal, this film or thin layer contain at least a oxide compound, oxyhydroxide, carbonate, vitriol, muriate.Can remove or the surface of this natural generation of modification by utilizing processing method of the present invention.
Can obtain electrolytic environments in any suitable manner, the coating that these modes are included in dipping substrate in the alternate manner, will contain silicate is applied in the substrate, applies electric current then.Can determine to obtain the preferred method of this environment according to the size of foundation base in known other parameter in the electrodeposition, electrodeposition time, the voltage that applied.Can strengthen the efficient of electrolytic environments by the energy that is provided at ultrasonic, laser in other form, UV-light, RF, IR form.Processing method of the present invention can segmentation or operate continuously.
The medium that contains silicate can be fluid bath, gel, the spraying in other method, so that substrate is contacted with the silicate medium.The example of silicate medium is included in the bath that contains at least a silicate in other method, contains the gel of at least a silicate and a kind of thickening material.This medium can comprise a kind of bath, and this bath is included in the compound of at least a potassium silicate, Calucium Silicate powder, lithium silicate, water glass, release silicate part or kind in other silicate.This bath can comprise any suitable polar support for example water in other carrier, ethanol, ether.Usually, this bath comprises water glass and deionized water and optional at least a doping agent.Usually, this at least a doping agent is water miscible or can be distributed in the water-bearing media.
The medium that contains silicate generally has the alkaline pH value.Usually, the scope of pH value is about greater than 9 in-about 13 the scope, generally in the scope of about 10-about 11.This medium is normally aqueous and comprise at least a water-soluble or water dispersible silicate, and the amount of silicate is typically about 3-15wt.% in the scope greater than the about 40wt.% of 0-, be generally about 10wt.%.This silicate medium also comprises at least a water dispersible or solubility doping agent.The medium that contains silicate does not comprise heavy metal, chromic salt and/or phosphoric acid salt usually basically.
Electrolytic environments can prior to and/or follow conventional back well known in the art and/or preconditioning technique, such as the cleaning in other treatment process or rinsing (for example dipping/spray in treatment solution), sound wave clean, two counter-current cascade is mobile; Alkalescence or acidic treatment.By adopting the appropriate postprocessing technology, can improve the adhesivity of solubility in other characteristic of the substrate surface that forms by method of the present invention, erosion resistance (for example when processing contains zinc surperficial, having reduced forming of white rust), closure and/or finish paint.If necessary, can be with silane, epoxy, latex, fluoropolymer, vinylformic acid, titanate, zincate, the carbonate in other coating for example, sealing, rinsing and/or face are coated with this aftertreatment surface.
In one aspect of the invention, pre-treatment comprises pending substrate is exposed at least a acid in other compound, the oxygenant.Adopting pre-treatment is in order to have the following advantage in other benefit: remove excessive oxide compound or dirt, make surperficial equi-potential so that the mineralising of carrying out is thereafter handled, this surface is changed into the mineral precursor.The ordinary method that is used for the acid treatment metallic surface is at ASM, and the Surface Engineering of Vol.5 (1994) and U.S.6 describe in 096,650 to some extent, and these two pieces of documents are incorporated herein by reference at this.
In one aspect of the invention, aftertreatment comprises substrate is exposed at least a carbonate source or its precursor.The example of carbonate comprises a member at least in the combination that is made of following material: gasiform carbonic acid gas, Quilonum Retard, lithium bicarbonate, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, rubidium carbonate, rubidium bicarbonate, acid rubidium carbonate, cesium carbonate, volatile salt, bicarbonate of ammonia, ammonium carbamate and ammonium zirconyl carbonate.Usually, carbon source is water miscible.When adopting a kind of carbonate precursor (for example carbonic acid gas), this precursor is by a kind of liquid (comprising the medium that contains silicate) and be immersed in substrate in this liquid.At U.S.2, an a kind of specific example of appropriate postprocessing method is disclosed in 462,763, the document is incorporated herein by reference at this.Another specific example of aftertreatment comprises surface treated is exposed to by at the distilled water (Bacote that is provided by Magnesium Elektron Corp for example
) in dilution ammonium zirconyl carbonate (1: 4) and in the solution that obtains.If necessary, can carry out face to the surface of this aftertreatment and be coated with (for example aqueous or aqueous finish paint).
In another aspect of this invention, aftertreatment comprises this surface of heating.Usually heat is enough to enrichment surface of the present invention, but can disadvantageous effect not arranged to the physical properties of following metal base.Can be such as heating under the environment that contains nitrogen in other gas under atmospheric condition.If necessary, the heating before, surface of the present invention is contacted with the solution that contains a kind of material, this material when temperature raises can with this surface reaction.
In another aspect of this invention, aftertreatment comprises substrate is exposed in the source that comprises at least a acid source or its precursor.The example of suitable acid source comprises a member at least of selecting in the combination of the following material formation from other acid source of at least a characteristic that can effectively improve the metallic surface of handling: carbonic acid, oxalic acid, lactic acid, oxysuccinic acid, tartrate that phosphoric acid, hydrochloric acid, molybdic acid, silicic acid, citric acid, nitric acid, hydroxyl replace.A member at least of selecting in the combination that constitutes by the following material that adopts from other material, improve the pH value of acid aftertreatment: two generation ammonium citrate (can obtain from commercial, commodity are called Citrosol
#503 and Multiprep
), fluoride salt (for example fluoram), fluoroboric acid, silicofluoric acid.Utilize the acid aftertreatment to activate this surface, improve the efficient that rinsing, encapsulant and/or face be coated with (for example the erosion resistance of surface treated is improved whereby improving corrodibility between surface and the encapsulant with being activated before encapsulant contacts in the surface) whereby.Usually, acid source be water miscible and consumption up to about 5wt.%, generally in the scope of the about about 2wt.% of 1-.
In another aspect of this invention, aftertreatment comprises the surface that utilizes processing method of the present invention to handle is contacted with a kind of rinsing liquid.The meaning of " rinsing " is meant, article or surface treated are sprayed, dipping bath, flood or it is exposed in the rinsing liquid, so that influence the characteristic on handled surface.For example, will utilize the surface impregnation of processing method processing of the present invention in the bath that comprises at least a rinsing liquid.In some cases, this rinsing liquid and at least a portion surface treated take place to interact or reaction.Also can be coated with, add dyestuff, lubricant and wax, come the surface of modification institute rinsing by multiple rinsing, heating, the face in other technology.The example of used suitable compound comprises a member at least of selecting in the combination that the following material from other material constitutes in the rinsing: the silicon-dioxide of titanate, titanium chloride, tin chloride, zirconate, acetic acid zirconium, basic zirconium chloride, fluorochemical (for example Calcium Fluoride (Fluorspan), Tin tetrafluoride., titanium fluoride, Zirconium tetrafluoride), copper compound, ammonium silicofluoride, metal treatment (Ludox for example
)/nitrate (for example aluminum nitrate), vitriol (for example sal epsom, sodium sulfate, zinc sulfate and copper sulfate), lithium compound (for example Lithium Acetate, Quilonum Retard, Lithium Citrate de, lithium metaborate, lithium vanadate, lithium tungstate).Rinsing liquid also comprises at least a organic compound for example vinylacrylic acid, fluorine-containing tensio-active agent, the polyethylene wax in other material.The example of commercial available rinsing liquid comprises a member at least of selecting from the combination that following material constitutes: other material is (by the Magni
The thermosetting paint that Group provides) Aqualac in
(aqueous solution that contains urethanum), W86
, W87
, B37
, T01
, E10
, the JS2030S in other material (rinsing liquid that contains water glass that provides by MacDermidIncorporated), JS2040I (the still rinsing liquid that contains molybdenum that provides by MacDermid Incorporated), EnSeal
C-23 (the acrylic coating that provides by Enthone), EnSeal
C-26, Enthone
C-40 (pigmented coating that provides by Enthone), Microseal
, Paraclene
99 (rinsing liquids that contain chromic salt), EcoTri
(silicate/polymkeric substance rinsing liquid), MCI Pius OS (providing) by MetalCoatings International.A kind of special rinsing liquid comprises the urethanum of water, water-dispersion and at least a silicate (for example common U.S.5 that transfers the possession of, disclosed in 871,668, this patent is incorporated herein by reference at this).Though it is purified that rinsing liquid can adopt, usually the rinsing liquid solubilized, dilute or be dispersed in another medium (for example water, the organic solvent in other medium).Though the amount of used rinsing liquid depends on needed result, rinsing liquid accounts for the about 50wt.% of about 0.1wt.%-in the rinsing liquid medium usually.This rinsing liquid can repeatedly be used, and if necessary, can heat.
The metallic surface is meant metal or metallic object and has the nonmetallic of adherent metal or conductive layer or the device of conduction.Though can utilize processing method of the present invention to handle any suitable surface, the example of suitable metallic surface comprises a member at least of selecting from the combination that following material constitutes: the alloy of the galvanizing surface in other material, sherardizing galvanizing surface, zinc, iron, steel, brass, copper, nickel, tin, aluminium, lead, cadmium, magnesium and these metals is zinc-nickel alloy, tin-zinc alloy, zinc-cobalt alloy, zinc-iron alloys for example.If necessary, can have at least one with the nonconductive matrix on the surface of electro-conductive material (for example metal polymeric object in other material or thin slice, be coated with or be wrapped in intrametallic stupalith) coating at the bottom of on form layer mineral.The example of metal-containing polymer comprises a member at least of selecting from the combination that following material constitutes: (phenolic), the nylon of the polycarbonate in other material, acronitrile-butadiene-styrene (ABS), rubber, siloxanes, phenol, PVC, polyimide, melamine, polyethylene, polypropylene, vinylformic acid, fluorocarbon, polysulfones, polyphenylene, poly-acetic ester, polystyrene, epoxy.Conductive surface also can comprise carbon or graphite and conductive polymers (for example polyaniline).
The metallic surface can have size and the fiber in structure example such as other kind, coil, thin slice (comprising the porous sound absorbing plate), short tangent line, draw line or steel hawser/rope, metal strip, coupling device (for example hydraulic hose coupling), fiber, particle, fastener (comprising industry and family expenses hardware), anchor clamps, nut, bolt, rivet, washer, cooling rib, pressing, powder metal goods in a big way.The determinant attributes that is used for the processing method of the present invention of process metal surfaces depends on the ability on electric current/energy contacting metal surface.That is to say that similar with the electroplating technology of routine, mineral surface is difficult to be applied on the metallic surface that limits hollow area or slit.By adopting conformal anode can overcome this difficulty.
Processing method of the present invention produces the flexible surface that can stand secondary processes (for example being used in other technology rivets, the flow of metal of forging, crimping) and continue to provide antiseptic property.This is opposite with general sanitas (for example chromic salt), and general sanitas can cause it to break when lower floor's shaping surface.If necessary, can be before secondary processes, face is coated with the surface that (for example using the heat curing-type epoxy) formed by processing method of the present invention.The goods of handling according to processing method of the present invention have kept the functionality of its required erosion resistance in numerous character, clagging, component after face is coated with and is exposed in the secondary processes.
The surface property that the surface that processing method of the present invention provides can strengthen metal or conductive surface is split corrodibility (for example stainless steel), hardness, thermotolerance of oxidation-resistance, the stress of erosion resistance, carbon (for example fiber) for example, improved the bonding strength in the matrix material, dielectric layer is provided, has improved the erosion resistance of printed wiring/wiring board and decorative metal finished product and reduced the electroconductibility of conductive polymers surface (being included in the application in the sandwich-like material).
Mineral coating also can influence the electricity and the magnetic properties on surface.That is to say that mineral coating makes surface treated have resistive or insulativity.Owing to have a non-conductive surface, the electro-galvanizing that the goods that therefore have thin layer of the present invention can reduce in (eliminating if having) device corrodes, and wherein electric current is with relevant such as the bridge in other goods, Corrosion of Pipeline.
In one aspect of the invention, utilize processing method of the present invention to improve to contain the resistance to fracture and the oxidation-resistance of aluminium, copper or plumbous substrate.For example, be specifically designed to plumbous perishable in the battery production, thereby cause breaking for example intergranular corrosion.Utilize processing method of the present invention can promote the grain growing at the bottom of aluminium, copper and the lead base and reduce the influence of surface imperfection.Need not with any theory or explain to combine, it is believed that the crystalline network of the layer mineral that forms according to processing method of the present invention can be partially polymerized silicate in these three kinds of substrates.But these lattice fusion pyrosilicate structures or chain silicate (for example pyroxene).Partially polymerized lattice silicate has the structural rigidity of not embrittlement.In order to obtain stable partially polymerized lattice, metallic cation has preferably occupied lattice, so that charge stability is provided.Aluminium substitution silicon has unique ability that occupies octahedral site or tetrahedral site.Trivalent aluminium needs extra metallic cation to replace tetravalence silicon.In using plumbous situation, extra positively charged ion can comprise lead.
In one aspect of the invention, by placing sodium silicate aqueous solution to carry out electropaining cloth electrolytic galvanized sheet (for example zinc surface).After placing in the silicate solutions, deposit mineral coating or the film that contains silicate by adopting quite low voltage potential (for example having about 24 volts of about 1-) and low current according to required current density.In the scope of current density under 12 volts the constant voltage at the about about 0.1A/in2 of 0.7A/in2-.Usually, discharge hydrogen, and discharge oxygen at anode at work piece/negative electrode.
In one aspect of the invention, as anode, electricity converts negative electrode to these work piece then at first.By pulsed voltage, can be on-the-spot (with the electrolytic mediator effect before) these work piece of pre-treatment.Pulse also can increase the thickness of the film that forms or layer on work piece.If necessary, doping agent (for example positively charged ion) can be present in the ionogen and by carrying out pulse before mineralising or after the mineralising and deposits from the teeth outwards.
In another aspect of this invention, metallic surface (for example alloy of zinc, aluminium, magnesium, steel, lead and these metals) can randomly carry out pre-treatment.The meaning of " pre-treatment " is meant, regulate the segmentation or the continuous processing of metallic surface, to clean and to regulate this surface, thereby the coating that is easy to for example to be contained mineral or silicate is accepted, and processing method of the present invention can be used as a step in the continuous processing for preparing corrosion resistant rolling steel.This pre-treatment is the coefficient result of expection functionality of the metallic surface and the coating/thin film that contains mineral that will form on this surface.Suitable pretreated example comprises at least a cleaning method for example ultrasonic clean, activation, heating, degreasing, acidleach, deoxidation, the processing of spray granulated glass sphere, sandblasting and rinsing.A kind of suitable steel pretreatment technology comprises:
1) in 3: 1 diluents of Metal Prep 79 (Parker Amchem), flooded 2 minutes,
2) secondary deionized water rinsing,
3) in the sodium hydroxide solution of pH14, flooded for 10 seconds,
4) remove the excessive solution line space air dry of going forward side by side,
5) in 50% superoxol, flooded 5 minutes,
6) remove the excessive solution line space air dry of going forward side by side.
In another aspect of this invention, by the anode clean surface pre-treatment is carried out in this metallic surface.By finishing such cleaning in the medium that work piece or substrate is impregnated into the silicate that contains in other sanitising agent, oxyhydroxide, phosphoric acid salt, carbonate.By with work piece as the anode in the DC battery and electric current is remained in the scope of the about 150A/ft2 of about 10A/ft2-, this technology can produce oxygen.Oxygen stirs the surface of work piece, the surface of simultaneous oxidation substrate.Also but mechanical agitation should the surface by utilizing conventional vibration device.If necessary, introduce foaming, the immersion that these gases for example are used for adding the alternate manner of gas, can increase the amount of in the process that layer mineral forms existing oxygen or other gas by physics.
Aspect further pre-treatment of the present invention, work piece are exposed to as in the anodic silicate medium of the present invention, clean these work piece (for example removing the compound of natural generation) whereby.Make these work piece convert negative electrode to then and carry out pre-treatment according to method of the present invention.
In still another aspect of the invention, make silicate medium modified, so that comprise at least a dopant material.The amount of doping agent changes according to the character of doping agent and required result.Usually, the amount of doping agent is in the scope of about about 5wt.% of 0.001wt.%-(perhaps higher, as long as ionogen is not had disadvantageous effect).The example of suitable doping agent comprises a member at least of selecting from the combination that following material constitutes: the water soluble salt of following these elements, oxide compound and precursor: tungsten, molybdenum, chromium, titanium (titanate), zircon, vanadium, phosphorus, aluminium (aluminate), iron (for example iron(ic) chloride), boron (borate), bismuth, gallium, tellurium, germanium, antimony, niobium (being also referred to as niobium (Columbium)), magnesium and manganese, sulphur, zirconium (zirconate), also have the mixture of these materials, and often comprise the salt and the oxide compound of aluminium and iron.This doping agent comprises a kind of in the following material at least: molybdic acid, hydrofluotitanic acid and its esters (for example hydrofluorination titanium, hydrofluotitanic acid ammonia, silicofluoric acid ammonia and titanium sodium fluoride); Fluorine zirconic acid and its esters (H for example
2ZrF
6, (NH)
2ZrF
6And Na
2ZrF
6).Or this doping agent comprises for example precursor (such as zinc) of the polymkeric substance, PTFE, boron nitride, silicon carbide, silicon nitride, aluminium nitride, titanium carbide, diamond, TiB2, tungsten nitride, metal oxide (for example cerium oxide), powder metal and the metal that transport of electrophoresis of at least a material of water-insoluble basically.
Above-mentioned doping agent can be used for increasing the formation speed of layer mineral, the chemistry that improves the final layer that forms and/or physical properties, is used as the thinner of the medium that contains ionogen or silicate.The example of these doping agents is molysite (iron protochloride, ferrous sulfate, Iron nitrate), aluminum fluoride, the silicofluoride (K for example in other metals and the halogen source
2SiF
6), (for example potassium fluoroaluminate is such as K for fluoaluminate
2ALF
5-H
2O), the mixture of these materials.Pre-treatment step that can be before galvanic deposit, the post-processing step after the galvanic deposit (for example rinsing) and/or contact (if silicate with doping agent (for example one or more water soluble dopants) formation stabilizing solution) by the electrolysis that changes dopant solution and silicate solutions, and dopant material is incorporated on metal or the conductive surface.Exist doping agent can cause forming special surface on metal or conductive surface in the electrolyte solution, the sodium silicate aqueous solution that for example contains aluminate can be used to form the thin layer of the oxide compound that contains silicon and aluminium.That is to say, at least a doping agent (for example zinc) can with at least a siliceous material (for example mineral) common deposited in substrate.
And, can improve above-mentioned purificant by at least a doping agent of fusion.This doping agent can be had an effect with surface treated or react.If necessary, this doping agent can be dispersed in the suitable medium (for example water) and be used as purificant.
Can improve the silicate medium by adding the polymkeric substance that entry/polar support disperses or dissolves, and in some cases, electric depositing solution itself is exactly the flowable gel with predetermined viscosity.If you are using, the amount of the material of polymkeric substance or water-dispersion is usually in the scope of about about 10wt.% of 0wt.%-.The examples of material that can be used for polymkeric substance in the silicate medium or water-dispersion comprises a member at least of selecting from the combination that following material constitutes: acrylic copolymer (commercial provide, commodity are called Carbopol), Natvosol, clay (for example bentonite), pyrogenic silica, comprise the solution (being provided by MacDermid as JS2030S commercial) of water glass.Suitable composition is to comprise the Carbopol EZ-2 (BF Goodrich) of about 3wt.%N-level sodium silicate solution (PQ Corp), optional about 0.5wt.%, the about aqueous composition of the mixture of the pyrogenic silica of the about 10wt.% of 5wt.%-and these materials.In addition, the polymkeric substance that used water is disperseed for example polyurethane is filled aqueous silicate solutions, so that galvanic deposit mineral-polymer composition coating.By utilize can with the anode material of mineral negatively charged ion and/or one or more doping agent common deposited as ion source, also can improve the characteristic of electric depositing solution.Doping agent can be used for providing the additional thickness of galvanic deposit layer mineral.
By adding also correctability silicate medium of at least a thinner or ionogen.The example of suitable diluent comprises a member at least of selecting from the combination that following material constitutes: sodium sulfate, tensio-active agent, defoamer, colorant/dyestuff.This thinner (for example sodium sulfate) can be used to improve the electroconductibility of bath, the effect that reduces to enter the pollutent in the silicate medium, minimizing bath bubble.When thinner was used as defoamer, used electrolytical amount was less than 5wt.% usually, for example in the scope of about about 2wt.% of 1-.The amount of the thinner of influence bath or electrolytical electroconductibility is generally the about 20wt.% of about 0wt.%-.
What below list is the parameter that is used to repair processing method of the present invention in order to obtain the required coating that contains mineral:
1, voltage
2, current density
3, device or groove
4, depositing time
5, sequencing electric current and the voltage change in the technological process
6, the concentration of silicate solutions
7, the kind of the cloudy example in the solution and concentration
8, the kind of the positive example in the solution and concentration
9, anodic composition/surface-area
10, the composition/surface-area of negative electrode
11, temperature
12, pressure
13, the kind of tensio-active agent and concentration
The concrete scope of above parameter depends on pending substrate and estimates sedimentary composition.Usually, the temperature of electrolyte bath is in the scope of about about 95C of 25-(for example about 75C), voltage is about 6-24 volt, the concentration of electrolyte solution is the silicate of the about 15wt.% of about 5wt.%-, current density is in about 0.025A/in2 and the scope greater than 0.60A/in2, with be about 10-about 50 minutes seconds and be typically about 1-about 15 minutes that the ratio of anode and cathodic surface area is about 0.5: about 2: 1 of 1-electrolytical duration of contact.1st, 2,7 and 8 chemistry and physical propertys for the finishing coating are effective especially.That is to say, the 1st and 2 thickness that can influence depositing time and coating, and the 7th and 8 can be used to introduce the doping agent of giving the required chemical property of coating.Dissimilar zwitterions can comprise a member at least of selecting from the combination that following material constitutes: the mixture of first family metal, second family metal, transition and rare-earth oxide, oxide anion (for example molybdic acid, phosphoric acid, metatitanic acid, boron nitride, silicon carbide, aluminium nitride, silicon nitride), these materials.
Typical processing condition will be provided at the negative electrode release hydrogen, discharge the environment of oxygen at anode.Need not in conjunction with any theory or explanation, it is believed that the release of hydrogen can make pending surface p H quite high.It is believed that also oxygen reduces or disappear environment and high pH can make processed substrate surface have an effect or react.It is believed that also zinc can be used as the barrier of hydrogen, reduce (if not eliminating) whereby and implement the hydrogen embrittlement that processing method of the present invention caused.
Can improve processing method of the present invention by being applied in relevant with electroplating technology traditionally apparatus and method.These method examples comprise pulse plating, horizontal electroplating system, rotating cylinder, tooth bar, ionogen properties-correcting agent is joined in the medium that contains silicate, use the film with bath.
Can improve processing method of the present invention by changing the anodic composition.Suitable anodic example comprises graphite, platinum, zinc, iron, steel, iridium oxide, beryllium oxide, tantalum, niobium, titanium, nickel, Monel
The alloy of alloy, palladium, these materials.Anode can be included in first material of lining on the niobium screen cloth of the second for example platinized titanium or platinum lining.This anode can have any suitable structure example as being close to the screen cloth of rotating cylinder electroplating system.In some situation, anode (for example iron or nickel) can be discharged into ion in the electrolyte bath that can be admixed in the layer mineral.Usually, the anode ion of ppm level concentration is enough to influence the composition of layer mineral.The anode of size constancy can adopt platinum lining or galvanized niobium so if desired.In the situation that the anode of size constancy need clean, in most cases, can utilize sodium hydroxide solution cleaning anode.By utilizing heat and/or electric current can strengthen the anodic cleaning.
Can in any suitable device, implement processing method of the present invention.The example of appropriate device comprises that plating, horizontal plating, continuous length are electroplated, brushed to tooth bar and the rotating cylinder in conventional other devices that use in the plated metal.To understand some aspect of processing method of the present invention better by the reference accompanying drawing.Referring now to Fig. 2, Fig. 2 is the synoptic diagram of a technology that adopts an aspect of electrolysis process of the present invention.In partial or continuous technological process, implement technology shown in Figure 2.Can utilize acid (for example hydrochloric acid or citric acid) cleaner that pending product with metallic surface (or work piece) (if necessary) is arranged, water carries out rinsing and with alkali (for example sodium hydroxide) rinsing, uses water rinse more then.If necessary, can repeat this cleaning and rinse step.If necessary, the ultrasonic clean device of available routine replaces acid/alkali cleaning.Then these work piece are carried out electrolysis process of the present invention, at least a portion work piece surface, form layer mineral whereby.Take out these work piece from electrolytic environments, drying is also used water rinse then, can remove the thin layer that for example comprises such as silicon-dioxide and/or yellow soda ash by rinsing.
Rinsing work piece no matter whether, processing method of the present invention also can provide improved erosion resistance without chromic salt (sexavalence or trivalent).When handling zinc surface with processing method of the present invention, can reduce the thickness (or total amount) of zinc, obtain (if not having improved words) erosion resistance of equivalence simultaneously.For example, when steel work is exposed about 30 minutes of about 2.5-in galvanized environment, in technology of the present invention, expose about 2.5-then in the time of about 30 minutes, white rust at first occurs about 24 hours-about 120 hours (when testing), and occurred the red rust breakage in about 800 hours at about 100-according to ASTM B-117.As a result, processing method of the present invention can be repaired the consumption of zinc, to reach required corrosion-resistant level.If necessary, can further improve erosion resistance by applying at least a finish paint.
Compare with the chromic salt technology (sexavalence or trivalent) of routine, processing method of the present invention also provides improved torque tensile property.Wilson-Garner M10 handles with conventional zinc chromate and chrome yellow acid, and handles according to processing method of the present invention.With about 20, about 42,300 newton's of 000-power, test the torque tension force of these bolts according to testing program USCAR-11.The standard deviation of the peak torque of the bolt that conventional zinc chromate/Huang handled is approximately 5.57Nm (having about 33.4 3-δ scope), and is approximately 2.56Nm (having about 15.4 3-δ scope) according to the standard deviation of the peak torque of the bolt of processing method processing of the present invention.
According to the expectation purposes of the work piece of being handled by processing method of the present invention, available second coating or thin layer are coated with this work piece.Or the work piece that first rinsing (as mentioned above) was handled are coated with second coating or thin layer then.The example of these second coatings or thin layer comprise following one or more: acrylic acid coatings (IRILAC for example
), silane (comprise have amine, those silane of vinylformic acid and fatty epoxy-functional), latex, amino acrylates, epoxies, type siloxane, alcohol acids, phenoxy lipid (powder and liquid form), the coating (for example coating of ultraviolet curing) of radiation curing, lacquer, lac, oleum lini.Second coating is solvent or aqueous systems.By utilizing any suitable ordinary method (for example dipping, dip-spin technique, spraying) can apply second coating.Utilize curable this second coating of any suitable method (for example uv light exposure, heating, under external environmental condition, carry out drying).The example of ultraviolet curing coating is at U.S.6, describes to some extent in 174,932 and 6,057,382, and these two pieces of documents are incorporated herein by reference at this.Usually, before applying finish paint with at least a surface of coming rinsing to form in deionized water, silane or the carbonic ether by processing method of the present invention.This second coating can provide the characteristic of broad range for example to improve erosion resistance to following layer mineral, reduces torque tension force, coating temporarily also has static dissipation, screening of nucleus, hydrogen and/or atomic oxygen barrier so that transport the work piece of handling, ornamental finished product.The work piece that scribble mineral that have or do not have second coating can be used as final product or are used for making the parts of another goods.
Need not in conjunction with any theory or explanation, can on mineral, form the thin layer that contains silicon-dioxide.The thin layer that contains silicon-dioxide can carry out chemistry or physically modified and be used as the middle layer or the knot layer.This knot layer can be used to strengthen the bonding force to the paint vehicle in the other materials of contact knot layer, coating, metal, glass.Can obtain this point by the top layer that contains silicon-dioxide is combined with one or more materials, wherein these materials contain can be with alkyl, fluorine, vinyl in other functional groups of silicon-dioxide or silicon hydroxide reaction, comprise the mixture of the two-part epoxy of epoxy and powder paints system, silane, hydroxyl, amino, these groups.Or, can remove the thin layer that this contains silicon-dioxide by utilizing conventional cleaning method (for example using rinsed with deionized water).Compare with the layer mineral of 100-500 dust, the knot layer that contains silicon-dioxide is quite thin, and that the mineral total thickness can reach the 1500-2500 dust is thick.If necessary, by adopt above-described post-treating method (for example being exposed at least a carbonic ether or the acid source) can chemistry and/or physically modified this contain the thin layer of silicon-dioxide.The surface of this aftertreatment is contacted with at least a above-mentioned second coating (for example heat curing-type epoxy).
On the other hand, have or the layer mineral that do not have above-mentioned silicon-dioxide can be used as the middle layer or the knot layer of one or more second coatings (second coating that for example contains silane).The example that can replenish these second coatings of the present invention and method is at U.S.5, and 759,629; 5,750,197; 5,539,031; 5,498,481; 5,478,655; 5,455,080; And describe to some extent in 5,433,976.The open text of these United States Patent (USP)s is incorporated herein by reference at this.For example, second coating that is combined with comprising of mineral surface of at least a suitable silane by employing can be improved the erosion resistance to metal base.The example of suitable silane comprises a member at least of selecting from the combination that following material constitutes: the 4-neighbour in other organofunctional silanes-ethyl-silicate (TEOS), two-1,2-(three methylamino ethoxies are silica-based) ethane (BSTE), vinyl silanes or aminopropyl silane, epoxy silane, organoalkoxysilane.Silane can with the mineralising surface bonding, silane can solidify then, is provided for receiving protectiveness finishing coat or surface of external coating (EC) or thin layer whereby.In some cases, need apply these silane successively.For example, can handle steel base (for example fastener) to form layer mineral, drying and rinsing in deionized water then, secondly with 5% BSTE solution coat, vinyl silanes solution with 5% is coated with again, and carrying out powder coatedly with thermoset epoxy lacquer (the Corvel 10-1002 of Morton), total thickness reaches 2 mils.Draw this steel base with the Wimet point, and make it in ASTM B117 salt fog, expose 500 hours.After the exposure, take out this substrate and rinsing, dry 1 hour then.Utilize scraping, scrape off this cut, remove any paint vehicle, and measure remaining slit owing to incision.The substrate of being surveyed demonstrates does not have the slit that can survey except this cut.
Processing method of the present invention has formed has improved fusible surface to external coating (EC) or thin layer (for example second coating).The example of suitable external coating (EC) comprises a member at least of selecting from the combination that following material constitutes: vinylformic acid, Resins, epoxy, electronics coating, latex, aminoacrylic acid methyl esters, silane (for example TEOS, the MEOS in other silane), fluoropolymer class, alcohol acids, type siloxane, polyester, oils, gel-like, lubricating grease.The coating as B17 or B18 finish paint that is provided by Magni Group is provided the example of suitable epoxy, for example, zinc coating has been handled according to method of the present invention and has been contacted with at least a silane and/or zirconium carbonic acid ammonia, use heat curing-type epoxy (Magni B18) face to be coated with then, form not chromate-containing corrosion-resistant goods whereby.By selecting suitable purificant, being applied to second on mineral or external coating (EC), need not chromic acidization or phosphorylation and just can obtain the corrosion resistant type goods.This selection can reduce the use of the surface of containing iron being carried out galvanized zinc, and for example steel surface of mineralising is used the coating that contains silane then and comprised that the external coating (EC) of epoxy is coated with.
Need not in conjunction with any theory or explanation, it is believed that processing method of the present invention has formed the surface that can discharge or provide water or relevant portion.Precipitate in hydrolysis that these parts can take place when the rinsing that is covered, sealing or finish paint solidify or the condensation reaction.This precipitation has improved the adhesive bond intensity between the solidified coating of should the surface and being covered.
The surface that is formed by processing method of the present invention also can be used as middle layer or the knot layer that is used for other coated with glass of using, glass-to-metal seal, sealing, and wherein wishing has one to be connected or combination between metal base and glass coating or goods.Surface of the present invention can be used to receive melten glass (for example borosilicate, the phosphoric acid salt in other glass), simultaneously metal base below the protection and formation sealing.
Processing method of the present invention can provide improves the substrate handled and the close-burning surface between the tamanori.The example of tamanori comprises a member at least of selecting from the combination that following material constitutes: thermometal (a member at least of selecting from the combination that following material constitutes for example: polymeric amide, polyimide, butyl, acrylic acid modified compound, maleic anhydride-modified ethyl vinyl ethyl ester, maleic anhydride-modified polyethylene, the ethyl vinyl ethyl ester of hydroxyl terminal knot, the ethyl vinyl ethyl ester of carbonyl end knot, acid terpolymer ethyl vinyl ethyl ester, ethylene-acrylate), monophase system (dicyanamide solidified epoxies for example, polymeric amide solidified system, Lewis acid solidified system, polysulphide, moisture cure urethanes), biphasic system (epoxies for example, activated acrylate polysulphide, urethane).By adopting tamanori two metal base with the surface of handling according to processing method of the present invention can be adhered to together.Or, a substrate with surface of the present invention can be adhered on the another kind of material, for example make the metal handled and the plastics in other surfaces, pottery, glass adhesion.A particular aspects, this substrate comprises an automatic clasp joint, and wherein tamanori is positioned at hook.
Improved between surface that is formed by processing method of the present invention and the polymeric material cohered or adhesion characteristic allow to form sound wave and mechanical damper for example the constraint damper in other goods (such as at U.S.5,678, described in 826, the document is incorporated herein by reference at this), engine erecting frame, bridge/building bearing, HVAC sourdine, expressway/airport sound barrier.The ability of improving the associativity between the bonding resilient material that is clipped between the damper metal sheet has reduced the transmission of sound, has improved the formation ability of these plates, has reduced process deviation.These metal sheets can comprise for example 304 steel, stainless steel, aluminium, cold-rolled steel, zinc alloy, galvanizing or the electro-galvanizing in the other materials of any suitable metal.Can be with surface bonding of the present invention and comprise for example chloroprene rubber, EPDM, SBR, the EPDM in other polymkeric substance of any suitable material with the example of following metal base bonded polymkeric substance again.Surface of the present invention also can provide the combination (at U.S.5, describe to some extent in 942,333, the document is incorporated herein by reference at this) of elastomerics-metal.
The surface that processing method of the present invention can be utilized doping agent, purificant and/or encapsulant to provide to have the heat-resisting and wearing quality of improvement.Such surface can be used for ground/grid, the heater block that gear (for example transmission), powder metal goods, exhaust system (comprising arm), metal in other application are mated formation, and wherein wishes to improve the resistance of metallic surface.
In another aspect of this invention, can utilize processing method generation of the present invention to reduce the surface of (eliminating) molten metal binding property (for example by reducing intermetallic formation) if having.Need not in conjunction with any theory or explanation, it is believed that processing method of the present invention on goods or parts, provide can have an effect with molten metal or react reduce whereby the bounding force of bulk article is ablated and/or reaction film or coating.For example, processing method of the present invention can provide ferric metasilicate or zinc silicate film or coating in substrate, so that shield or isolate this substrate from molten metal (for example molten aluminum or magnesium).By applying the efficient that the additional coatings that comprises silicon-dioxide (for example in being exposed to molten metal time can be used as ablator) can improve this film or coating.In other purposes,, need to suppress molten metal adherent ability at zinc nuclear patrix cast aluminium or magnesium, when die casting is used for the aluminium of electronic unit.By applying for example Magni B18, vinylformic acid, the polyester in other materials of above-described finish paint, can further reduce the bounding force of molten metal.By applying for example colloided silica (Ludox for example of heat-stable material
), can make finish paint modification (for example more heat-resisting).
Though above description lay special stress on forms the thin layer that contains mineral on the metallic surface, processing method of the present invention can combine or substitute with the front or rear processing and/or the finished product practice of common metal.Conventional back coating baking can be used to the physical properties of modified mineral layer in other improve, remove and anhydrate and/or hydrogen.Layer mineral of the present invention can be used to protect the metal finished product to avoid corrosion; substitute conventional phosphorylation technology whereby; for example; in the situation of automobile metal finished product, utilize processing method of the present invention and for example adopt processing method of the present invention before the E-coating without phosphoric acid salt and chromic salt and applying coating.And, use the aqueous solution of the polyurethane-base that contains soluble silicate to replace above-mentioned mineral water solution, and this mineral water solution can be used to replace so-called automobile E-coating and/or powder paints technology.Mineral form technology and can be used to strengthen for example erosion resistance of motor shaft (as what routine 10-11 confirmed) of electronic unit.Processing method of the present invention also can be used in for example conventional electroplating technology of end-use that reality do not limit and is suitable for on-the-spot service.For example, can utilize the coating that contains mineral of the present invention to make the corrosion-resistant metal product, this product is utilizing zinc as supercoat traditionally, and these products comprise such as the car body in many other end-uses and parts, cartridge type silo, bridge.And, according to existing doping agent and concentration thereof in the mineral deposition liquid, processing method of the present invention can produce the microelectronics film such as metal or conductive surface, thereby enhanced electromagnetism (corrodibility of for example EMI in other character shielding, the electric connector that reduces, reduce the corrosion that is caused by different metallic contact) property and erosion resistance are provided, perhaps hold out against ultraviolet ray and contain the environment of antozone for example extraneous.
Following example is in order to set forth some aspect of the present invention, and should be appreciated that such example not delimit the scope of the invention (being limited as the back appending claims).The sub-spectroscopy data acknowledgement of x-ray photoelectric in the following example in mineralized layer, have unique pyrosilicate species, for example ESCA measures the photoelectron bound energy of atom, thereby measures binding characteristic.
Example 1
Adopt following device and material in this example:
The electro-galvanizing test board of standard, the ACT laboratory
The N-level sodium silicate solution of 10% (by weight)
12 volts EverReady battery
1.5 the Ray-O-Vac Heavy Duty Dry Cell Battery of volt
Triple RMS digital multimeter
The electrical condenser of 30 μ F
29.8k the electrical condenser of Ω
Fig. 1 shows and is used to implement this routine circuit and schematic representation of apparatus.Referring now to Fig. 1, above-mentioned brassboard is contacted with the solution that contains 10% sodium mineral and deionized water.Make electric current flow through this circuit and solution in mode shown in Figure 1.This brassboard exposes 74 hours under external environmental condition.The visual inspection of this brassboard shows, deposits grayish coating or film on brassboard.
In order to determine, according to the applied brassboard of ASTM rules No.B117 test by the erosion resistance that coating provided that contains mineral.Cover the cross section of brassboard with band, thereby only expose applied zone, thereafter this plate is placed salt fog.In order to compare, following plate also tests 1 according to ASTM rules No.B117) naked electrolytic galvanized sheet, and 2) in 10% sodium mineral solution, soak 70 hours naked electrolytic galvanized sheet.In addition, the steel plate (ACTB952, no Parcolene) of naked zinc phosphate coating and the steel plate (ACTB1000, no Parcolene) of naked tertiary iron phosphate coating are placed salt fog, so that as reference.
Listed the result of ASTM rules in the following table
Above table indicates, and the present invention has formed the coating or the film that can obviously improve erosion resistance.Show that also this processing method has caused prolonging the formation of the electro-galvanizing metal base and the anticorrosive film in the life-span on surface.
According to the technology of routine, on zinc surface, carry out esca analysis under the following conditions:
The analysis condition of ESCA:
Instrumental Physics electronics model is 5701 Lsci
The monochromatic aluminium of X-ray source
350 watts of source power
Analyzed area 2mm * 0.8mm
50 ° of exit angle
Electronics acceptance angle ± 70 °
Charge neutralization electronical reading electron beam gun
Electric charge proofread and correct the C-in the 1s spectrum under 284.6eV (C, H)
* exit angle is the angle between sample panel and the electrical analysis meter lens.
Utilize the photoelectron bound energy of silane to make the nature and characteristicization of formed species in the mineralized layer that on negative electrode, forms.Utilize the bound energy of the photoelectronic 102.1eV of Si (2p) that these species are accredited as the disilicic acid zinc of modification owing to the existence of sodium ion.
Example 2
This example has been described and implemented electrodeposition technology of the present invention under the voltage and current of comparing increase with example 1.
Before galvanic deposit, the anticathode plate carries out preconditioning technology:
1) in the Metal Prep 79 (Parker Amchem) of dilution in 3: 1, flooded 2 minutes,
2) secondary deionized water rinsing,
3) in the sodium hydroxide solution of pH14, flooded for 10 seconds,
4) remove the excessive solution line space air dry of going forward side by side,
5) in 50% superoxol, flooded 5 minutes,
6) remove the excessive solution line space air dry of going forward side by side.
Power supply is linked to each other with the galvanic deposition cell that comprises plastic cup, and this plastic cup is equipped with ACT cold-rolled steel (cleaning, the not polishing) test board of two standards.The impregnation area (1 side) that one end of test board is immersed in each plate in the deionized water solution that contains 10%N-level sodium mineral (PQ Corp.) is approximately 3 inches * 4 inches (12 square inches), and the ratio of anode and negative electrode is 1: 1.These plates directly link to each other with the DC power supply and apply 6 volts voltage and reach 1 hour.Last electric current is in the scope of about 0.7-1.9 ampere.Last current density is in the scope of 0.05-0.16 amps/square.
After the electrolytic process, dry this coated panel under external environmental condition, test the wet fastness that No.D2247 assesses this plate according to ASTM then: promptly the visual monitoring corrosion activity is till red rust occurring on the plate surf zone 5%.These coated test plates just occurred red rust in lasting 25 hours first and just occurred 5% red rust in lasting 120 hours.In contrast, the conventional iron and the steel plate of zinc phosphorylation continue just to occur first in 7 hours corrosion and red rust nearly 5% in ASTM D2247 humidity exposure.Therefore, above-mentioned example shows that processing method of the present invention can provide than iron and the better erosion resistance of zinc phosphorylation steel plate.
Example 3
Utilize two stereotypes of coml lead sheath preparation and in the HCl of 6M, clean 25 minutes.Stereotype with cleaning places the solution that 1wt.%N-level water glass (being provided by PQ Corporation) is provided then.
A stereotype is linked to each other with the DC power supply as anode, and another stereotype is as negative electrode.Apply 20 volts current potential at first so that produce the electric current of 0.9-1.3 ampere.After about 75 minutes, these plates are taken out from sodium silicate solution and carried out rinsing with deionized water.
On plumbous surface, carry out esca analysis.Utilize the photoelectron bound energy of silane to make the nature and characteristicization of formed species in mineralized layer.Utilize the bound energy of the photoelectronic 102.1eV of Si (2p) that these species are accredited as the disilicic acid lead of modification owing to the existence of sodium ion.
Example 4
Form a layer mineral on the tangible aluminium substrate of this illustration.Utilize with example 1 in identical device, make aluminium stopple coupon (3 " * 6 ") reaction, with formation metal silicate surface.Adopt two different aluminium alloys (Al2024 and Al7075).Before these plates are carried out electrolysis process, utilize method listed among the following table A to prepare each plate.Wash each plate to remove any excessive dirt and oils with solvent alcohol.Carry out the negatively charged ion cleaning or two kinds of methods all adopt with Alumiprep 33 these plates of cleaning or to these plates.These two kinds of cleaning modes are in order to remove excessive aluminum oxide.Can followingly finish the negatively charged ion cleaning: working plate is put into as anode contained 5% NaOH, 2.4% Na
2CO
3, 2% Na
2SiO
3, 0.6% Na
3PO
4The aqueous solution in, and apply a current potential so that will pass the 100mA/cm of test board impregnation zone
2Current density kept 1 minute.
In case clean this plate, just put it in the 1 liter of beaker that is filled with 800mL solution.Utilize the content preparation shown in deionized water and the following table to bathe.Utilize electric wire that this plate is connected on the negative wire head of DC power supply, and another plate is connected on positive the end of a thread.2 inches of these two plate each intervals.With potential setting on the voltage shown in this table and groove work 1 hour.
Table A
Utilize ESCA to analyze the surface of each substrate.Each sample of being surveyed is expressed the mixture of silicon-dioxide and metal silicate.Need not in conjunction with any theory or explanation, it is believed that metal silicate is the metallic cation on surface and the reaction result between the alkaline silicate of coating.It is believed that also silicon-dioxide is from the excess silicon hydrochlorate of this reaction or from the product of the precipitated silica of coating removal technology.Si (2p) bound energy (BE) of utilization in lower 102eV (generally between 102.1-103.6eV) scope indicates this metal silicate.Resulting spectrum going in the scope of representing metal silicate and silicon-dioxide demonstrates the eclipsed peak on the flatung colour developing bound energy.
Example 5
This example has been described the another kind dipping that is used to produce the medium that contains silicate.
Utilization mixes 5% water glass with 10% fumed silica and the aqueous gel for preparing is coated with cold-rolled steel sheet.With plate of reagent alcohol washing, and prepare another piece plate of washing in the liquid, implement sodium hydroxide washing and bath of hydrogen peroxide then at the phosphate base metal.By utilizing the DC power supply that positive the end of a thread is connected on the steel plate, the negative wire head is connected on the platinum line that wraps up with glass wool, set up this device.This device can be simulated the brushing electroplating operations." brush " is immersed in the gelating soln so that saturated fully.Potential setting is coated onto gel on the plate at 12V and with brush.When passing through on the surface of brush at plate, can see having hydrogen to discharge.Brushing gel 5 minutes is then with this plate of deionized water wash, to remove any excessive gel and unreacted silicate.
Utilize ESCA to analyze the surface of each steel plate.Reaction product between the environment that ESCA detection metal base and electrolysis process are brought up.Each sample of being surveyed indicates the mixture of silicon-dioxide and metal silicate.Metal silicate is the metallic cation on surface and the reaction result between the alkaline silicate of coating.Silicon-dioxide is from the excess silicon hydrochlorate of this reaction or from the product of the precipitated silica of coating removal technology.Si (2p) bound energy (BE) of utilization in lower 102eV (generally between 102.1-102.3eV) scope indicates this metal silicate.Utilize Si (2p) BE between the 103.3-103.6eV can see silicon-dioxide.Resulting spectrum going in the scope of representing metal silicate and silicon-dioxide demonstrates the eclipsed peak on the flatung colour developing bound energy.
Example 6
Utilize with example 1 in identical device, make cold-rolled steel stopple coupon (ACT laboratory) reaction, with formation metal silicate surface.Before these plates are carried out electrolysis process, utilize method listed among the following table B to prepare each plate.Wash each plate to remove any excessive dirt and oils with reagent alcohol.Clean these plates or these plates are carried out negatively charged ion cleaning or two kinds of methods all adopt with Metalprep 79 (ParkerAmchem).These two kinds of cleaning modes are in order to remove excessive metal oxide.Can followingly finish the negatively charged ion cleaning: working plate is put into as anode contained 5% NaOH, 2.4% Na
2CO
3, 2% Na
2SiO
3, 0.6% Na
3PO
4The aqueous solution in, and apply a current potential so that will pass the 100mA/cm of test board impregnation zone
2Current density kept 1 minute.
In case clean this plate, just put it in the 1 liter of beaker that is filled with 800mL solution.Utilize the content preparation shown in deionized water and the following table to bathe.Utilize electric wire that this plate is connected on the negative wire head of DC power supply, and another plate is connected on positive the end of a thread.2 inches of these two plate each intervals.With potential setting on the voltage shown in this table and groove work 1 hour.
Table B
1Cold-rolled steel contrast-this plate is not handled.
2With the further processing of parkerized cold-rolled steel (ACT laboratory)-do not do.
Electrolysis process is tested as continuous current or constant voltage carry out, represent with symbol CV or CC in the table.The constant voltage experiment is applied to a constant potential on the groove that allows fluctuation of current, and the continuous current experiment is kept electric current by regulating current potential.Utilize the erosion resistance of ASTM B117 test panel.Red rust surface coverage place 5% determines breakage.
Utilize ESCA to analyze the surface of each substrate.Reaction product between the environment that ESCA detection metal base and electrolysis process are brought up.Each sample of being surveyed indicates the mixture of silicon-dioxide and metal silicate.Metal silicate is the metallic cation on surface and the reaction result between the alkaline silicate of coating.Silicon-dioxide is from the excess silicon hydrochlorate of this reaction or from the product of the precipitated silica of coating removal technology.Si (2p) bound energy (BE) of utilization in lower 102eV (generally between 102.1-102.3eV) scope indicates this metal silicate.Utilize Si (2p) BE between the 103.3-103.6eV can see silicon-dioxide.Resulting spectrum going in the scope of representing metal silicate and silicon-dioxide demonstrates the eclipsed peak on the flatung colour developing bound energy.
Example 7
Utilize with example 1 in identical device, make galvanized steel stopple coupon (EZG 60GACT laboratory) reaction, with formation metal silicate surface.Before these plates are carried out electrolysis process, utilize method listed among the following table C to prepare each plate.Wash each plate to remove any excessive dirt and oils with reagent alcohol.
In case clean this plate, just put it in the 1 liter of beaker that is filled with 800mL solution.Utilize the content preparation shown in deionized water and the following table to bathe.Utilize electric wire that this plate is connected on the negative wire head of DC power supply, and another plate is connected on positive the end of a thread.2 inches of these two plate each intervals.With potential setting on the voltage shown in this table and groove work 1 hour.
Table C
1Galvanized steel contrast-this plate is not handled.
Utilize the erosion resistance of ASTM B117 test panel.Red rust surface coverage place 5% determines breakage.Utilize ESCA to analyze the surface of each substrate.Reaction product between the environment that ESCA detection metal base and electrolysis process are brought up.Each sample of being surveyed indicates the mixture of silicon-dioxide and metal silicate.Metal silicate is the metallic cation on surface and the reaction result between the alkaline silicate of coating.Silicon-dioxide is from the excess silicon hydrochlorate of this reaction or from the product of the precipitated silica of coating removal technology.Si (2p) bound energy (BE) of utilization in lower 102eV (generally between 102.1-102.3eV) scope indicates this metal silicate.Utilize Si (2p) BE between the 103.3-103.6eV can see silicon-dioxide.Resulting spectrum going in the scope of representing metal silicate and silicon-dioxide demonstrates the eclipsed peak on the flatung colour developing bound energy.
Example 8
Utilize with example 1 in identical device, make copper stopple coupon (C110 Hard, Fullerton Metal) reaction, with the formation metalized surface.Before these plates are carried out electrolysis process, utilize method listed among the following table D to prepare each plate.Wash each plate to remove any excessive dirt and oils with reagent alcohol.
In case clean this plate, just put it in the 1 liter of beaker that is filled with 800mL solution.Utilize the content preparation shown in deionized water and the following table to bathe.Utilize electric wire that this plate is connected on the negative wire head of DC power supply, and another plate is connected on positive the end of a thread.2 inches of these two plate each intervals.With potential setting on the voltage shown in this table and groove work 1 hour.
Table D
1Copper contrast-this plate is not handled.
Utilize the erosion resistance of ASTM B117 test panel.Owing to the existence of cupric oxide determines breakage, and the half-light mist that is occurred on the surface indicates the existence of cupric oxide.
Utilize ESCA to analyze the surface of each substrate.Reaction product between the environment that ESCA detection metal base and electrolysis process are brought up.Each sample of being surveyed indicates the mixture of silicon-dioxide and metal silicate.Metal silicate is the metallic cation on surface and the reaction result between the alkaline silicate of coating.Silicon-dioxide is from the excess silicon hydrochlorate of this reaction or from the product of the precipitated silica of coating removal technology.Si (2p) bound energy (BE) of utilization in lower 102eV (generally between 102.1-102.3eV) scope indicates this metal silicate.Utilize Si (2p) BE between the 103.3-103.6eV can see silicon-dioxide.Resulting spectrum going in the scope of representing metal silicate and silicon-dioxide demonstrates the eclipsed peak on the flatung colour developing bound energy.
Example 9
Set up an electrochemical cell with 1 liter of beaker.This beaker is filled with the sodium silicate solution of the N sodium silicate solution (PQCorp) that comprises 10wt.%.By beaker is put into can controlled temperature the water-bath temperature of regulating this solution.Utilize the material of cold-rolled steel stopple coupon (ACT laboratory, 3 * 6 inches) as anode and negative electrode.These two plates are put into beaker, make the two face with each other 1 inch at interval.With active gage as anode.Anode is linked to each other with the DC power supply with negative electrode.Voltage, solutions employed, electrolysis time, current density, temperature and corrosive nature have been shown in the following table.
Table E
With these plates of rinsed with deionized water to remove any excessive silicate of from body lotion, having extracted out.According to ASTM B117 these plates are carried out the corrodibility test.Be recorded in these plates in the oorroding house and reach the time (as above shown in the table) that 5% red rust (as what measure by visual observation) is spent.Example I-H shows the Corrosion results of not carrying out the same steel plate of any processing.
Example 10
Example 10,11 and 4 has confirmed a special aspect of the present invention, that is, make the steel axle of incorporating in the motor have erosion resistance.Motor shaft is from Emerson Electric Co.from St.Louis, and Missouri obtains and be used for the support rotor assembly.The length that records axle is that 25cm, diameter are 1.5cm, and prepares these axles with the commercial steel that obtain.
Similar in the foundation of electrochemical cell and the example 9, just the layout of this groove makes it can hold above-mentioned steel motor axle.This axle is established as negative electrode, and two cold-rolled steel sheets are used as anode, the layout of these two plates makes each plate all on the relative both sides of axle.Regulating voltage as shown in the table and temperature.Also show the anodic current density in the table.
Table F
With rinsed with deionized water these to remove any excessive silicate of from body lotion, having extracted out.Owing to handle, routine II-A compares with routine II-B to II-F and does not demonstrate the obvious color variation.Example II-B shows faint yellow/gold tone.Example II-C shows pale blue and light pearly-lustre look.Example II-D and II-F show avy blue owing to handling.According to ASTMB117 these axles are carried out the corrodibility test.Be recorded in interior these plates of oorroding house and reach for 5% the time that red rust spent (as above shown in the table).Example II-G shows the Corrosion results of the same steel axle that does not carry out any processing, and routine II-H shows the Corrosion results of the same steel axle with coml phosphoric acid zinc coating.
Example 11
The foundation and the example 10 of electrochemical cell that is used for handling the steel axle is similar.Motor shaft is from Emerson Electric Co.from St.Louis, and Missouri obtains and be used for the support rotor assembly.The length that records axle is that 25cm, diameter are 1.5cm, and prepares these axles with the commercial steel that obtain.This axle is established as negative electrode, and two cold-rolled steel sheets are used as anode, the layout of these two plates makes each plate all on the relative both sides of axle.Regulating voltage as shown in the table and temperature.Also show the anodic current density in the table.
Table G
With rinsed with deionized water these to remove any excessive silicate of from body lotion, having extracted out.According to ASTM B117 these plates are carried out the corrodibility test.Be recorded in the oorroding house these and reach the time (as above shown in the table) that 5% red rust coverage is spent.Example III-C shows the Corrosion results of the same steel axle that does not carry out any processing, and routine III-D shows the Corrosion results of the same steel axle with coml phosphoric acid zinc coating.
Example 12
Set up an electrochemical cell with 1 liter of beaker.Solution is filled with and comprises 5,10 or the sodium silicate solution of the N sodium silicate solution (PQ Corporation) of 15wt.%.By beaker is put into can controlled temperature the water-bath temperature of regulating this solution.Utilize cold-rolled steel stopple coupon (ACT laboratory, 3 * 6 inches) as anode and cathode material.These two plates are put into beaker, make the two face with each other 1 inch at interval.With active gage as anode.Anode is linked to each other with the DC power supply with negative electrode.The dimension scale of voltage, solutions employed, electrolysis time, the current density by negative electrode, temperature, anode and negative electrode has been shown in the following table, and corrosive nature.
Table H
With these plates of rinsed with deionized water to remove any excessive silicate of from body lotion, having extracted out.According to ASTM B117 these plates are carried out the corrodibility test.Be recorded in these plates in the oorroding house and reach the time (as above shown in the table) that 5% red rust coverage is spent.Example IV-28 shows the Corrosion results of not carrying out the same steel plate of any processing.Last table explanation utilizes the concentration of bath mesosilicic acid salt and the temperature of rising can strengthen corrosive nature.Also can in 15 minutes, realize anticorrosive.Utilize higher current density can further strengthen corrosive nature.
Example 13
Set up an electrochemical cell with 1 liter of beaker.This solution is filled with the sodium silicate solution of the N sodium silicate solution (PQCorp) that comprises 10wt.%.By beaker is put into can controlled temperature the water-bath temperature of regulating this solution.Utilize galvanized steel stopple coupon (ACT laboratory, 3 * 6 inches) as cathode material.Utilize zine plate as anode material.These two plates are put into beaker, make the two face with each other 1 inch at interval.With active gage as anode.Anode is linked to each other with the DC power supply with negative electrode.Voltage, solutions employed, electrolysis time, current density and corrosive nature have been shown in the following table.
Table I
With these plates of rinsed with deionized water to remove any excessive silicate of from body lotion, having extracted out.According to ASTM B117 these plates are carried out the corrodibility test.Time representation when these plates are demonstrated rust staining and zinc oxide formation is corrosion (W).Be recorded in these plates in the oorroding house and reach the time (as above showing shown corrosion (R)) that 5% red rust coverage is spent.Example V-E shows the Corrosion results of not carrying out the same steel plate of any processing.
Example 14
The foundation and the routine 10-12 of electrochemical cell that is used for handling the steel axle is similar.Motor shaft is from Emerson ElectricCo.from St.Louis, and Missouri obtains and be used for the support rotor assembly.The length that records axle is that 25cm, diameter are 1.5cm, and the alloy data is as shown in following table.This axle is established as negative electrode, and two cold-rolled steel sheets are used as anode, the layout of these two plates makes each plate all on the relative both sides of axle.Regulating voltage as shown in the table and temperature.Also show the anodic current density in the table.
Table J
With rinsed with deionized water these to remove any excessive silicate of from body lotion, having extracted out.According to ASTMB117 these plates are carried out the corrodibility test.Be recorded in the oorroding house these and reach the time (as above shown in the table) that 5% red rust coverage is spent.
Example 15
This example has been set forth and has been utilized electrolysis process to form layer mineral on steel fiber, but wherein steel fiber can be pressed into end article or form the compressing tablet of another kind of material infiltrate.
Fiber is to be 0.026 inch, cold-draw to 260 by diameter, 000-280, (0.20-0.26in) of the 1070 carbon steel wires cutting of 000PSI.The fiber of 20grams is put in the plastic beaker of 120mL.Platinum filament is put in this beaker, makes it to contact with steel fiber.Make 1 inch * 1 inch Angle Steel Ruler on steel fiber, keep 1 inch, and supporting so that do not contact platinum filament.Water glass (N-level, the PQ Corp) deionized water solution of 75mL 10% is joined in this beaker, flood Angle Steel Ruler and steel fiber whereby and form electrolyzer.The DC power supply of 12V is linked to each other with this groove, and with steel fiber as negative electrode,, and transmit as anode with Angle Steel Ruler up to 3 amperes/inch
2The anionic electrodeposition flow density.This groove is put on the Vortex agitator, thereby makes steel fiber make steady motion.Opening power also passed through 5 minutes the current potential of 12V in groove.After this time, excess solution is dismantled and poured out to groove, only remaining steel fiber.When stirring, on steel grit, blow warm air so that carry out drying.
According to ASTM B117 these fibers are carried out SaltSprayTest.Listed the visual measurement result of ASTM B117 test in the following table.
Table K
Example 16-24
In routine 16-24, verified processing method of the present invention adopt as described in Example 21 liter of beaker and DC power supply.Regulate silicate concentration, the current potential that is applied and the bath temperature in bathing and in table L-A, listed these parameters.
Table L-A
Example 16
In order to test the effect of the metal ion in the electrolytic solution, iron(ic) chloride is joined in the bath solution with concentration listed in the following table.Because iron easily and silicate is compound or form ferric hydroxide precipitate, therefore is difficult to iron is incorporated in this solution.Because the cationic acid matter of iron can be destroyed the solvability of silicon-dioxide in basic solution, so the adding of iron also is restricted.Yet discovery can join the iron(ic) chloride (＜0.5%) of limited amount lower concentration in 20% the N-level silicate solutions, FeCl
3Concentration in the silicate solutions of 10wt.% is less than 0.025wt%.Table L shows comparison electrolytic solution and keeps the constant truth table of other conditions.Utilize inert anode, compare solution effect without any the negatively charged ion solvency action.
The L-B table
The result of table L-B shows in 10% silicate solutions the processing method of the present invention of carrying out under 12V in 75C 30 minutes.Used anode is also iron plate of platinum guaze both.This solution is 10% silicate solutions with 0-0.0025% ferric chloride Solution.Measure corrosive nature in ASTM B117 exposure duration.
This trend shows that the effect that amount produced of utilizing the increase of inertia platinum electrode to be doped to the iron in the body lotion is similar with the bath that does not have doping iron, employing iron anode.The real iron of being introduced by the steel anode of this illustration strengthens erosion resistance, and this can be reappeared by introducing iron salt solutions.
Example 17
Need not in conjunction with any theory or explanation, it is believed that the mineralising reaction mechanism comprises condensation reaction.Rinsing studies show that out the existence of condensation reaction, is showing the rinse test plate afterwards of the electrolysis treatment shown in the M-A in this research.Table M-A shows that etching time also increases when the rinsing time increases.It is believed that and easily in water rinse, to remove this layer mineral so in layer mineral if crosslinked or polymerization takes place layer mineral irrelevantly.On the contrary, when dry quite a long time of test board, the corrosion failure time is improved, and indicates whereby and has formed complete crosslinked or polymeric layer mineral.May there be for example crosslinking reaction of further step of reaction in this further hint.
By heating, can strengthen the erosion resistance of layer mineral.Table M-B indicates the effect of heating to corrosive nature.Approximately this performance begins weak after the 600F.Need not in conjunction with any theory or explanation, it is crosslinked to it is believed that heating can improve at first, and the continuous heating at the high temperature place can cause the cross-linked layer degraded.
Table M-A
Table M-A indicates with CEM silicate and handles, handles the corrosion failure time (ASTMB117) that carries out the later steel test board of rinsing afterwards at different time.
Table M-B
Table M-B-handles the CEM of steel base.Technology B is meant the 12V in 10% silicate solutions, 30 minutes cationic mineralising processing.Technology C is meant the 18V in 15% silicate solutions, 30 minutes cationic mineralising processing.Breakage is meant the time that occurs 5% red rust coverage in the ASTMB117 salt mist environment.
Example 18
Analyze the bound energy of the layer mineral that on stainless steel, forms in this example.Stainless steel is ANSI 304 alloys.Sample is carried out solvent wash and utilizes technology B (being doped with 10% silicate solutions of iron(ic) chloride, 75C, 12V, 30 minutes) to handle.According to ordinary method these samples of handling are implemented ESCA.The result of ESCA indicates Si (2p) bound energy of 103.4eV.
Utilize ultromotivity microscope (AFM) also can analyze this layer mineral.It is wide that the shown crystallization in surface is approximately 0.1-0.5 μ m.
Example 19
According to ordinary method, utilize Auger electron can praseodymium to learn (AES) to analyze the layer mineral that the method B according to example 18 forms.Based on the general thickness that measures this silicate layer containing of silicon, metal and oxygen is about 5000 dusts (500nm).Measure the thickness of silicon dioxide layer less than about 500 dusts (50nm) based on metal content with respect to the amount of silicon and oxygen.
The layer mineral that will form according to the method B of example 16 is applied to ANSI304 at stainless steel-based the end.According to the testing method of routine, utilize ultromotivity microscope (AFM) to analyze this layer mineral.AFM discloses the crystal grain boundary that is grown in of metal silicate crystallization (about 0.5 micron) to be assembled on every side.
Example 20
This example indicates the influence of the concentration of silicate to processing method of the present invention.But the concentration consume silicon hydrochlorate of electrolytic solution after implementing processing method of the present invention.In an experiment, utilize 1 liter 10% sodium silicate solution to test the number of bathing the technology that is stood before the efficient that is reducing to bathe.Bathe and use after 30 times, utilize to expose 15in
2Test board, the corrosive nature of the plate of handling has obviously weakened.
Aggegation makes its insoluble silicate in acid or the metal but water glass is exposed to.If a certain Cmin of silicate is useful, the adding of acid or metal-salt will be settled out gel so.If this solution consumption silicate or do not have enough amounts can not form precipitation so.Various acid and metal-salt are joined in the electrolytic bath of five equilibrium.Processing method of the present invention in same bath, carry out 40 take turns after, this mineral barrier can not provide the protection of par.This example shows the efficient that can utilize iron(ic) chloride and zinc chloride to come the test silicon hydrochlorate to bathe.
Table N
Table N-the 5th takes turns the body lotion sample that takes out 50mL and tests with the ppt test at each."-" expression not precipitation forms."+" expression has precipitation to form.
Example 21
This example will compare in the erosion resistance that contains on the surface of zinc and contain the layer mineral that forms on the surface of iron (steel) according to example 16.Table O shows comparison iron, and ((electro-galvanizing-EZG) is as the truth table of cold rolled steel substrate and the suprabasil lattice construction material of electro-galvanizing for cold-rolled steel-CRS) and zinc.Relatively the result of rinsing is also included among the table O.Only the sample of rinsing more can obtain stronger erosion resistance by adopting different anode materials.Adopt the iron negatively charged ion on steel plate, to carry out technology B and compare, the enhanced resistance to salt(spray)fog is provided with adopting Zinc material.
Table O
The result of table O shows in order to set up the Corrosion results of the ASTMB117 that mineral lattice obtains with different anode material positively charged ion mineralising processing cold-rolled steel and electrogalvanizing steel plate.
Example 22
This example set forth on layer mineral adopt the second layer in case provide further erosion resistance (second layer generally comprise have can with the compound of layer mineral bonded hydrophilic composition).
Motor shaft according to example 10 mineralisings is contacted with second coating.These used two kinds of coating are 4-ethyl-ortho-silicate (TEOS) or organofunctional silane (VS) in the coating of axle.Table P-A and P-B have also listed the influence of heating second coating.Table P-A and P-B show the effect to B technology of the present invention of TEOS and vinyl silanes.
Table P-A
Table P-A shows the performance effect to B technology of TEOS and heat.
Table P-B
The DI=deionized water
A151=vinyltriethoxysilane (Witco)
A186=β-(3, the 4-epoxycyclohexyl) ethyl-trimethyl silane (Witco)
A187=γ-epoxypropyl-Trimethoxy silane (Witco)
Table P-B shows the effect that vinyl silanes is handled ElishaB.
Table P-A shows that thermal treatment has improved erosion resistance.These results also show if be used in combination with TEOS can shorten depositing time.The application of TEOS and heating has 100% improvement than the technology B of standard.The use of vinyl silanes shows the performance that can improve technology B.One of additional benefit of organic coating is that can obviously reduce table can and repel water.
Example 23
This example has been described when substituting possible phosphoric acid salt with the E-coat system be used for forming the assessment of the processing method of the present invention of coating on naked and galvinized steel.This assessment comprises four classes: apply the E-coating on mineral surface; E-coating bonding; The corrodibility test of mineral/E-coat system; And the ultimate analysis of mineral coating.With phosphoric acid salt is that contrast is assessed four mineral coatings (technology A, B, C, D).The electronics coating comprises the Resins, epoxy blocked isocyanate coating that negative electrode applies.
Table Q
It is found that the E-coating can be applied on the mineral surface that is formed by technology A-D equably and best applying occurs on the mineral that form with technology A and B.Find that also surfaces A and B bathe the E-coating or E-coating curing technology is not had tangible deleterious effect.This bond test shows that surfaces A, B and D compare the binding property that can improve the E-coating with phosphoric acid salt.Similarly the result on galvinized steel surface C and D in also can see.Surface B and D show usually than other evaluated modification to have bigger erosion resistance.
In order to understand the relation between coating and the performance, carry out ultimate analysis.Demonstrate, the depth section of coating B and D is very big,＞5000 dusts.
Example 24
This example has been verified the effect that processing method counter stress corrosion of the present invention is split.Carry out these tests so that check the influence of the susceptibility that electrolysis treatment of the present invention is split to AISI304 stainless steel stopple coupon counter stress.This test discloses the pitting resistance of implementing technology of the present invention sample afterwards and makes moderate progress.In this testing sequence, use four AISI304 Corrosion of Stainless Steel stopple coupons.Do not carry out surface treatment and test a sample.After the electrolysis process of the method B of embodiment 16, test another sample.
Method A (iron(ic) chloride pittingtest) exposure test sample according to ASTM G48.These tests comprise at room temperature in ferric chloride Solution (about by weight 6%) and expose 72 hours.
Table R has provided the result of corrodibility test.Stopple coupon with electrolysis treatment is corroded by the end grain that untreated stopple coupon stood mainly.
The result of table R-ASTM G48 spot corrosion test
ASTM G48,304 are exposed in the iron(ic) chloride, and 72 hours, ambient temperature
Example 25
This example has verified that processing method of the present invention can be improved binding property and erosion resistance when the lacquer top layer is carried out pre-treatment.Technology B according to example 16 forms a layer mineral on steel plate.With the plate of handling be immersed in 5% two-1, in 2-(trimethoxy silylation) ethane (BSTE-Witco) and carry out drying, be immersed in then in γ-epoxypropyl-Trimethoxy silane (Witco) solution of 2% vinyltriethoxysilane (Wtco) or 2%.In order to compare the steel plate that preparation is only used BSTE, handled with the steel plate and the zinc phosphate of vinyl silanes processing then.With heat curing-type epoxy-based lacquers (Corvel 10-1002 by Morton) all plates are carried out powder coatedly, thickness reaches 2 mils.Draw these plates and make it in ASTM B117 salt fog, expose 500 hours with carbonization point tool.After the exposure, take out plate and rinsing, dry 1 hour then.Scrape off cut with scraper, remove any paint vehicle, and measure remaining slit owing to incision.The plate that zinc phosphate that contrast is implemented and BSTE handle demonstrates the average gap size of 23mm.Demonstrating with the mineralized plate of silane aftertreatment does not have measurable slit except cut.The mineralising technology that combines enforcement with silane treatment demonstrates than independent enforcement silane treatment and improves to some extent.Real this layer mineral of this illustration provides BSTE layer better adherent surface or thin layer.
Example 26
This example has been described containing the layer mineral of the present invention that forms on the metallic surface and can be used as electrical insulator.Utilize Miller hand-held point welding machine (model is #AASW 1510M/110V input value/4450 two stage amplifier output valves) to assess the insulating property of the steel plate of mineral coating.Also assessing control board is cold-rolled steel (CRS) and 60g galvanized steel.All plate thickness are .032 ".The employing tip also keeps about 5.0 seconds time.Check associativity, discolouration and the weld size of the spot welding of being finished.CRS and galvanized sheet demonstrate associativity preferably and have about .25 " the dark solder joint of diameter.The steel plate of mineral coatings does not have enough electric weight to produce solder joint and has the .06 of variable color slightly " circle of diameter.
Example 27
This example has been described and formed thin layer of the present invention on the zinc surface that utilizes the commercial sherardising process of buying to obtain.
The mineralizing solution that 1900mL is comprised 10wt.%N sodium silicate solution (PQ Corp) and 0.001wt.% iron(ic) chloride injects in 2 liters of glass beakers.On the stirring hot plate, solution is heated to 75C.A sight glass is put into the top of beaker, so that vaporization losses minimum and solution obtains heating simultaneously.Two standard A CT cold-rolled steels (100008) test board (3 inches * 6 inches * 0.032 inch) is also hung the copper bar contact that hangs down from the copper rod of 3/16 inch diameter as anode.Negative electrode is that diameter is that 1.1875 inches, thickness are 0.125 inch and the Sherardized washer of one 0.5 inch centre hole is arranged.By electric wire washer and steel anode are connected on the power supply with stainless steel cover holder folder.Power supply is Hull Cell rectifier (a 3-electronic circuit).At 2.5 volts of constant (1 ampere/inch of ∽
2Current density) voltage under electrolysis treatment washer 15 minutes.Washer is taken out the back under external environmental condition, carry out drying from CM bathes.Implement the SaltSprayTest (ASTM B117) of postorder and compare with untreated contrast washer, the result is as follows:
Example 28
This example has been verified the character of utilizing aftertreatment technology to improve thin layer of the present invention.
Utilize the groove that the dipping well heater will contain 25 gallons the mineralizing solution that comprises 10wt.%N sodium silicate solution (PQ Corp) and 0.001wt.% iron(ic) chloride to be heated to 75C.Six standard A CT cold-rolled steels (100008) test board (3 inches * 6 inches * 0.032 inch) is also hung the copper bar contact that hangs down from the copper rod of 3/16 inch diameter as anode.The copper anode bus that 3/16 inch copper rod contact is 0.5 inch, this bus links to each other with rectifier.Three standard A CT electro-galvanized steel test boards (2 03 inch * 06 inches * .030 of ACT E60 EZG inch) are suspended between three steel anodes of two rows, and these anodes are approximately 3 inches apart from the distance of electro-galvanized steel test board.Electrogalvanizing steel plate is linked to each other with negative busbar.Under 12 volts constant voltage, handled the electro-galvanizing test board 15 minutes.Electric current is approximately 40 amperes at first, exposes 15 minutes and drops to about 25 amperes afterwards.In the following aqueous solution, these plates are carried out aftertreatment.
As implied above, some samples are carried out rinsing, handle immediately then, earlier some samples are carried out drying, handle with the shown aqueous solution then.After the drying, with two-layer flat non-zinc-plated (7776) high-quality ruthenium osmiridium protection enamel spraying sample 3,6,7 and 10.0.00145 inch of final dry film coat-thickness average out to.Under external environmental condition,, secondly placed 24 hours wet the exposure in (ASTM-D2247) with dry 24 hours of the test board that is coated with, then before carrying out bonding test under external environmental condition drying 24 hours.As follows, the plate of handling is carried out SaltSprayTest (ASTM-B117) or adhesion of coatings property testing (ASTM D-3359).
The above results shows that zirconyl carbonate ammonia has favourable effect to the improvement of the erosion resistance on the binding property of postorder coating and uncoated surface.The salt fog result shows by rinsing immediately and is exposed in the strong phosphoric acid and can weaken erosion resistance.
Example 29
This example has been verified the effect that processing method counter stress corrosion of the present invention is split.Carry out these tests so that check the influence of the susceptibility that electrolysis treatment of the present invention is split to AISI304 and 316 stainless steel stopple coupon counter stresses.This test discloses the pitting resistance of implementing technology of the present invention sample afterwards and makes moderate progress.Comprise three corrosion stopple coupon steel in each test group.Electrolysis treatment (15 minutes) at the method B of embodiment 16 is tested the mineralising sample afterwards.
Method A (iron(ic) chloride pittingtest) exposure test sample according to ASTM G48.These tests comprise at room temperature in ferric chloride Solution (about by weight 6%) and expose 72 hours.
Table R has provided the result of corrosion test.Stopple coupon with electrolysis treatment is corroded by the end grain that untreated stopple coupon stood mainly.
Mineralising of the present invention is handled the number that has reduced the spot corrosion that is occurred effectively.
Example 30
This example has been verified the effect of method of the present invention to the resistance to breakage of improving following substrate.Before the described mineral processing of method B (5 and 15 minutes) of using, the stress corrosion sample of 9 U-shaped bendings of being made by the AISI304 stainless steel is carried out heat-sensing processing 8 hours under 1200F as example 16.Each test group comprises 8 inches long, 2 inches wide and 1/16 inch three thick sample.Use after the mineral processing, be put on the stainless steel tube cross section sample and extruding.Identical with described in the ASTM C692 of exposure order, and comprise around the U-Bemd sample that conforms to its shape and apply foam gas heat insulator.A kind of 2.473g/L NaCl solution of combination is incorporated on the tensile surface of sample continuously by the hole in the isolator.Regulate flow velocity and wet/dried condition so that obtain the part of sample.Utilize cartridge heater and heat-transfer fluid that the cross section of pipe is carried out the inside heating and test temperature is controlled at 160F.This test was carried out 100 hours, visual inspection test sample then, and the result is as follows:
Mineralising of the present invention is handled and has been reduced the number and the length of breaking and occurring effectively.
Example 31
This example has been described with the chromic salt 1 of routine and has been handled zinc-plated improved thermotolerance of parking brake spool end connector telescopic and the erosion resistance of comparing according to the present invention's processing.
Hours and erosion resistance (exposure of ASTM B-117 salt fog) that heat exposes
*Carry out cathode treatment according to the present invention
+ above each value is represented the mean value of 6 single samples
Length is approximately the cylindrical galvanizing line pipe end adapter sleeve that 1.5 inches, diameter are approximately 0.50 inch is divided into six groups.One group of surface treatment of not carrying out postorder.Handle with the commercial cleaning chromate conversion type coating buied for one group.Use chrome yellow hydrochlorate transformant to handle for one group, use olive brown chromate conversion type coating to handle for one group.Two groups are carried out negative electrode charging 15 minutes under 12 volts (70-80 ℃) in the bath that comprises deionized water and about 10wt.%N sodium silicate solution.One of anticathode charging group is carried out drying and is not further handled.Another group is carried out rinsing with following solution successively: deionized water, comprise the 2vol.%1 that has of 10wt.% Denatured alcohol, the deionized water solution of 2 (two three methylamino ethoxy silylation) ethane (providing by Aldrich), comprise the deionized water solution with 2vol.% epoxy silane (provided by OSF Specialties commercial, commodity are called Silquest A-186) of 10wt.% Denatured alcohol commercial.
Each group in these six groups is segmented again and be exposed in the following condition: (A) do not heat up.(B) 200
15 minutes.(C) 400
15 minutes.(D) 600
15 minutes.Perhaps (E) 700
15 minutes, and in ASTM B-117 salt fog, test till breakage.The result is as implied above.
Example 32
This example has been described a kind of technology that comprises processing method of the present invention, carries out aftertreatment after technology of the present invention.Aftertreatment comprises makes previously treated goods contact with the water-bearing media that contains water-soluble or dispersed compound.
Processing method of the present invention is carried out in a kind of ionogen, joins in the process tank of the deionized water that contains 2.8L by the N sodium silicate solution with 349.98g, prepares this ionogen.With solution mixing 5-10 minute.The iron(ic) chloride of 0.1021g is mixed in the deionized water of 352.33g.Making these two kinds of solution then is that water glass and iron(ic) chloride merge stirring in the process tank internalization.Joining jar a certain amount of deionized water interior is 3.5L so that make final liquor capacity.ACT zinc (plating) plate was flooded in this ionogen about 15 minutes as negative electrode.Anode comprises the niobium screen cloth with the platinum clad.
Join by compound and to prepare following post-processing medium in the deionized water listed amount:
A) zirconium acetate (200g/L)
B) zirconyl chloride (100g/L)
C) Calcium Fluoride (Fluorspan) (8.75g/L)
D) aluminum nitrate (200g/L)
E) sulfuric acid U.S. (100g/L)
F) Tin tetrafluoride. (11) (12g/L)
G) zinc sulfate (100g/L)
H) titanium fluoride (5g/L)
I) Zirconium tetrafluoride (5g/L)
J) titanium chloride (150g/L)
K) tin chloride (20g/L)
Test the erosion resistance of the zine plate of aftertreatment according to ASTM B-117.Below listed test result.
Example 33
This example has been described doping agent has been joined the ionogen (perhaps bathing) that is used for implementing processing method of the present invention.In following each example, work piece comprise negative electrode, and anode comprises the niobium screen cloth with the platinum clad.The doping agent for preparing ionogen and the adding amount of illustrating according to the method for example 32.To comprise that zinc, iron or 304 stainless ACT test boards are impregnated in the ionogen and introduce shown electric current.
Example 34
This example has been described and has been applied encapsulant (for example Enthonw (R) encapsulant) before with acidic rinse liquid activation mineralising surface.Make length be approximately the end connector sleeve that 1.23 inches, diameter are approximately 5/8 inch zinc plated mild carbon steel cylindrical thread cutting mechanism and resolve,, in the plating shielding of laboratory size, electroplate again and mineralising then so that remove zinc-platedly.The mineralising sleeve is flooded aftertreatment in citric acid (A group) or nitric acid (B group), and apply the commercial encapsulant of buying (Enthone (R) C-23).After 24 hours, the sleeve that seals is carried out the ASTMB-117 salt fog expose test.The A group is exposed 144 hours till observing white rust in ASTM B-117, and the B group about 120 hours have been exposed before the white rust outbreak.
Utilize following parameter on the processing line of laboratory size, to carry out mineralising:
Tankage: 25 gallons
Orientation: Stirling 6X12 inch minisize shielding
Anode: platinized niobium screen cloth
Working area: 736 divide inch equally
Job category: galvanized spool end connector sleeve
Workload: 184
Working time: 15 minutes
Running voltage: 12.0 volts
Ultimate current: AVG28 ampere
Operating temperature: 78-79.5 ℃
Electrolyte solution: deionized water, contain the silicate solutions of the 10wt.% of iron doping agent
Power supply: Aldonex model T-224-7.5 CR-CCV
The aftertreatment of following enforcement mineralising technology: dipping is 5 seconds in the Bacote of 20wt.% (R) 20 zirconyl carbonate ammonia, then in New Holland Model K-11 spin moisture eliminator, spinning dry 30 seconds under the ambient temperature, 15 seconds forward circulation wherein, 15 seconds recycle back.The time and the temperature of every step process of implementing in this example have been listed in the following table.
Example 35
This example has been described and has been implemented processing method of the present invention, and wherein anode comprises the niobium screen cloth.Negative electrode comprises the ACT electrolytic galvanized sheet.
By with the N sodium silicate solution of 349.98g, the FeCl of 0.1021g
3Merge so that the cumulative volume of solution reaches 3.5L with enough distilled water, prepare ionogen.Zine plate is every took turns operation 15 minutes and need not rinsing and just begin drying.Before each is taken turns and plate after the drying, the weighing zine plate is so that be determined in the electrochemical process weight pick-up by negative electrode caused.After experiment beginning, 10 is taken turns, 20 take turns after and 23 also want weighing niobium screen cloth after taking turns.This makes can calculate the anodic weight pick-up.In all are taken turns, voltage is set in 12.0V.
23 each data of taking turns in taking turns that in following table, can find to be finished.Following data show that the electric current and the voltage that pass through between the motor all keep stable in all are taken turns.
Table: in the water glass ionogen, utilize a plurality of samsaras of niobium screen cloth anode and zinc negative electrode
Example 36A-36C shows that using processing method of the present invention handles parts and the assembly that is used to make motor.
Example 36A
This example shows utilizes processing method of the present invention to handle the assembling goods that comprise the motor tinkertoy module.
Direct current (9-10 ampere at 80C and 12V; 9.75 the mean value of ampere), the electric motor tinkertoy module that 2.75 inch diameter X0.40 inches are thick was handled 15 minutes, this tinkertoy module comprises 13 independent laminated products that are casted into together and comprise high si fe alloy.This processing of enforcement in the jar of the mineralizing solution of the iron(ic) chloride that contains 25 gallons N water glass that comprises 10wt.% (PQ Corp.) and 0.001wt.%.Adopt the niobium screen cloth anode that is coated with platinum of size constancy, and by with the copper hook with its suspension and negative electrode connects this tinkertoy module, described copper hook passes the centre hole insertion of tinkertoy module.After finishing dealing with,, can remove excessive solution by under ambient temperature, in the blue formula New Holland spin drying machine of 6 inches of laboratory sizes, the spin in positive 30 seconds, anti-30 seconds of this tinkertoy module being circulated.Thereafter, at two (triethoxysilyl) ethane that comprise 2vol.% (from Gelest, Inc. CAS#16086-37-4) and in the solution of the ethanol of 98vol.% (10vol.%) solution and deionized water (90vol.%) this tinkertoy module was flooded for 5 seconds, spin as previously mentioned then so that remove excessive solution.Thereafter, tinkertoy module is immersed in second solution of silane, the preparation of this solution and first solution of silane are similar, just contain β-(3, the 4-epoxycyclohexyl) ethyl-trimethyl silane (from Gelest, the CAS#3388-04-3 of Inc.).Tinkertoy module is spinning off excess solution and under ambient temperature after dry 1 hour certainly, be coated with according to the epoxy finish (B18-Magni Industries) of following operation with the metallic particles filling: dipping is so that cover fully, make excessive finish paint drip, in New Holland spin drying machine, spin as mentioned above then.In the convection furnace of laboratory, make this coating curing 10 minutes in 90C, solidified again 20 minutes at 205C then., by utilize ASTM B-117 method place salt fog expose altogether 500 hour this tinkertoy module, assess the erosion resistance of this assembly thereafter.When exposing 168 hours, the surface less than 5% has the red rust product and produces.When exposing 500 hours, 25% surface has main edge and inner red rust from tinkertoy module, obviously, does not have the coating adhesion loss.
Example 36B
This example has been described the surface that utilizes processing method of the present invention to form and has been reduced the bonding of molten metal.
Direct current (4.8-10.7 ampere at 75-77C and 12V; 6.4 the mean value of ampere), the motor core laminates that will contain 2.75 inch diameters of high silicon steel was handled 15 minutes.In the beaker of the mineralizing solution of the iron(ic) chloride that contains N water glass (PQ Corp.) that 1.8L comprises 10wt.% and 0.001wt.%, implement this processing.Adopt two steel anodes (the 3X6 cold-rolled steel stopple coupon of standard, ACT laboratory), and by laminates is suspended on be fastened on the copper cash and the stainless steel cover holder that links to each other with the edge of laminates folder on, and negative electrode connects this clean laminates.After finishing dealing with,, can remove excessive solution by under ambient temperature, in the blue formula NewHolland spin drying machine of 6 inches of laboratory sizes, the spin in positive 30 seconds, anti-30 seconds of this laminates being circulated.Thereafter, at two (triethoxysilyl) ethane that comprise 2vol.% (from Gelest, Inc. CAS#16086-37-4) and in the solution of the ethanol of 98vol.% (10vol.%) solution and deionized water (90vol.%) this laminates was flooded for 5 seconds, spin as previously mentioned then so that remove excessive solution.Thereafter, laminates is immersed in second solution of silane, the preparation of this solution and first solution of silane are similar, just contain β-(3, the 4-epoxycyclohexyl) ethyl-trimethyl silane (from Gelest, the CAS#3388-04-3 of Inc.).Laminates is spinning off excess solution and under ambient temperature after dry 1 hour certainly, high-temperature finish system (B68/B70-Magni Industries) with the metallic particles filling is coated with according to following operation: dipping is so that cover fully, make excessive finish paint drip, in New Holland spin drying machine, spin as mentioned above then.In the convection furnace of laboratory, make this coating curing 10 minutes in 90C, solidified again 20 minutes at 288C then.Assess resistance that this laminates with molten aluminum contact thereafter.In about 1500 ° metallic crucible, melt aluminium alloy (Alcanal 801737).This finishing coat overlapping piece temporarily is impregnated in the molten aluminum midway, when observation has aluminium to adhere on the laminates, this laminates is not taken out then.Observing that aluminium has covered the edge of laminates and along dipping when the edge is full of stacked groove, should flood 5 seconds of repetition.After the cooling of this laminates, can be observed the face that manually peels off aluminum coating and this laminates from the laminates edge and be coated with and do not reveal.This uses confirmation, can utilize the present invention to form a barrier between steel laminates and molten aluminum.
Example 36C
This example has been verified and has been utilized processing method of the present invention to come partially disposed assembling goods.
Direct current (6-7 ampere at 75-80C and 12V; 6.75 the mean value of ampere), the stacked magnetic core assembly of the motor that 2.75 inch diameter X6 inches are long was handled 15 minutes, this assembly comprises and a plurality ofly independent be casted into together and and be assembled into laminated product (high si fe alloy) on the simulation axle.This processing of enforcement in the jar of the mineralizing solution of the iron(ic) chloride that contains 25 gallons N water glass that comprises 10wt.% (PQ Corp.) and 0.001wt.%.Adopt the niobium screen cloth anode that is coated with platinum of size constancy.Artificial position of rotating this assembly and assembly makes 0.5 inch outside one side having only magnetic core also flood in solution on the bus of negative electrode connection, and assembly keeps rotating.After finishing dealing with,, can remove excessive solution by under ambient temperature, in the blue formula New Holland spin drying machine of 6 inches of laboratory sizes, the spin in positive 30 seconds, anti-30 seconds of this tinkertoy module being circulated.Observe from the end of assembly, the outside surface of magnetic core (mineralising zone) is different with the center of magnetic core on visual.
Example 37
This example is visual utilizes processing method of the present invention to form flexible, bonding and corrosion resistant surface on rivet.
Load 18 inch diameters, 36 inches long plating bucket with 150 pounds of galvanized rivets that are coated with the 0.2-0.3 mil in advance.Each rivet has the head of 0.75 inch diameter, the bar and the total length of 0.25 inch diameter is 1.05 inches.In 180 gallons the solution under the 75C temperature in the rectangle jar rivet being carried out mineralising handled 30 minutes.Utilize and keep this temperature by the outflow of Chromalox well heater (NWHIS-18-075P-E4XX).Be beneficial to AldonexUltimatic DC power supply (model is T-412-20CFR-COV) at 12V supply direct current and electric current in the scope of 102-126 ampere (113 amperes mean values).Negative electrode connects this bucket, and anode is made of the niobium screen cloth that the platinum of the size constancy that forms in the jar of paraboloidal is coated with, thus barrel in side and bottom by anode part around.After mineralising is finished dealing with, bucket is produced 30 seconds so that make the excess solution drip-dry from solution, bucket was rotated 30 seconds in deionized water so that drip-dry and from solution, producing once more.Then rivet is poured into from bucket in the dipping-spin indigo plant of the commercial size of standard, and utilized in the anti-New of the circulating in HollandK-90 spin drying machine of 30 seconds normal circulation and 30 seconds from spinning off excessive solution.Thereafter, at two (triethoxysilyl) ethane that comprise 2vol.% (from Gelest, Inc. CAS#16086-37-4) and in the solution of the ethanol of 98vol.% (10vol.%) solution and deionized water (90vol.%) this rivet was flooded for 5 seconds, spin as previously mentioned then so that remove excessive solution.Thereafter, rivet is immersed in second solution of silane, the preparation of this solution and first solution of silane are similar, just contain β-(3, the 4-epoxycyclohexyl) ethyl-trimethyl silane (from Gelest, the CAS#3388-04-3 of Inc.).From spin off excess solution and under 49-54C with dry 5 minutes of rivet, spin simultaneously.In Ronci dipping-spin machine, utilize epoxy finish (B17-Magni Industries) the coating rivet of dipping-spinning technology with the metallic particles filling.In comprising the commercial band oven of 90C exposure zone, make this coating curing 10 minutes, solidified again 20 minutes at 205C then.Then, rivet (have or do not have B17 finish paint) is exposed in the salt fog, assesses the erosion resistance of rivet by utilizing the ASTMB-117 method.The result is as follows:
Only be zinc-plated rivet: mean hours number=124 red rusts that occur red rust first reach 5% mean hours number=288
Rivet w/ Kuang Wu ﹠amp; Silane: mean hours number=416 red rusts that occur red rust first reach 5% mean hours number=728
Rivet w/ mineral, silane, B17 coating: mean hours number=1184 red rusts that occur red rust first reach 5% mean hours number=1336
Example 38
This example has been described Dorriform (R) E (A31) and the adhesion characteristic of Dorritech (R) Silver (B17) on the galvanized sheet with mineralising of the present invention surface.By with each 4 " * 12 " plate be suspended between the niobium anode of platinum coating of two orthogonal size constancies in 25 gallons of solution described in the example 28, implement mineralising technology.Under the direct current of 70-80C and 12V, carried out mineralising 15 minutes.Electric current is in the scope of 22-35 ampere (27 amperes mean values).Dorriform and Dorritech are the commercial heat curing-type epoxy finishs of buying.Come aftertreatment mineralising of the present invention surface by carrying out rinsing according to example 36 usefulness silane, difference is to carry out the external environment dry air and is beneficial to static suspension to replace New Holland spin drying machine.
Three dome height (0.150,0.200,0.300 inch) on Timius Olsen machine locate to carry out binding property test and every Gerneral Motor GM6190M branch one-level.Also carry out the intersection binding property grade of every Gerneral Motor GM6190M.Testing scheme GM6190M and GM907P are incorporated herein by reference at this.Can test this binding property by the 3M610 band that applies and remove standard.
With 4 * 12 inches plates of epoxy coating coating, carry out thermofixation then.With 0.150,0.200,0.300 inch of these samples protuberance and the binding property grade of testing every GM6190M.Sample every GM9071P value of intersecting and being write down all like this is the branch one-level just.
Every GM9071P of coating finished product is with fusible bonding grade to show, adopts the vanish system method for pretreating not have coating to be removed.This experiment representative does not have the result of the film of formation or bending.
For the Olsen tensile testing machine, just divide one-level with the every GM6190M of tensile plate that receives domed form, so that provide the photograph standard of paint loss.Corresponding coating finished product, this adhesion test is stricter than the test of GM9071P band adhesion test.Based on these grades, adopt the mineralising technology of the present invention of silane rinsing to increase binding property and satisfied above evaluation explanation.
Example 39
This example has been verified flexible, the erosion resistance on the surface that forms according to processing method of the present invention and the patience of secondary processes.
Load 6 inch diameters, 12 inches long plating bucket with being coated with galvanized 200 the parking brake spool end connector sleeves of 0.2-0.3 mil in advance.The length that each cylindrical sleeve records is that about 1.5 inches, diameter are about 0.5 inch, and has about 4.0 surface-area of dividing inch equally.In 25 gallons the solution under the 75C temperature in the rectangle jar sleeve being carried out mineralising handled 15 minutes.Utilize Aldonex DC power supply at 12V supply direct current and electric current in the scope of 20-32 ampere (24 amperes mean values).Negative electrode connects this bucket, and adopts the niobium screen cloth anode of the platinum coating of size constancy.After mineralising is finished dealing with, bucket is produced 30 seconds so that make the excess solution drip-dry from solution, from bucket, pour into then in the New Holland spin drying machine of 6 inches laboratory sizes, and utilize 30 seconds normal circulation and 30 seconds counter circulating in from spinning off excessive solution.Thereafter, at two (triethoxysilyl) ethane that comprise 2vol.% (from Gelest, Inc. CAS#16086-37-4) and in the solution of the ethanol of 98vol.% (10wt.%) solution and deionized water (90wt.%) this half sleeve was flooded for 5 seconds, spin as previously shown then so that remove excessive solution.Then, sleeve is immersed in second solution of silane, the preparation of this solution and first solution of silane are similar, just contain β-(3, the 4-epoxycyclohexyl) ethyl-trimethyl silane (from Gelest, the CAS#3388-04-3 of Inc.).From spin off excess solution and under ambient temperature with dry 5 minutes of sleeve, spin simultaneously.At the Bacote20 of 20wt.% (Magnesium Elektron) solution, contain in the solution of zirconyl carbonate ammonia second half sleeve flooded for 5 seconds; Drying then as mentioned above spins.Thereafter the sleeve with each above-mentioned two groups group is divided into two groups and is coated with each group in order to one of following finish paint: (A) clean is the epoxy finish (W86-Magni Industries) of water-based basically; And (B) clean be the polyurethane finish that contains 80.5wt.%Neorez R9637 (Zeneca Resins), 6.5wt.%N water glass (PQ Corp.) and 13.0wt.% deionized water of water-based basically.New Holland spin drying machine shown in more than utilizing applies coating by dipping-spin.In the convection furnace of laboratory, make W86 coating curing 10 minutes in 90C, solidified again 30 minutes at 177C then.In 60C polyurethane coating was solidified 10 minutes, solidified again 30 minutes at 125C then.In addition, preparation has the comparative group sleeve of above disclosed silane rinsing liquid as mentioned above, but this comparative group also will be curled on spool so that assess the ability that coating system is restrained oneself manufacturing process.Also under following curling condition, test two extra coatings: (C) epoxy finish (B18-Magni Industries) of metallic particles filling; (D) epoxy finish (B17-MagniIndustries) of metallic particles filling.In the convection furnace of laboratory, made B18 and B17 coating curing 10 minutes in 90C, solidified again 20 minutes at 205C then.Then, sleeve (curl or do not curl) is exposed in the salt fog, assesses the telescopic erosion resistance by utilizing the ASTMB-117 method.
The test-results of salt fog ASTMB-117
1) mineral+W86 does not curl: mean hours number=312 that occur white rust first occur the mean hours number of red rust=1584 red rusts first and reach 5% mean hours number=2112 (silane)
2): mineral+W86 does not curl: mean hours number=312 that occur white rust first occur the mean hours number of red rust=1244 red rusts first and reach 5% mean hours number=1744 (Bacote20)
3) mineral+W86 does not curl: mean hours number=280 that occur white rust first occur the mean hours number of red rust＞408 red rusts first and reach 5% mean hours number＞408 (silane)
4) mineral+PU does not curl: mean hours number=312 that occur white rust first occur the mean hours number of red rust=1456 red rusts first and reach 5% mean hours number=1596 (silane)
5) mineral+PU does not curl: mean hours number=320 that occur white rust first occur the mean hours number of red rust=1460 red rusts first and reach 5% mean hours number=1652 (Bacote 20)
6) mineral+PU curls: mean hours number=320 that occur white rust first occur the mean hours number of red rust＞408 red rusts first and reach 5% mean hours number＞408
7) mineral+B17 curls: mean hours number＞408 that occur white rust first occur the mean hours number of red rust＞408 red rusts first and reach 5% mean hours number＞408
8) mineral+B18 curls: mean hours number＞408 that occur white rust first occur the mean hours number of red rust＞408 red rusts first and reach 5% mean hours number＞408
Example 40
This example has been verified when being coated with heat curing-type epoxy face flexible, the erosion resistance on the surface that forms according to processing method of the present invention and the patience of secondary processes.
Load 6 inch diameters, 12 inches long plating bucket with being coated with the galvanized 15 pounds of rivets of 0.2-0.3 mil in advance.Each rivet has the head of 0.75 inch diameter, the bar and the total length of 0.25 inch diameter is 1.05 inches.In 25 gallons the solution under the 70-75C temperature in the rectangle jar rivet being carried out mineralising handled 15 minutes.Utilize Aldonex DC power supply at 12V supply direct current and electric current in the scope of 22-28 ampere (24 amperes mean values).Negative electrode connects this bucket, and 4 inches * 12 inches the cold-rolled steel stopple coupon (ACT laboratory) that adopts two standards is as anode and the both sides that are arranged in jar.After mineralising is finished dealing with, bucket is produced 30 seconds so that make the excess solution drip-dry from solution, in rinsed with deionized water liquid, rotated 30 seconds and drip-dry once more then, from solution, rotate simultaneously.Then rivet is poured into from bucket in the New Holland spin drying machine of 6 inches laboratory sizes, and utilized 30 seconds normal circulation and 30 seconds anti-circulation to spin off excessive solution certainly.Thereafter, at two (triethoxysilyl) ethane that comprise 2vol.% (from Gelest, Inc. CAS#16086-37-4) and in the solution of the ethanol of 98vol.% (10wt.%) solution and deionized water (90wt.%) rivet was flooded for 5 seconds, spin as previously shown then so that remove excessive solution.Then, rivet is immersed in second solution of silane, the preparation of this solution and first solution of silane are similar, just contain β-(3, the 4-epoxycyclohexyl) ethyl-trimethyl silane (Silquest A-186, OSI Specialties).From spin off excess solution and under ambient temperature with dry 5 minutes of rivet, spin simultaneously.In Ronci dipping-spin machine, utilize epoxy finish (B17-Magni Industries) the coating rivet of dipping-spinning technology with the metallic particles filling.In comprising the commercial band oven of 90C exposure zone, make this coating curing 10 minutes, solidified again 20 minutes at 205C then.Prepare a comparative group rivet with same group of zinc-plated rivet, but utilize the convection current of xanchromatic hexavalent chromate to be coated with the proxy-mineral coating, carry out same coating with Magni B17 thereafter.Then, rivet is installed on the papering as accumulation and non-accumulation sample.By utilizing ASTM B-117 method that rivet is exposed in the salt fog, assess the erosion resistance of rivet.The result is as follows: (hours of exposure)
Mineral+B17 does not pile up: mean hours number＞3240 that occur white rust first occur the mean hours number of red rust＞4736 red rusts first and reach 5% mean hours number＞5400
Mineral+B17 piles up: mean hours number=1680 that occur white rust first occur the mean hours number of red rust＞5400 red rusts first and reach 5% mean hours number＞5400
Chromic salt+B17 does not pile up: mean hours number=928 that occur white rust first occur the mean hours number of red rust=2360 red rusts first and reach 5% mean hours number=2856
Chromic salt+B17 piles up: mean hours number=72 that occur white rust first occur the mean hours number of red rust=888 red rusts first and reach 5% mean hours number=1651
The above results shows that mineral processing makes the hexavalent chromate that is combined with the B17 finish paint have superior performance, and as what bulk property disclosed, this mineral processing also has goodish anti-damageability.
Example 41
This example has been described the fluoropolymer that will contain finish paint and has been applied on the mineralising surface.Utilize Sterling 6 inch diameters, 12 inches miniature buckets of long rotation, in 25 gallons of solution under the temperature of 70-75C in the rectangle jar following five kinds of parts are carried out mineralising and handle.
4.25 inch is long, the zinc-plated B7 alloy double hook bolt (19) of 5/8 inch diameter
The zinc-plated 2H nut of 5/8 inch diameter
Zinc-plated 10.9 grades of flat head screws of the M10 part spiral that 60mm is long
2.25 inch is long, the zinc-plated level 8 six flange angle type flat head screws of the complete spiral of 3/8 inch diameter
2.25 inch is long, the zinc-plated level 8 six flange angle type flat head screws of the part spiral of 3/8 inch diameter
In same the wheel, handle C, D and E group, and in independent one takes turns, handle A﹠amp; The B group.For handling C, D﹠amp; The same wheel of E group, utilize Aldonex DC power supply at 12V supply direct current and electric current in the scope of 25-30 ampere (27 amperes mean values).And be used to handle A﹠amp; That electric current of taking turns of B group is in the scope of 23-32 ampere (27 amperes mean values).Negative electrode connects this bucket and is being used to handle A﹠amp; During taking turns, adopt that of B group niobium screen cloth anode of the platinum coating of size constancy.And be used to handle C, D﹠amp; During taking turns, that of E group adopt 4 inches * 12 inches cold-rolled steel stopple coupon (ACT laboratory) of six standards as anode.After mineralising is finished dealing with, bucket is produced 30 seconds so that the drip-dry excess solution from solution, from bucket, pour into then in the New Holland spin drying machine of 6 inches laboratory sizes, and utilize 30 seconds normal circulation and 30 seconds anti-circulation to spin off excessive solution certainly.Thereafter, at two (triethoxysilyl) ethane that comprise 2vol.% (from Gelest, Inc. CAS#16086-37-4) and in the solution of the ethanol of 98vol.% (10wt.%) solution and deionized water (90wt.%) these parts were flooded for 5 seconds, spin as previously shown then so that remove excessive solution.Then, these parts are immersed in second solution of silane, the preparation of this solution and first solution of silane are similar, just contain β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (from Gelest, the CAS#3388-04-3 of Inc.).From spin off excess solution and under ambient temperature with dry 5 minutes of parts, spin simultaneously.
The zinc-plated threaded stud of mineralising 5/8 inch diameter and with above-mentioned solution of silane rinsing uses fluoropolymer finish paint (Xylan (R) that is provided by Whitford) to be coated with then.All flat head bolts receive two-layer 1424/524 finish paint (viscosity: 49sec.#2Zahn, 72
), and one group of flat head bolt also receives metal filled epoxy (Magni B06J:49sec.#2Zahn, 72 under the Xylan finish paint
) priming operation.Require the color homogeneous of two-layer Xylan.The standard nut debond is on applied flat head bolt.Below listed the salt fog result.
Xylan 1424/524+ Kuang Wu ﹠amp on the zine plate; B silane
Xylan 1424/524+ mineral on the zine plate, Gui Wan ﹠amp; Magni B06J priming paint
* test is discontinuous in 5616 hours salt fog exposure
Xylan on zinc-plated (threaded stud that has nut)+Kuang Wu ﹠amp; Silane
*Test is discontinuous in 4008 hours salt fogs expose
*White rust occurs on the nut of the edge between the surface
Claims (1)
1. goods that comprise a conductive substrates, wherein at least a portion conductive substrates has a surface, wherein, described surface comprises: comprise at least a silicate, inorganic, not chromate-containing the first film, with second film that comprises silicon-dioxide on the first film, with at least a composition that applies that is coated on described second film, described composition comprises a member at least of selecting from the combination that following material constitutes: vinylformic acid, Resins, epoxy, the electronics coating that comprises the Resins, epoxy blocked isocyanate coating that negative electrode applies, latex, the aminoacrylic acid methyl esters, silane, the fluoropolymer class, alcohol acids, type siloxane, polyester, oils, gel-like, lubricating grease.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/532,982 US6322687B1 (en) | 1997-01-31 | 2000-03-22 | Electrolytic process for forming a mineral |
| US09/532,982 | 2000-03-22 | ||
| US09/775,072 | 2001-02-01 | ||
| US09/775,072 US6592738B2 (en) | 1997-01-31 | 2001-02-01 | Electrolytic process for treating a conductive surface and products formed thereby |
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| CN 200510090986 Expired - Lifetime CN1740401B (en) | 2000-03-22 | 2001-03-22 | An energy enhanced process for treating a conductive surface and products formed thereby |
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| CN102173244B (en) * | 2010-12-27 | 2013-08-21 | 东莞劲胜精密组件股份有限公司 | Surface printing process for leather paint layer |
| SI23452A (en) * | 2011-05-19 | 2012-02-29 | KOVINOPLASTIKA LOĹ˝ industrija kovinskih in plastiÄŤnih izdelkov d.d. | Process of electrolytic zincing with increased anticorrosive protection |
| CN105332031A (en) * | 2015-12-10 | 2016-02-17 | 苏州市嘉明机械制造有限公司 | Preparation process of insulated runner plate |
| CN113122885A (en) * | 2021-04-05 | 2021-07-16 | 莫日根 | Application of aluminum alloy composite board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040811A (en) * | 1988-08-12 | 1990-03-28 | 艾尔坎国际有限公司 | Be used for the surface-treated method and composition |
| US6015855A (en) * | 1997-01-31 | 2000-01-18 | Elisha Technologies Co Llc | Paint formulations |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264113A (en) * | 1991-07-15 | 1993-11-23 | Technology Applications Group, Inc. | Two-step electrochemical process for coating magnesium alloys |
| US5455080A (en) * | 1992-08-26 | 1995-10-03 | Armco Inc. | Metal substrate with enhanced corrosion resistance and improved paint adhesion |
| US5938976A (en) * | 1994-10-21 | 1999-08-17 | Elisha Technologies Co. L.L.C. | Corrosion resistant coatings containing an amorphous phase |
| EP0958410B1 (en) * | 1997-01-31 | 2006-05-17 | Elisha Holding LLC | An electrolytic process for forming a mineral containing coating |
-
2001
- 2001-03-22 CN CN200610109588XA patent/CN1920106B/en not_active Expired - Lifetime
- 2001-03-22 CN CN 200510090987 patent/CN1740402A/en active Pending
- 2001-03-22 CN CN 200510090986 patent/CN1740401B/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040811A (en) * | 1988-08-12 | 1990-03-28 | 艾尔坎国际有限公司 | Be used for the surface-treated method and composition |
| US6015855A (en) * | 1997-01-31 | 2000-01-18 | Elisha Technologies Co Llc | Paint formulations |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1740401A (en) | 2006-03-01 |
| CN1920106A (en) | 2007-02-28 |
| CN1920106B (en) | 2011-03-16 |
| CN1740402A (en) | 2006-03-01 |
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