CN1740401A

CN1740401A - An energy enhanced process for treating a conductive surface and products formed thereby

Info

Publication number: CN1740401A
Application number: CN 200510090986
Authority: CN
Inventors: 罗伯特·L·海曼; 威廉姆·M·多尔顿; 约翰·哈恩; 戴维·M·普赖斯; 韦恩·L·苏西; 尚德龙·拉维
Original assignee: Elisha Holding LLC
Current assignee: Acoo Ryder company
Priority date: 2000-03-22
Filing date: 2001-03-22
Publication date: 2006-03-01
Anticipated expiration: 2021-03-22
Also published as: CN1740401B; CN1740402A; CN1920106B; CN1920106A

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

A kind of enhancement process for handling conductive surface and the product being consequently formed

The subject requirement applying date of this paper is on 2 1st, 2001, application No. is 09/775, the equity of 072 U.S. Patent application, this application be the applying date be on March 22nd, 2000, application No. is 09/532, continue 982 part, and it is on August 6th, 1999 the applying date that the latter, which is, application No. is 09/369, 780 (present U.S. Patent No. U.S.6, 153, 080) continue part, 09/369, No. 780 are applied for that being is on July 24th, 1998 applying date, application No. is 09/122, continue 002 part, 09/122, No. 002 is applied for that being is on January 30th, 1998 applying date, by entitled " being used to form of Robert L.Heimann et al. proposition The part of the 09/016 of the electrolysis process of mineral ", 250 (present U.S. Patent No.s 6,149,794) is continued, and the entire disclosure text of above-mentioned application is incorporated herein by reference herein.Subject of the present invention requires proposition on January 31st, 1997, Provisional Application No. 60/036, the equity of 35U.S.C.111 (a), the 35U.S.C.1198 (e) of 024 U.S. Patent application and the equity under 35U.S.C.120 and No. 60/045,446 application propose on May 2nd, 1997, entitled " Mineral Deposition of non-equilibrium enhancing ".The disclosure of these provisional applications proposed in the past is incorporated herein by reference herein.

Invention field

This application involves a kind of on metal surface or conductive surface forms the process of deposit.The process using electrolysis process by for example containing mineral coating or film deposit on surface metal, containing metal or conductive.

Background of invention

Steel, the tin in other surfaces were cleaned using silicate already in electric clean operation.Electricity cleaning is typically used as the cleaning before electroplating operations.This article, the document " using silicate as the detergent in sheet tin preparation " are described by L.J.Brown in the plating that 2 months 1966 publish to be incorporated herein by reference herein.

The process that protective layer or film are formed by being electrolysed using anode process is disclosed in United States Patent (USP) U.S.3,658,662 (Casson, Jr. et al.) and the United Kingdom U.K.498,485, this two patents are incorporated herein by reference herein.

In publication on October 4th, 1994, the Riffe of entitled " method and apparatus for avoiding corrosion of metal structure " United States Patent (USP) U.S.5,352, it is described in 342 and electromotive force is applied on the zinc solvent containing coating, which is incorporated herein by reference herein.

Summary of the invention

The present invention forms the anode process of protective layer (such as protective layer is in about 100- about 2,500 angstroms of thick ranges) by providing in metal or containing metal substrate, solves Railway Project related with conventional practice.Can usually anode process be implemented as follows: the substrate contact (such as dipping) with conductive surface be arrived in the bath containing silicate or medium, wherein electric current is introduced in (such as passing through) bath and makes substrate as cathode.

Process of the invention can form the layer mineral including an amorphous matrix, which surrounds or blend the metal silicate crystals in substrate.The characteristic of layer mineral is described in more detail in the common trial being listed below and in commonly assigned patent application.

Using the conductive surface of process processing (such as forming layer mineral) of the invention can have in other characteristics higher corrosion resistance, the resistance of increase, heat resistance, flexibility, resistance to stress crack corrosion, to the adhesiveness of finishing coat.Processed surface has bigger corrosion resistance (such as ASTM B-117) than conventional trivalent or hexavalent chromate system in other beneficial characteristics.Process of the invention can provide the zinc-plate article of the resistance to white embroidery property of at least about 72 hours (and being typically larger than about 96 hours) with ASTM B-117 and at least about 168 hours (and being typically larger than about 400 hours) resistance to red embroidery property.It can provide corrosion resistance by using rinsing and/or at least one finishing coat of application.

Process of the invention has significant improvement than conventional method due to forming anti-corrosion layer such as layer mineral without the system with multi-solvents or containing solvent.Compared with conventional method, process of the invention is substantially without solvent.And refer to there is the volatile organic compounds (V.O.C.s) less than about 5wt%, generally less than about 1wt% in electrolytic environments " substantially without solvent ".

Process of the invention also has significant improvement than conventional method due to reducing (if not eliminating) containing chromate and/or phosphatic compound (and the attached work of the discharge using these compounds in other unfavorable environmental impact factors such as waste processing, electrotyping are exposed to the sun).Although process of the invention can be used to enhance chromated or phosphated surfaces, process of the invention can be with more replacing these surfaces to the surface of environmental beneficial.Therefore, process of the invention " substantially without chromate " and " substantially without phosphate ", to make product also substantially free of chromate (sexavalence and trivalent) and substantially free of phosphate.Process of the invention is also substantially free of the heavy metal in other materials such as chromium, lead, cadmium, cobalt, palladium.Mean there is chromate, phosphate and/or the heavy metal less than 5wt%, typically about 0wt% in the process for being used to prepare product or final products substantially without chromate, substantially without phosphate and substantially without heavy metal.Other than eliminating the technique containing chromate, method of the invention is yet formed compared with conventional chromate rubbing method with the bigger heat resistance in other characteristics, flexible coating.This improved heat resistance has widened processing range, can be in heat cure face coating, the stamping method/forming process, riveting implemented in for example other techniques of these techniques later for forming coating of the invention.

Compared with conventional electric cleaning procedure, the present invention is formed on the substrate in the cathode technique of layer mineral using silicate.Conventional electric cleaning procedure tries to avoid the formation of the product containing oxide (such as greenalite), and the present invention relates to the methods that one kind is used to form the product containing silicate (such as mineral).

The cross reference of related patents and patent application

Subject of the present invention is related to trying and commonly assigned WO 98/33960, non-provisional U.S. Patent Application Serial 08/850,323 (present U.S. Patent No. 6,165,257) jointly；Respectively on May 2nd, 1997 and on January 30th, 1998 propose 08/850, 586 (present U.S. Patent No.s 6, 143, and 09/,016 420), 853 (unauthorizeds), and Robert L.Heimann et al. proposed on January 31st, 1997 08/791, 337 (present U.S. Patent No.s 5, 938, 976), 08/791, No. 337 applications are Robert L.Heimann et al., the 08/634 of entitled " the corrosion-resistant Laemmli buffer system Laemmli for metal product ", continue the part of 215 (applying date is on April 18th, 1996) number applications, and 08/634, No. 215 applications are again Heimann et al., with The corresponding non-provisional U.S. Patent Application Serial 08/476 of WO 96/12770, continue the part of 271 (applying date is on June nineteen ninety-five 7), 08/476, No. 271 applications are non-provisional U.S. Patent Application Serials 08/327,438 (applying date be on October 21st, 1994, present U.S. Patent No. 5,714,093) part continue.

Subject of the present invention is related to the non-provisional U.S. Patent Application Serial Number 09/016,849 (agent certificate EL004RH-1) that the applying date is on January 30th, 1998, entitled " corrosion-inhibiting coating ".Subject of the present invention further relates to the applying date as on January 30th, 1998, entitled " aqueous gel combination and application thereof " (present U.S. Patent No. 6,033,495) non-provisional U.S. Patent Application Serial Number 09/016,462 (agent certificate EL005NM-1).These above-mentioned patents, patent application and publication are incorporated herein by reference herein.

Brief description

Fig. 1 is the circuit of one aspect for carrying out the present invention and the schematic diagram of device.

Fig. 2 is the schematic diagram using a technique of electrolytic method of the invention.

Detailed description of the invention

The present invention relates to it is a kind of metal or on conductive surface deposit or formed one layer of beneficial surface (such as coating or film containing mineral) process.The process using silicate containing medium (such as containing soluble mineral components or its precursor) and handled using electric Enhancement Method conductive surface (such as metal or on conductive surface obtain coating or film containing mineral)." coating containing mineral ", " mineralising film " or " mineral " is meant that, the relatively thin coating or film formed on metal or conductive surface, wherein at least a part of coating or film include that at least one mineral containing metal for example surround or the amorphous phase or matrix of incorporating crystals (including zinc silicate).Mineral and the mineral contained are limited in above-mentioned common trial and commonly assigned patents and patent applications, are incorporated herein by reference herein." electrolysis " either " electro-deposition " perhaps " electricity enhancing " is meant that wherein substrate is used as cathode by making electric current flow into or through the environment that the medium containing silicate is generated with conductive substrates (or with conductive surface) contact and simultaneously." metal contained ", " metal " or " metal " is meant that, thin slice, formed article, fiber, stick, particle in other structures, are coated with metallic surface at continuous length (such as coil and metal wire), and a kind of alloy of these structures using at least one metal and including metal is basis, included this metal has naturally occur or chemistry, mechanical or heat modification surface.The surface usually naturally occurred on metal will include that perhaps the thin layer film or thin layer contain at least one oxide, hydroxide, carbonate, sulfate, chloride to a film in other structures.By that can remove or be modified this surface naturally occurred using process of the invention.

Electrolytic environments can be obtained in any suitable manner, these modes include dipping substrate in other way, the coating containing silicate is applied in substrate, then apply electric current.It can determine the preferred method for obtaining the environment according to the size of foundation base in other parameters well known in electrodeposition, electrodeposition time, the voltage applied.By provide ultrasound in other forms, laser, ultraviolet light, RF, IR form energy can enhance the efficiency of electrolytic environments.Process of the invention can be segmented or operate continuously.

Medium containing silicate can be fluid bath in other methods, gel, spraying, to contact substrate with silicate containing medium.The example of silicate containing medium includes the bath containing at least one silicate in other methods, containing at least one silicate and a kind of gel of thickener.The medium may include a kind of bath, and this bath includes the compound at least one of other silicates potassium silicate, calcium silicates, lithium metasilicate, sodium metasilicate, release silicate moieties or type.This bath may include water, ethyl alcohol, ether of any polar support appropriate for example in other carriers.In general, this bath includes sodium metasilicate and deionized water and optionally at least one dopants.In general, at least one dopant is water-soluble or can be distributed in water-bearing media.

Medium containing silicate generally has alkaline ph values.In general, the range of pH value be greater than 9 or so-about 13 in the range of, generally in the range of about 11 about 10-.The medium is usually aqueous and including at least one water-soluble or water dispersible silicate, and the amount of silicate is in the range of being greater than 0- about 40wt.%, typically about 3-15wt.%, generally about 10wt.%.The silicate containing medium further includes at least one water dispersible or soluble dopant.Medium containing silicate does not include heavy metal, chromate and/or phosphate substantially usually.

Electrolytic environments can be prior to and/or with cleaning or rinsing (such as dipping/spray in treatment fluid), sound wave cleaning, the flowing of double countercurrent cascades after routine well known in the art and/or preconditioning technique, in such as other processing methods；Alkalinity or acidic treatment.By using post-processing technology appropriate, the adhesiveness of the solubility in other characteristics of the substrate surface formed by method of the invention, corrosion resistance (such as formation that white rust is reduced when handling the surface containing zinc), closure and/or finishing coat can be improved.If necessary, silane, the epoxy, latex, fluoropolymer, acrylic acid, titanate, zincate, carbonate in for example other coating can be used, closing, rinsing and/or face apply the post-processing surface.

In one aspect of the invention, pretreatment includes substrate to be processed being exposed to at least one of other compounds acid, in oxidant.It is as follows in other benefits in order to have the advantages that using pretreatment: removes excessive oxide or dirt, makes surface equipotential to carry out mineralising processing thereafter, by the surface conversion into mineral precursor.Conventional method for acid processing metal surface is in ASM, the Surface Engineering (1994) and U.S.6 of Vol.5, is described in 096,650, this two documents are incorporated herein by reference herein.

In one aspect of the invention, post-processing includes that substrate is exposed at least one carbonate source or its precursor.The example of carbonate includes at least a member in combination constituted by the following substances: gaseous carbon dioxide, lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, rubidium carbonate, rubidium bicarbonate, bicarbonic rubidium, cesium carbonate, ammonium carbonate, ammonium hydrogen carbonate, aminoquinoxaline and ammonium zirconyl carbonate.In general, carbon source is water-soluble.When using a kind of carbonate precursor (such as carbon dioxide), which passes through a kind of liquid (including the medium containing silicate) and be immersed in the liquid substrate.An a kind of specific example of post-processing approach appropriate is disclosed in U.S.2,462,763, the document is incorporated herein by reference herein.Another specific example of post-processing includes being exposed to processed surface in the solution as obtained from diluting ammonium zirconyl carbonate (1: 4) in distilled water (such as the Bacote provided as Magnesium Elektron Corp).If necessary, face painting (such as aqueous or aqueous finish paint) can be carried out to the surface of the post-processing.

In another aspect of this invention, post-processing includes heating the surface.Usual heat is enough enrichment surface of the invention, but not adversely affects to the physical property of following metallic substrates.Can in atmospheric conditions such as in other gases contain nitrogen in the environment of being heated.If necessary, before heating, surface of the invention can be made to contact with the solution containing a kind of material, this material can react when the temperature rises with the surface.

In another aspect of this invention, post-processing includes that substrate is exposed in the source including at least one acid source or its precursor.The example of suitable acid source includes at least a member selected from the combination that the following substance in the other acid sources of at least one characteristic that can be efficiently modified processed metal surface is constituted: carbonic acid, the ethanedioic acid, lactic acid, malic acid, tartaric acid that phosphoric acid, hydrochloric acid, molybdic acid, silicic acid, citric acid, nitric acid, hydroxyl replace.By using at least a member selected from the combination that the following substance in other materials is constituted, to improve the pH value of acid post-processing: two generation ammonium citrates (can be commercially available, trade name Citrosol #503 and Multiprep ), fluoride salt (such as fluoram), fluoboric acid, fluosilicic acid.The surface is activated using acid post-processing, rinsing is improved whereby, efficiency that sealer and/or face apply (such as surface is activated the corrosivity that can improve between surface and sealer before contacting with sealer, improves the corrosion resistance on processed surface whereby).In general, acid source is water-soluble and dosage is up to about 5wt.%, generally in the range of about 1- about 2wt.%.

In another aspect of this invention, post-processing includes contacting the surface handled using process of the invention with a kind of rinsing liquid." rinsing " is meant that, is sprayed to article or processed surface, dipping bath, impregnates or be exposed in rinsing liquid, to influence the characteristic on handled surface.For example, by being impregnated into the bath including at least one rinsing liquid using the surface of process processing of the invention.In some cases, which occurs interaction with the processed surface of at least part or reacts.It can also be applied by the multiple rinses in other techniques, heating, face, dyestuff, lubricant and wax is added, to be modified rinsed surface.The example of suitable compound used in rinsing includes at least a member selected from the combination that the following substance in other materials is constituted: titanate, titanium chloride, stannic chloride, zirconates, acetic acid zirconium, basic zirconium chloride, fluoride (such as calcirm-fluoride, tin fluoride, titanium fluoride, zirconium fluoride), copper compound, ammonium fluosilicate, silica (such as Ludox )/nitrate (such as aluminum nitrate) of metal processing, sulfate (such as magnesium sulfate, sodium sulphate, zinc sulfate and copper sulphate), lithium compound (such as lithium acetate, lithium carbonate, lithium citrate, lithium metaborate, lithium vanadate, tungstate lithium).Rinsing liquid further includes at least one of other materials organic compound such as vinylacrylic acid, fluorine-containing surfactant, polyethylene wax.The example of commercially available rinsing liquid includes from at least a member selected in the combination that following substance is constituted: the Aqualac (aqueous solution containing urethanes) in other materials (thermosetting paint provided by the Magni Group), W86 , W87 , B37 , T01 , E10 , JS2030S (rinsing liquid containing sodium metasilicate provided by MacDermidIncorporated) in other materials, JS2040I (or the rinsing liquid containing molybdenum provided by MacDermid Incorporated), EnSeal C-23 (the acrylic coating provided by Enthone), EnSeal C-26, Enth One C-40 (pigmented finiss provided by Enthone), Microseal , Paraclene 99 (rinsing liquid containing chromate), EcoTri (silicate/polymer rinsing liquid), MCI Pius OS (being provided by MetalCoatings International).A kind of special rinsing liquid includes water, the urethanes of water dispersion and at least one silicate (such as commonly assigned U.S.5, disclosed in 871,668, which is incorporated herein by reference herein).Although rinsing liquid can be used pure, usual rinsing liquid be can dissolve, diluted or be dispersed in another transfer (such as water, organic solvent in other media).Although the amount of rinsing liquid used depends on required as a result, still usual rinsing liquid accounts for about 0.1wt.%- about 50wt.% in rinse medium.The rinsing liquid can be applied multiple times, and if necessary, can heat.

Metal surface refers to the nonmetallic or conductive device of metal or metallic object and metal or conductive layer with adherency.Although can use process of the invention handles any suitable surface, the example of suitable metal surface includes at least a member selected from the combination that following substance is constituted: alloy such as Zinc-nickel alloys, tin-kirsite, zinc-cobalt alloy, the zinc-ferroalloy of galvanizing surface, sherardizing surface, zinc, iron, steel, brass, copper, nickel, tin, aluminium, lead, cadmium, magnesium and these metals in other materials.If necessary, layer mineral can be formed on the nonconductive matrix bottom on the surface being coated with at least one with conductive material (such as metallized polymeric article in other materials or thin slice, be coated with or be wrapped in intrametallic ceramic material).The example of metal-containing polymer includes at least a member selected from the combination that following substance is constituted: polycarbonate, acronitrile-butadiene-styrene (ABS), rubber, siloxanes, (phenolic) of phenol, nylon, PVC, polyimides, melamine, polyethylene, polypropylene, acrylic acid, fluorocarbon, polysulfones, polyphenylene, poly- acetic acid esters, polystyrene, epoxy in other materials.Conductive surface may also include carbon or graphite and conducting polymer (such as polyaniline).

Metal surface can have fiber, coil, thin slice (including porous sound absorbing plate), be chopped line, draw line or hawser/rope, metal strip, coupling device (such as hydraulic hose coupling), fiber, particle, fastener (including industry and residential hardware), fixture, nut, bolt, rivet, washer, cooling fin, molded article, powder metal article in for example other types of large range of size and structure.Determinant attributes for handling the process of the invention of metal surface depends on electric current/energy contacts metal surface ability.That is, similar with conventional electroplating technology, mineral surfaces are difficult to apply on the metal surface for limiting hollow area or gap.This difficulty can be overcome by using conformal anode.

Process of the invention generate can be subjected to secondary processes (such as in other techniques for riveting, forging, the flow of metal of crimping) and continue to provide the flexible surface of antiseptic property.This is with general preservative (such as chromate) on the contrary, general preservative can lead to its rupture when underlying surfaces shape.If necessary, can be before secondary processes, face applies the surface that (such as with heat cured epoxy) is formed by process of the invention.The product of process according to the invention processing corrosion resistance needed for remaining its in numerous properties after face is applied and is exposed in secondary processes, coating adhesion, component degree of functionality.

The surface that process of the invention provides can enhance the surface characteristic such as inoxidizability of corrosion resistance, carbon (such as fiber), stress crack corrosion (such as stainless steel), hardness, heat resistance of metal or conductive surface, improve the bond strength in composite material, dielectric layer is provided, the corrosion resistance of printed circuit/wiring board and decorative metal finishes is improved and reduces the electric conductivity of conductive polymer surfaces (including the application in interlayer type material).

Mineral coating can also influence the electrically and magnetically characteristic on surface.That is, mineral coating makes processed surface have resistive or insulating properties.Since with non-conducting surfaces, the product with thin layer of the invention can reduce the plating zine corrosion (if not eliminating) in device, and wherein electric current is related with the bridge in such as other products, the corrosion of pipeline.

In one aspect of the invention, the resistance to fracture and inoxidizability of the substrate containing aluminium, copper or lead can be improved using process of the invention.For example, it is perishable dedicated for the lead in battery production, so as to cause rupture such as intercrystalline corrosion.Using process of the invention can promote aluminium, copper and lead base bottom grain growth and reduce the influence of surface defect.Without being combined with any theoretical or explanation, it is believed that the lattice structure of the layer mineral formed in these three substrates according to present invention process method can be partially polymerized silicate.These lattices can mix disilicate structure or chain silicate (such as pyroxene).Partially polymerized lattice silicate has not brittle structural rigidity.In order to obtain stable partially polymerized lattice, metal cation has preferably taken up lattice, in order to provide charge stability.Aluminium replaces silicon, has the unique ability for occupying octahedral site or tetrahedral site.Trivalent aluminium needs additional metal cation to replace tetravalence silicon.In the situation of application lead, additional cation may include lead (II) ion.

In one aspect of the invention, electropaining cloth is carried out and electrolytic galvanized sheet (such as zinc surface) is placed in sodium silicate aqueous solution.After being placed in silicate solutions, the mineral coating or film containing silicate are deposited by using rather low voltage potential (such as there is about 24 volts of about 1- according to required current density) and low current.Current density is in the range of about 0.7A/in2- about 0.1A/in2 under 12 volts of constant pressure.In general, releasing hydrogen in semi-products/cathode, and oxygen is released in anode.

In one aspect of the invention, which is initially used as anode, and then electricity is converted into cathode.By pulse voltage, live the semi-products can be pre-processed (before acting on electrolytic mediator).Pulse can also increase the thickness of the film or layer that are formed on semi-products.If necessary, dopant (such as cation) may be present in electrolyte and be deposited on the surface and carrying out pulse before mineralising or after mineralising.

In another aspect of this invention, metal surface (such as zinc, aluminium, magnesium, steel, lead and these metals alloy) optionally pre-processed." pretreatment " is meant that, adjust segmentation or the continuous processing of metal surface, to be cleaned and be adjusted the surface, to be easy to be received by the coating for example containing mineral or silicate, process of the invention can be used as preparing a step in the continuous processing of corrosion resistant coil steel.The pretreatment is metal surface and on a surface by the coefficient result of expection degree of functionality of the coating/thin film containing mineral of formation.Pretreated example appropriate includes at least one clean method such as ultrasonic clean, activation, heating, degreasing, acidleach, deoxidation, the processing of spray bead, blasting treatment and rinsing.A kind of suitable steeis pretreament technique includes:

1) it is impregnated 2 minutes in 3: 1 dilutions of Metal Prep 79 (Parker Amchem),

2) secondary deionized water rinses,

3) it is impregnated 10 seconds in the sodium hydroxide solution of pH14,

4) it removes excessive solution and is air-dried,

5) it is impregnated 5 minutes in 50% hydrogenperoxide steam generator,

6) it removes excessive solution and is air-dried.

In another aspect of this invention, the metal surface is pre-processed by anode clean surface.By by semi-products or substrate be impregnated into containing in other detergents silicate, hydroxide, phosphate, carbonate medium in achievable such cleaning.In the range of using semi-products to be maintained at about 10A/ft2- about 150A/ft2 as the anode in DC battery and by electric current, which can produce oxygen.Oxygen stirs the surface of semi-products, the surface of simultaneous oxidation substrate.It can also the mechanical agitation surface by the vibratory equipment using routine.If necessary, the foaming in other way of these gases for example for gas to be added is introduced by physics, is immersed, it is possible to increase the amount of existing oxygen or other gases during layer mineral formation.

It in terms of further pretreatment of the invention, is exposed to semi-products in the silicate containing medium of the invention as anode, cleans the semi-products (such as removing the compound naturally occurred) whereby.Then make that the semi-products are converted into cathode and the method according to the invention is pre-processed.

In still another aspect of the invention, make silicate containing medium modified, to include at least one dopant material.The amount of dopant changes according to the property and required result of dopant.In general, the amount of dopant is in the range of about 0.001wt.%- about 5wt.% (or higher, as long as not adversely affecting to electrolyte).The example of suitable dopant includes at least a member selected from the combination that following substance is constituted: water soluble salt, oxide and the precursor of these following elements: tungsten, molybdenum, chromium, titanium (titanate), zircon, vanadium, phosphorus, aluminium (aluminate), iron (such as iron chloride), boron (borate), bismuth, gallium, tellurium, germanium, antimony, niobium (also referred to as niobium (Columbium)), magnesium and manganese, sulphur, zirconium (zirconates), there are also the mixtures of these substances, and often include the salt and oxide of aluminium and iron.The dopant includes at least one of following substance: molybdic acid, fluotitanic acid and its esters (such as hydrofluorination titanium, fluotitanic acid ammonia, fluosilicic acid ammonia and titanium sodium fluoride)；Fluorine zirconic acid and its esters (such as H₂ZrF₆、(NH)₂ZrF₆And Na₂ZrF₆).Either, the dopant include at least one substantially water-insoluble material for example electrophoresis transport polymer, PTFE, boron nitride, silicon carbide, silicon nitride, aluminium nitride, titanium carbide, diamond, titanium diboride, tungsten nitride, metal oxide (such as cerium oxide), powdered-metal and metal precursor (such as zinc).

Above-mentioned dopant can be used for increasing formation speed, the chemistry for improving finally formed layer and/or the physical property of layer mineral, as the diluent containing electrolyte or the medium of silicate.The example of these dopants is molysite (frerrous chloride, ferrous sulfate, ferrous nitrate) in other metals and halogen source, aluminum fluoride, fluosilicate (such as K₂SiF₆), fluoaluminate (such as potassium fluoroaluminate such as K₂ALF₅-H₂O), the mixture of these substances.Dopant material can be introduced on metal or conductive surface in the pre-treatment step before electro-deposition, the post-processing step after electro-deposition (such as rinsing) and/or the electrolytic contacts (if silicate does not form stablizing solution with dopant (such as one or more water soluble dopants)) by changing dopant solution and silicate solutions.It can lead in electrolyte solution there are dopant and form tailored surfaces on metal or conductive surface, such as the sodium silicate aqueous solution containing aluminate can be used to form the thin layer of the oxide containing silicon and aluminium.That is, at least one dopant (such as zinc) can be at least one siliceous substance (such as mineral) co-deposition in substrate.

Moreover, above-mentioned purificant can be improved by blending at least one dopant.The dopant can have an effect or react with processed surface.If necessary, which is dispersed in suitable medium (such as water) and is used as purificant.

Polymer by the way that water/polar carrier dispersible or dissolution is added can improve silicate containing medium, and in some cases, electric depositing solution inherently has the flowable gel of predetermined viscosity.If you are using, the amount of polymer or the material of water dispersion is usually in the range of about 0wt.%- about 10wt.%.The example that can be used for the material of the polymer in silicate containing medium or water dispersion includes at least a member selected from the combination that following substance is constituted: acrylic copolymer (provided by commercially, trade name Carbopol), hydroxyethyl cellulose, clay (such as bentonite), pyrogenic silica, the solution (commercially being provided as JS2030S by MacDermid) including sodium metasilicate.Suitable composition be include about 3wt.%N- grades of sodium silicate solution (PQ Corp), the Carbopol EZ-2 (BF Goodrich) of about 0.5wt.% optionally, the pyrogenic silica of about 5wt.%- about 10wt.% and these substances mixture Aquo-composition.In addition, chresard scattered polymer such as polyurethane fills aqueous silicate solutions, so as to electro-deposition mineral-polymer composite coating.By using can also improve the characteristic of electric depositing solution with the anode material of mineral anions and/or one or more dopants co-deposition as ion source.Dopant can be used for providing the additional thickness of electro-deposition layer mineral.

It also may modify silicate containing medium by the way that at least one diluent or electrolyte is added.The example of suitable diluent includes at least a member selected from the combination that following substance is constituted: sodium sulphate, surfactant, defoaming agent, colorant/dyestuff.The diluent (such as sodium sulphate) can be used to improve the electric conductivity of bath, the effect for reducing the pollutant entered in silicate containing medium, reduce bath bubble.When diluent is used as defoaming agent, the amount of electrolyte used is typically less than 5wt.%, such as in the range of about 1- about 2wt.%.The amount for influencing the diluent of the electric conductivity of bath or electrolyte is generally about 0wt.%- about 20wt.%.

What is be listed below is the parameter for being used to modify process of the invention in order to obtain the required coating containing mineral:

1, voltage

2, current density

3, device or slot

4, sedimentation time

5, the programming current and voltage change in technical process

6, the concentration of silicate solutions

7, the type and concentration of the negative example in solution

8, the type and concentration of the positive example in solution

9, composition/surface area of anode

10, composition/surface area of cathode

11, temperature

12, pressure

13, the type and concentration of surfactant

The specific range of the above parameter depends on substrate and it is expected that the composition deposited to be processed.Usually, the temperature of electrolyte bath is in the range of about 25- about 95C (such as about 75C), voltage is about 6-24 volt, the concentration of electrolyte solution is the silicate of about 5wt.%- about 15wt.%, current density about 0.025A/in2 and be greater than 0.60A/in2 in the range of, time of contact with electrolyte is about 10 seconds-about 50 minutes and typically about 1- about 15 minutes, and the ratio of anode and cathodic surface area is about 0.5: 1- about 2: 1.1st, 2, the 7 and 8 chemically and physically characteristic for modifying coating is particularly effective.That is, the 1st and 2 can influence the thickness of sedimentation time and coating, and the 7th and 8 can be used to introduce assign coating needed for chemical property dopant.Different types of zwitterion may include at least a member for selecting from the combination that following substance is constituted: first family metal, second family metal, transition and rare-earth oxide, oxide anion (such as molybdic acid, phosphoric acid, metatitanic acid, boron nitride, silicon carbide, aluminium nitride, silicon nitride), these substances mixture.

Typical process conditions, which will be provided, discharges hydrogen, in the environment of anode release oxygen in cathode.Without combining any theoretical or explanation, it is believed that the release of hydrogen can make surface p H to be processed quite high.It is also believed that oxygen reduction or the environment to disappear and high pH can make processed substrate surface have an effect or react.It is also believed that zinc can be used as the barrier of hydrogen, reduces (if not eliminating) whereby and implement hydrogen embrittlement caused by process of the invention.

By application, traditionally device and method related with electroplating technology can improve process of the invention.These method examples include pulse plating, horizontal plating systems, rotating cylinder, rack gear, electrolyte modifying agent are added in the medium containing silicate, using the film with bath.

Composition by changing anode can improve process of the invention.The example of suitable anode includes graphite, platinum, zinc, iron, steel, yttrium oxide, beryllium oxide, tantalum, niobium, titanium, nickel, MonelAlloy, palladium, these substances alloy.Anode may include the first material of the lining on the titanium of the second such as platinum plating or the niobium sieve of platinum lining.The anode can have any suitable structure for example adjacent to the sieve of barrel plating system.In some situations, anode (such as iron or nickel) can be by plasma diffusing W,Mo into the electrolyte bath that can be admixed in layer mineral.In general, the anode ion of ppm grades of concentration is enough to influence the composition of layer mineral.If necessary to the anode of size constancy, then the niobium of platinum lining or plating can be used.It is needed in clean situation in the anode of size constancy, in most cases, cleans anode using sodium hydroxide solution.By the cleaning that can enhance anode using heat and/or electric current.

It can implement process of the invention in any suitable device.The example of appropriate device includes the rack gear and rotating cylinder plating, brushing plating, horizontal plating, continuous length in plating metal in other conventional use of devices.It is better understood with some aspects of process of the invention by referring to accompanying drawing.Referring now to Fig. 2, Fig. 2 is the schematic diagram using a technique of the one aspect of electrolytic method of the invention.Implement technique shown in Fig. 2 in partial or continuous technical process.Has the product (or semi-products) (if necessary) of pending metal surface using sour (such as hydrochloric acid or citric acid) cleaning, then rinsing is carried out with water and rinsed with alkali (such as sodium hydroxide), then rinsed with water.If necessary, repeating the cleaning and rinse step.If necessary, acid/base cleaning can be replaced with conventional sonic cleaning apparatus.Then the semi-products are carried out with electrolytic method of the invention, forms layer mineral at least part workpiece surface whereby.The semi-products are taken out from electrolytic environments, then dry and are rinsed with water, and the thin layer for example including such as silica and/or sodium carbonate can be removed by rinsing.

Regardless of whether rinsing semi-products, process of the invention, which does not have to chromate (sexavalence or trivalent), also can provide improved corrosion resistance.When handling zinc surface with process of the invention, the thickness (or total amount) of zinc can be reduced, while obtaining equivalent (if not improving) corrosion resistance.Such as, it is exposed in zinc-plated environment about 2.5- about 30 minutes when by steel part, when then exposing in the process of the invention about 2.5- about 30 minutes, occurred white rust first (when being tested according to ASTM B-117) at about 24 hours-about 120 hours, and red rust failure occurred at about 100- about 800 hours.As a result, process of the invention can modify the dosage of zinc, to reach required corrosion-resistant level.If necessary, corrosion resistance can be further improved by applying at least one finishing coat.

Compared with conventional chromate processes (sexavalence or trivalent), process of the invention additionally provides improved torque tension properties.The zinc chromate and chrome yellow acid of Wilson-Garner M10 routine is handled, and process according to the invention is handled.The torque tension of these bolts is tested with the power of about 42,300 newton of about 20,000-, according to testing program USCAR-11.The standard deviation of the peak torque of conventional zinc chromate/Huang processing bolt is about 5.57Nm (the 3- δ range with about 33.4), and the standard deviation of the peak torque of the bolt of process according to the invention processing is about 2.56Nm (the 3- δ range with about 15.4).

According to the anticipated applications of the semi-products by process processing of the invention, the semi-products can be coated with second coating or thin layer.Either, (as described above) processed semi-products are first rinsed, are then coated with second coating or thin layer.The example of these second coatings or thin layer includes one or more of: acrylic acid coatings (such as IRILAC), silane (including with those of amine, acrylic acid and aliphatic epoxy functional groups silane), latex, amino acrylates, epoxies, type siloxane, alcohol acids, phenoxy lipid (powder and liquid form), radiation curing coating (such as coating of ultraviolet curing), lacquer, lac, linseed oil.Second coating is solvent or aqueous systems.By the way that second coating can be applied using any suitable conventional method (such as dipping, dip-spin technique, spraying).Utilize the curable second coating of any suitable method (such as UV light exposure, heating, under external environmental condition be dried).The example of ultraviolet curing coating is described in U.S.6,174,932 and 6,057,382, and this two documents are incorporated herein by reference herein.In general, rinsing the surface formed by process of the invention at least one of deionized water, silane or carbonic ester before applying finishing coat.The characteristic that the second coating can provide broad range for example improves the corrosion resistance to following layer mineral, reduces torque tension, is temporarily coated with to transport processed semi-products, decorative finish, and there are also static dissipation, electronic shield, hydrogen and/or atomic oxygen barriers.It can be used as final product with or without the semi-products for being coated with mineral of second coating or be used to manufacture the component of another product.

Without combining any theoretical or explanation, the thin layer containing silica can be formed on mineral.Thin layer containing silica can be chemically or physically modified and be used as middle layer or knot layer.The knot layer can be used to enhance the binding force to paint vehicle, coating, metal, glass in the other materials for contacting knot layer.By making the top layer containing silica can get this point in conjunction with one or more materials, wherein these materials contain alkyl in other functional groups that can be reacted with silica or silicon hydroxide, fluorine, vinyl, including epoxy and the two-part epoxy of powder paint systems, silane, hydroxyl, amino, these groups mixture.Either, by can remove this thin layer for containing silica using conventional clean method (such as being rinsed with deionized water).Compared with 100-500 angstroms of layer mineral, the knot layer containing silica is relatively thin, and mineral overall thickness is up to 1500-2500 angstroms of thickness.It if necessary, can chemistry and/or physical modification this thin layer for containing silica by using above-described post-processing approach (such as being exposed at least one carbonic ester or acid source).Contact the surface of the post-processing at least one above-mentioned second coating (such as heat cured epoxy).

On the other hand, the layer mineral with or without above-mentioned silica can be used as the middle layer or knot layer of one or more second coatings (such as second coating containing silane).The example of these second coatings and method of the invention can be supplemented in U.S.5,759,629；5,750,197；5,539,031；5,498,481；5,478,655；5,455,080；And it is described in 5,433,976.The disclosure of these United States Patent (USP)s is incorporated herein by reference herein.For example, the corrosion resistance to metallic substrates can be improved by using the second coating including at least one suitable silane for being combined with mineral surfaces.The example of suitable silane includes at least a member selected from the combination that following substance is constituted: the o- ethyl-silicate of 4- (TEOS), double -1,2- (three methylamino ethoxy silicon substrates) ethane (BSTE), vinyl silanes or γ-aminopropylsilane, epoxy silane, alkoxy silane in other organofunctional silanes.Silane can be in conjunction with mineralised surface, and then silane can solidify, and provides the protectiveness finishing coat for receiving external coating or thin layer or a surface whereby.In some cases, it needs successively to apply these silane.Such as, steel base (such as fastener) can be handled to form layer mineral, then it dries and rinses in deionized water, secondly with 5% BSTE solution coating, it is coated again with 5% vinyl silane solution, and being carried out with thermoset epoxy paint (the Corvel 10-1002 of Morton) powder coated, total thickness is up to 2 mils.This steel base is drawn with hard alloy point, and makes its exposure 500 hour in 117 salt fog of ASTMB.It after exposure, takes out the substrate and rinses, then dry 1 hour.Using scraping, the scratch is scraped off, removes any paint vehicle due to incision, and measure remaining gap.The substrate surveyed is shown does not have measurable gap other than the scratch.

Process of the invention forms the surface for having improved adhesiveness to external coating or thin layer (such as second coating).The example of suitable external coating includes at least a member selected from the combination that following substance is constituted: acrylic acid, e- coating, latex, urethanes, silane (such as TEOS, MEOS in other silane), fluoropolymer class, alcohol acids, type siloxane, polyesters, oils, gel-like, lubricating grease.The example of Suitable epoxy includes the coating that B17 or B18 finishing coat is provided as by Magni Group, such as, the method according to the invention handle and contact at least one silane and/or zirconium carbonic acid ammonia zinc coating, then it is applied with the heat cured epoxy face (Magni B18), forms not chromate-containing corrosion resistant article whereby.By selecting suitable purificant, second or external coating being applied on mineral, corrosion resistant type product is achieved with without chromated or phosphorylation.This selection can reduce the use that zinc-plated zinc is carried out to the surface containing iron, such as one steel surface of mineralising, be then coated with the coating containing silane and the external coating including epoxy.

Without combining any theoretical or explanation, it is believed that process of the invention forms releasable or offer water or relevant portion surface.It is precipitated in the hydrolysis or condensation reaction that these parts can occur in the rinsing, closing or topcoating cures covered.This precipitating improves the adhesive bond intensity between the surface and the solidify coating covered.

It is also acted as by the surface that process of the invention is formed for coated with glass, glass-to-metal seal, the middle layer of sealing or the knot layer in other application, wherein it is desirable to having a connection between metallic substrates and glassy layer or product or combining.Surface of the invention can be used to receive melten glass (such as borosilicate, phosphate in other glass), while protecting following metallic substrates and forming sealing.

Process of the invention can provide the surface for improving the caking property between processed substrate and binder.The example of binder includes from at least a member selected in the combination that following substance is constituted: thermometal (such as at least a member selected from the combination that following substance is constituted: polyamide, polyimides, butyl, acrylic acid modified compound, maleic anhydride-modified ethyl vinyl acetates, maleic anhydride-modified polyethylene, the ethyl vinyl acetates of hydroxyl terminal knot, the ethyl vinyl acetates of carbonyl end knot, acid terpolymer ethyl vinyl acetate, ethylene-acrylate), monophase system (such as the cured epoxies of cdicynanmide, the system of polyamide cure, the system of lewis acid cure, polysulfide, moisture cure urethanes), binary system (such as epoxies, the acrylate polysulfide of activation, polyurethane).Two metallic substrates on the surface handled with process according to the invention can be adhered to together by using binder.Either, a substrate with surface of the invention can be adhered on another material, such as makes plastics, the ceramics, vitronectin in processed metal and other surfaces.In a particular aspects, which includes an automatic clasp joint, and wherein binder is located in hook.

Improved between the surface formed by process of the invention and polymeric material is cohered or adhesion characteristic allows to be formed the constraint damper in sound wave and mechanical dampeners such as other products (such as in U.S.5,678, described in 826, the document be incorporated herein by reference herein), motor mounts, bridge/building bearing, HVAC silencer, expressway/airport sound barriers.The ability for improving the associativity being clipped between the bonding elastic material between damper metal plate reduces the transmission of sound, the Forming ability for improving these plates, reduces process deviation.These metal plates may include 304 steel, stainless steel, aluminium, cold-rolled steel, kirsite, galvanizing or the electrogalvanizing in any suitable metal such as other materials.It can the example of the polymer in conjunction with following metallic substrates includes neoprene, EPDM, SBR, EPDM in any suitable material such as other polymers in conjunction with surface of the invention and again.The combination of elastomer-metal (being described in U.S.5,942,333, the document is incorporated herein by reference herein) can also be provided in surface of the invention.

Process of the invention can be provided using dopant, purificant and/or sealer with improved heat-resisting and durability surface.Ground/grid, the heating element that gear that such surface can be used in other application (such as transmission), powder metal article, exhaust system (including branch pipe), metal are mated formation, wherein it is desirable to improving the resistance of metal surface.

In another aspect of this invention, the surface for reducing (if not eliminating) molten metal adhesiveness (such as by reducing intermetallic formation) is generated using process of the invention.Without combining any theoretical or explanation, it is believed that process of the invention provides on product or component can have an effect with molten metal or react reduce the bonding force ablation to bulk article whereby and/or reaction film or coating.For example, process of the invention can provide ferrosilite or zinc silicate film or coating in substrate, so as to the shielding from molten metal (such as molten aluminum or magnesium) or the substrate is isolated.It include that the efficiency of the film or coating can be improved in the additional coatings of silica (such as can be used as ablative agent when being exposed in molten metal) by applying.At other on the way, in die-cast aluminum on zinc core or magnesium, when molding is used for the aluminium of electronic component, the ability that needs that molten metal is inhibited to bond.By applying Magni B18, acrylic acid, polyester in above-described finishing coat such as other substances, the bonding force of molten metal can be further decreased.By applying heat proof material such as colloidal silica (such as Ludox ), finishing coat can be made modified (such as more heat-resisting).

Although above description is especially emphasized to form the thin layer containing mineral on the metal surface, process of the invention in conjunction with front or rear processing with common metal and/or finishing practices or can be substituted.Conventional rear coating baking can be used to the physical property of modified mineral layer in other improvements, remove water and/or hydrogen.Layer mineral of the invention can be used to protect final metal product from corrosion; conventional phosphating process is substituted whereby; such as; in the situation of automobile metal finished product, phosphate and chromate are not had to using process of the invention and uses process of the invention before applying coating such as E- coating.Moreover, replacing above-mentioned mineral aqueous solution with the aqueous solution of the polyurethane containing soluble silicate, and the mineral aqueous solution can be used to replace so-called automobile E- coating and/or powder painting process.Mineral formation technique can be used to enhance the corrosion resistance of electronic component such as motor shaft (as example 10-11 is confirmed).Process of the invention can also be used in for example conventional electroplating technology of practical unlimited final use and be suitable for Site Service.For example, corrosion-resistant metal product can be manufactured using the coating of the invention containing mineral, for the product traditionally using zinc as protective coating, these products include car body and component, barrel type granary, bridge in such as many other final uses.And, according to the dopant and its concentration in the presence of mineral deposition liquid, process of the invention can generate microelectronics film in such as metal or conductive surface, to provide enhancing electro magnetic (such as the EMI shielding, the electric connector reduced in other properties corrosivity, reduce by corroding caused by different metal contacts) property and corrosion resistance, or withstand ultraviolet light and environment containing antozone is for example extraneous.

Following example is to illustrate certain aspects of the invention, and it should be understood that such example is not delimit the scope of the invention (as defined by claims included below).X- ray Photoelectronic Spectroscopy data confirm that in following example in mineralized layer there are unique mesosilicate species, such as ESCA measurement atom photoelectron combine can, to measure binding characteristic.

Example 1

Device below and material are used in this example:

The electrogalvanizing breadboard of standard, the laboratory ACT

The N- grade sodium silicate solution of 10% (by weight)

12 volts of EverReady battery

1.5 volts of Ray-O-Vac Heavy Duty Dry Cell Battery

Triple RMS digital multimeter

The capacitor of 30 μ F

The capacitor of 29.8k Ω

Fig. 1 shows the schematic diagram of circuit and device for implementing this.Referring now to fig. 1, above-mentioned experimental plate is contacted with the solution containing 10% sodium mineral and deionized water.Electric current is set to flow through the circuit and solution in the manner shown in fig. 1.Experimental plate exposure 74 hours under external environmental condition.The visual inspection of the experimental plate shows to be deposited with grayish coating or film on experimental plate.

In order to determine the corrosion resistance as provided by the coating containing mineral, the experimental plate being applied is tested according to ASTM regulation No.B117.The plate is placed in salt fog thereafter to only expose the region being applied with the section with covering experimental plate.In order to be compared, following plates are also tested according to ASTM regulation No.B117,1) naked electrolytic galvanized sheet and 70 hours naked electrolytic galvanized sheets 2) are soaked in 10% sodium Mineral Solution.In addition, the steel plate (ACT B952, no Parcolene) that naked trbasic zinc phosphate is coated with and the steel plate (ACT B1000, no Parcolene) of naked ferric phosphate coating are placed in salt fog, so as to as reference.

The result of ASTM regulation is listed in following table

Plate description	Hourage in B117 salt fog
Plate description	Hourage in B117 salt fog	The steel of trbasic zinc phosphate coating	1
The steel of ferric phosphate coating	1	The steel of trbasic zinc phosphate coating	1
The steel of ferric phosphate coating	1	The naked electrolytic galvanized sheet of standard	≈120
The on-gauge plate soaked with sodium mineral	≈120	The naked electrolytic galvanized sheet of standard	≈120
The on-gauge plate soaked with sodium mineral	≈120	Coated cathode of the invention	240+

Above table indicates that the present invention forms the coating or film that may significantly improve corrosion resistance.It is also shown that the process already leads to extending the formation of the anti-corrosion film in the service life of electrogalvanizing metallic substrates and surface.

Esca analysis is carried out according to conventional technique, under the following conditions on zinc surface:

The analysis condition of ESCA:

The Lsci of Instrumental Physics electronics model 5701

X-ray source monochrome aluminium

350 watts of source power

Analyzed area 2mm × 0.8mm

50 ° of the angle of outlet

Electronics acceptance angle ± 70 °

Charging neutrality electronical reading electron gun

Charge corrects the C- (C, H) at 284.6eV in 1s spectrum

^*The angle of outlet is the angle between sample panel and electrical analysis meter lens.

It can make the nature and characteristic that species are formed by the mineralized layer formed on cathode using the photoelectron combination of silane.Using Si (2p) photoelectronic 102.1eV in conjunction with the disilicic acid zinc that by the species identification can be presence due to sodium ion and modification.

Example 2

This example, which is described, implements electrodeposition technology of the invention under the voltage and current increased compared with example 1.

Before electro-deposition, preconditioning process is carried out to cathode plate:

1) dipping 2 minutes in 3: 1 diluted Metal Prep 79 (ParkerAmchem),

2) secondary deionized water rinses,

3) it is impregnated 10 seconds in the sodium hydroxide solution of pH14,

4) it removes excessive solution and is air-dried,

5) it is impregnated 5 minutes in 50% hydrogenperoxide steam generator,

6) it removes excessive solution and is air-dried.

Power supply is set to be connected with the galvanic deposition cell for including plastic cup, there are two the ACT cold-rolled steel of standard (cleaning, do not polish) breadboards for plastic cup dress.It is about 3 inches × 4 inches (12 square inches) by the impregnation area (1 side) that one end of breadboard is immersed in each plate in the deionized water solution containing 10%N- grades of sodium mineral (PQ Corp.), and the ratio of anode and cathode is 1: 1.These plates are directly connected with DC power supply and apply 6 volts of voltage up to 1 hour.Last electric current is in the range of about 0.7-1.9 amperes.Last current density is in the range of 0.05-0.16 amps/square.

After electrolytic process, dry coated panel under external environmental condition, the moisture-proof of the plate is then assessed according to ASTM test No.D2247: i.e. visual monitoring corrosion activity is until there is red rust on the plate surface region 5%.These coated test plates continue the red rust for just first appearing red rust in 25 hours and continuing just to occur 5% for 120 hours.In comparison, the steel plate of conventional iron and zinc phosphorylation continues just to first appear corrosion within 7 hours and red rust up to 5% in ASTM D2247 humidity exposure.Therefore, above-mentioned example shows that process of the invention is capable of providing corrosion resistance more better than iron and zinc phosphated steel panels.

Example 3

Two stereotypes are prepared using commercial lead sheath and are cleaned 25 minutes in the HCl of 6M.Then clean stereotype is placed in the solution containing 1wt.%N- grades of sodium metasilicate (being provided by PQ Corporation).

Make a stereotype as anode to be connected with DC power supply, and another stereotype is as cathode.Apply 20 volts of current potential initially to generate 0.9-1.3 amperes of electric current.After about 75 minutes, these plates are taken out from sodium silicate solution and are rinsed with deionized water.

Esca analysis is carried out on lead surface.It can make the nature and characteristic that species are formed by mineralized layer using the photoelectron combination of silane.Using Si (2p) photoelectronic 102.1eV in conjunction with the disilicic acid lead that by the species identification can be presence due to sodium ion and modification.

Example 4

This example confirms to form a layer mineral on aluminum substrates.Using with identical device in example 1, make aluminium probe tube (3 " × 6 ") react, to form metal silicate surface.Using two different aluminium alloys (Al2024 and Al7075).Before carrying out electrolysis process to these plates, each plate is prepared using method listed in following table A.Each plate is washed with solvent alcohol to remove any excessive dirt and oils.These plates are cleaned with Alumiprep 33 or anionic detersive or both of which use are carried out to these plates.Both cleaning modes are to remove excessive aluminium oxide.It can complete as follows anionic detersive: be put into the Na of the NaOH containing 5%, 2.4% using working plate as anode₂CO₃, 2% Na₂SiO₃, 0.6% Na₃PO₄Aqueous solution in, and apply a current potential to pass through the 100mA/cm of breadboard impregnation zone²Current density keep 1 minute.

Once cleaning the plate, it is placed in 1 liter of beaker filled with 800mL solution.Bath is prepared using deionized water and content shown in the following table.The plate is connected on the negative wire head of DC power supply using electric wire, and another plate is connected on positive the end of a thread.The two plates are spaced each other 2 inches.By potential setting in the table shown on voltage and slot works 1 hour.

Table A

Example A B C D E F G H

Types of alloys 2,024 2,024 2,024 2,024 7,075 7,075 7,075 7075

Anionic detersive be whether it is no be whether it is no

Pickling is to be

Bath foam

Na₂SiO₃1% 10% 1% 10% 1% 10% 1% 10%

H₂O₂1% 0% 0% 1% 1% 0% 0% 1%

Current potential 12V 18V 12V 18V 12V 18V 12V 18V

The surface of each substrate is analyzed using ESCA.The each sample surveyed represents the mixture of silica and metal silicate.Without combining any theoretical or explanation, it is believed that metal silicate is the reaction result between the metal cation on surface and the alkaline silicate of coating.It is also believed that silica is the product of the excess silicon hydrochlorate from the reaction or the precipitated silica from coating removal technique.Energy (BE) is combined to indicate the metal silicate using the Si (2p) in lower 102eV (generally between 102.1-103.6eV) range.Obtained spectrum in the range of representing metal silicate and silica go flatung colour developing combine can on show the peak of overlapping.

Example 5

This example describes another dipping for generating the medium containing silicate.

Using 5% sodium metasilicate being mixed with 10% fumed silica and the aqueous gel for preparing is come coat cold rolled steel panels.One block of plate is washed with reagent alcohol, and washs another block of plate in phosphate base metal preparation solution, then implements sodium hydroxide washing and bath of hydrogen peroxide.It is connected in the platinum line wrapped up with mineral wool by the way that positive the end of a thread is connected on steel plate using DC power supply, by negative wire head, to establish the device.The device analog brushing electroplating operations." brush " is immersed in gel solution so as to fully saturated.Gel is coated on plate by potential setting in 12V and with brush.When brush passes through on the surfaces of the board, it can be seen that there is hydrogen to release.Brushing gel 5 minutes, the plate is then washed with deionized, to remove any excessive gel and unreacted silicate.

The surface of each steel plate is analyzed using ESCA.The reaction product between environment that ESCA detection metallic substrates and electrolysis process are brought up.The each sample surveyed indicates the mixture of silica and metal silicate.Metal silicate is the reaction result between the metal cation on surface and the alkaline silicate of coating.Silica is the product of the excess silicon hydrochlorate from the reaction or the precipitated silica from coating removal technique.Energy (BE) is combined to indicate the metal silicate using the Si (2p) in lower 102eV (generally between 102.1-102.3eV) range.Silica can be seen using Si (2p) BE between 103.3-103.6eV.Obtained spectrum in the range of representing metal silicate and silica go flatung colour developing combine can on show the peak of overlapping.

Example 6

Using with identical device in example 1, make cold-rolled steel probe tube (laboratory ACT) react, to form metal silicate surface.Before carrying out electrolysis process to these plates, each plate is prepared using method listed in following table B.Each plate is washed with reagent alcohol to remove any excessive dirt and oils.These plates are cleaned with Metalprep 79 (ParkerAmchem) or anionic detersive or both of which use are carried out to these plates.Both cleaning modes are to remove excessive metal oxide.It can complete as follows anionic detersive: be put into the Na of the NaOH containing 5%, 2.4% using working plate as anode₂CO₃, 2% Na₂SiO₃, 0.6% Na₃PO₄Aqueous solution in, and apply a current potential to pass through the 100mA/cm of breadboard impregnation zone²Current density keep 1 minute.

Table B

Example AA BB CC DD EE

Base type CRS CRS CRS CRS CRS

Whether anionic detersive is no no

Pickling is to be

Bath foam

Na₂SiO₃1% 10% 1%--

Current potential 14-24 6 (CV) 12V--

(CV)

(CC) 23-10 of current density 23 85-48--

(mA/cm²)

B117 0.25 hour 0.25 hour 1 hour 1 hour 2 hours

¹Cold Rolled Steel Control object-is not handled the plate.

²It is handled with parkerized cold-rolled steel (laboratory ACT)-is not further.

Make electrolysis process as constant current or constant voltage experiment to carry out, is indicated with the symbol CV or CC in table.One constant potential is applied on the slot for allowing current fluctuation by constant voltage experiment, and constant current experiment maintains electric current by adjusting current potential.Utilize the corrosion resistance of ASTM B117 test board.Breakage is determined at 5% red rust surface coverage.

The surface of each substrate is analyzed using ESCA.The reaction product between environment that ESCA detection metallic substrates and electrolysis process are brought up.The each sample surveyed indicates the mixture of silica and metal silicate.Metal silicate is the reaction result between the metal cation on surface and the alkaline silicate of coating.Silica is the product of the excess silicon hydrochlorate from the reaction or the precipitated silica from coating removal technique.Energy (BE) is combined to indicate the metal silicate using the Si (2p) in lower 102eV (generally between 102.1-102.3eV) range.Silica can be seen using Si (2p) BE between 103.3-103.6eV.Obtained spectrum in the range of representing metal silicate and silica go flatung colour developing combine can on show the peak of overlapping.

Example 7

Using with identical device in example 1, make galvanized steel probe tube (laboratory EZG 60GACT) react, to form metal silicate surface.Before carrying out electrolysis process to these plates, each plate is prepared using method listed in following table C.Each plate is washed with reagent alcohol to remove any excessive dirt and oils.

Table C

Example A1 B2 C3 D5

Base type GS GS GS GS

Bath foam

Na₂SiO₃10% 1% 10%-

Current potential (V) 6 (CV) 10 (CV) 18 (CV)-

Current density 22-3 7-3 142-3-

(mA/cm²)

B117 96 hours 216 hours 224 hours 336 hours

¹Galvanized steel reference material-is not handled the plate.

Utilize the corrosion resistance of ASTM B117 test board.Breakage is determined at 5% red rust surface coverage.

Example 8

Using with identical device in example 1, make copper probe tube (C110Hard, Fullerton Metal) react, to form metalized surface.Before carrying out electrolysis process to these plates, each plate is prepared using method listed in following table D.Each plate is washed with reagent alcohol to remove any excessive dirt and oils.

Table D

Example AA1 BB2 CC3 DD4 EE5

Base type Cu Cu Cu Cu Cu

Bath foam

Na₂SiO₃10% 10% 1% 1%-

Current potential (V) 12 (CV) 6 (CV) 6 (CV) 36 (CV)-

Current density 40-17 19-9 4-13 6-10-

(mA/cm²)

B117 2 hours 5 hours 5 hours 11 hours 11 hours

¹Copper reference material-is not handled the plate.

Utilize the corrosion resistance of ASTM B117 test board.Due to copper oxide presence and the half-light mist that determines breakage, and occur on surface indicates the presence of copper oxide.

Example 9

An electrochemical cell is established with 1 liter of beaker.Sodium silicate solution of the beaker filled with the N sodium silicate solution (PQCorp) including 10wt.%.The temperature of the solution is adjusted by the way that beaker to be put into the water-bath for can control temperature.Material using cold-rolled steel probe tube (laboratory ACT, 3 × 6 inches) as anode and cathode.The two plates are put into beaker, the two 1 inch of interval facing with each other is made.Using active gage as anode.Anode and cathode is set to be connected with DC power supply.Voltage, solution used, electrolysis time, current density, temperature and corrosive nature are shown in following table.

Table E

Sample silicate concentration bath temperature voltage and current density bathes time etching time

# Wt% DEG C lies prostrate mA/cm²Hour minute (B117)

10% 24 12 44-48 51 of A

10% 24 12 49-55 52 of I-B

10% 37 12 48-60 30 71 of I-C

10% 39 12 53-68 30 5 of I-D

10% 67 12 68-56 60 2 of I-F

10% 64 12 70-51 60 75 of I-G

I-H NA NA NA NA NA 0.5

These plates are rinsed with deionized water to remove any excessive silicate extracted out from bath foam.Erosion test is carried out to these plates according to ASTM B117.It is recorded in the red rust that these plates reach 5% in corroding chamber and (is measured) the time it takes (as shown above) as observing by visual observation.Example I-H shows the Corrosion results for not carrying out the same steel plate of any processing.

Example 10

Example 10,11 and 4 confirms the especially aspect of of the invention one, that is, the steel shaft being incorporated in motor is made to have corrosion resistance.Motor shaft obtains from Emerson Electric Co.from St.Louis, Missouri and is used to support rotor assembly.The length for measuring axis is 25cm, diameter 1.5cm, and these axis are prepared with steel available commercially.

The foundation of electrochemical cell is similar with example 9, and only the arrangement of the slot makes it that can accommodate above-mentioned steel motor axis.The axis is established as cathode, and two cold-rolled steel sheets are used as anode, the two plates are arranged such that each plate in the opposite sides of axis.It is as shown in the table to adjust voltage and temperature.The current density of anode is also shown in table.

Table F

# Wt% DEG C lies prostrate mA/cm²Hour minute

10% 27 6 17-9 60 3 of II-A

10% 60 12 49-35 60 7 of II-B

10% 75 12 59-45 60 19 of II-C

10% 93 12 99-63 60 24 of II-D

10% 96 18 90-59 60 24 of II-F

II-G NA NA NA NA NA 21

II-H NA NA NA NA NA 31

These axis are rinsed with deionized water to remove any excessive silicate extracted out from bath foam.Due to processing, example II-A does not show apparent color change compared with example II-B to II-F.Example II-B shows faint yellow/gold tone.Example II-C shows pale blue and light pearly-lustre color.Example II-D and II-F aobvious avy blue due to processing.Erosion test is carried out to these axis according to ASTMB117.It is recorded in red rust the time it takes (as shown above) that these plates in corroding chamber reach 5%.Example II-G shows the Corrosion results for not carrying out the same steel shaft of any processing, and example II-H shows the Corrosion results of the same steel shaft with commercial phosphoric acid zinc coating.

Example 11

Foundation for handling the electrochemical cell of steel shaft is similar with example 10.Motor shaft obtains from Emerson Electric Co.from St.Louis, Missouri and is used to support rotor assembly.The length for measuring axis is 25cm, diameter 1.5cm, and these axis are prepared with steel available commercially.The axis is established as cathode, and two cold-rolled steel sheets are used as anode, the two plates are arranged such that each plate in the opposite sides of axis.It is as shown in the table to adjust voltage and temperature.The current density of anode is also shown in table.

Table G

# Wt% DEG C lies prostrate mA/cm²Hour minute

10% 92 12 90-56 60 504 of III-A

10% 73 12 50-44 60 552 of III-B

III-C NA NA NA NA NA 3

III-D NA NA NA NA NA 3

These axis are rinsed with deionized water to remove any excessive silicate extracted out from bath foam.Erosion test is carried out to these plates according to ASTM B 117.It is recorded in red rust coverage the time it takes (as shown above) that these axis in corroding chamber reach 5%.Example III-C shows the Corrosion results for not carrying out the same steel shaft of any processing, and example III-D shows the Corrosion results of the same steel shaft with commercial phosphoric acid zinc coating.

Example 12

An electrochemical cell is established with 1 liter of beaker.Sodium silicate solution of the solution filled with the N sodium silicate solution (PQ Corporation) including 5,10 or 15wt.%.The temperature of the solution is adjusted by the way that beaker to be put into the water-bath for can control temperature.Anode and cathode material is used as using cold-rolled steel probe tube (laboratory ACT, 3 × 6 inches).The two plates are put into beaker, the two 1 inch of interval facing with each other is made.Using active gage as anode.Anode and cathode is set to be connected with DC power supply.Shown in following table voltage, solution used, electrolysis time, by the current density of cathode, temperature, the dimension scale of anode and cathode and corrosive nature.

Table H

Sample silicate concentration bath temperature voltage and current density A/C ratio bathes time etching time

# Wt% DEG C lies prostrate mA/cm²Hour minute (B117)

IV-1 5 55 12 49-51 0.5 15 2

IV-2 5 55 18 107-90 2 45 1

IV-3 5 55 24 111-122 1 30 4

IV-4 5 75 12 86-52 2 45 2

IV-5 5 75 18 111-112 1 30 3

IV-6 5 75 24 140-134 0.5 15 2

IV-7 5 95 12 83-49 1 30 1

IV-8 5 95 18 129-69 0.5 15 1

IV-9 5 95 24 196-120 2 45 4

IV-10 10 55 12 101-53 2 30 3

IV-11 10 55 18 146-27 1 15 4

IV-12 10 55 24 252-186 0.5 45 7

IV-13 10 75 12 108-36 1 15 4

IV-14 10 75 18 212-163 0.5 45 4

IV-15 10 75 24 248-90 2 30 16

IV-16 10 95 12 168-161 0.5 45 4

IV-17 10 95 18 257-95 2 30 6

IV-18 10 95 24 273-75 1 15 4

IV-19 15 55 12 140-103 1 45 4

IV-20 15 55 18 202-87 0.5 30 4

IV-21 15 55 24 215-31 2 15 17

IV-22 15 75 12 174-86 0.5 30 17

IV-23 15 75 18 192-47 2 15 15

IV-24 15 75 24 273-251 1 45 4

IV-25 15 95 12 183-75 2 15 8

IV-26 15 95 18 273-212 1 45 4

IV-27 15 95 24 273-199 0.5 30 15

IV-28 NA NA NA NA NA NA 0.5

These plates are rinsed with deionized water to remove any excessive silicate extracted out from bath foam.Erosion test is carried out to these plates according to ASTM B117.It is recorded in red rust coverage the time it takes (as shown above) that these plates in corroding chamber reach 5%.Example IV-28 shows the Corrosion results for not carrying out the same steel plate of any processing.Upper table explanation, can enhance corrosive nature using the concentration and raised temperature of silicate in bath.It can also be realized in 15 minutes anticorrosive.Corrosive nature can be further enhanced using higher current density.

Example 13

An electrochemical cell is established with 1 liter of beaker.Sodium silicate solution of the solution filled with the N sodium silicate solution (PQCorp) including 10wt.%.The temperature of the solution is adjusted by the way that beaker to be put into the water-bath for can control temperature.Cathode material is used as using galvanized steel probe tube (laboratory ACT, 3 × 6 inches).Using zine plate as anode material.The two plates are put into beaker, the two 1 inch of interval facing with each other is made.Using active gage as anode.Anode and cathode is set to be connected with DC power supply.Voltage, solution used, electrolysis time, current density and corrosive nature are shown in following table.

Table I

Sample silicate concentration voltage and current density bathes time corrosive attack

# Wt% lies prostrate mA/cm²(R) hour (W) hour minute

10% 6 33-1 60 16 168 of V-A

10% 3 6.5-1 60 17 168 of V-B

10% 18 107-8 60 22 276 of V-C

10% 24 260-7 60 24 276 of V-D

V-E NA NA NA NA 10 72

These plates are rinsed with deionized water to remove any excessive silicate extracted out from bath foam.Erosion test is carried out to these plates according to ASTM B 117.Time when these plates are shown rust staining and zinc oxide formation is expressed as corrosion (W).It is recorded in red rust coverage the time it takes (corrosion (R) gone out as shown above) that these plates in corroding chamber reach 5%.Example V-E shows the Corrosion results for not carrying out the same steel plate of any processing.

Example 14

Foundation for handling the electrochemical cell of steel shaft is similar with example 10-12.Motor shaft obtains from Emerson ElectricCo.from St.Louis, Missouri and is used to support rotor assembly.The length for measuring axis is 25cm, diameter 1.5cm, and alloy information is for example shown in the following table.The axis is established as cathode, and two cold-rolled steel sheets are used as anode, the two plates are arranged such that each plate in the opposite sides of axis.It is as shown in the table to adjust voltage and temperature.The current density of anode is also shown in table.

Table J

# alloy silicate concentration bath temperature voltage and current density bathes time corrosion

Wt% DEG C of volt mA/cm²Hour minute

10% 75 12 94-66 30 16 of VI-A 1018

10% 95 18 136-94 30 35 of VI-B 1018

10% 75 12 109-75 30 9 of VI-C 1144

10% 95 18 136-102 30 35 of VI-D 1144

10% 75 12 92-52 30 16 of VI-F 1215

10% 95 18 136-107 30 40 of VI-G 1215

These axis are rinsed with deionized water to remove any excessive silicate extracted out from bath foam.Erosion test is carried out to these plates according to ASTM B117.It is recorded in red rust coverage the time it takes (as shown above) that these axis in corroding chamber reach 5%.

Example 15

This example elaborates to form layer mineral on steel fibre using electrolytic method, and wherein steel fibre can be pressed into final product or form the permeable tabletting of another material.

Fiber is (0.20-0.26in) for being 0.026 inch, the cold 1070 carbon steel wires cutting for being extracted into 260,000-280,000PSI by diameter.The fiber of 20grams is put into the plastic beaker of 120mL.Platinum filament is put into the beaker, is allowed to contact with steel fibre.So that 1 inch × 1 inch of steel set-square is kept 1 inch on steel fibre, and supports so as not to contact platinum filament.Sodium metasilicate (N- grades, PQ Corp) deionized water solution of 75mL 10% is added in the beaker, impregnate steel set-square and steel fibre whereby and forms electrolytic cell.So that the DC power supply of 12V is connected with the slot, and using steel fibre as cathode, using steel set-square as anode, and transmits the anionic electrodeposition current density for being up to 3 amperes/inch 2.The slot is put on Vortex blender, so that steel fibre be made to make steady motion.It opens power supply and makes the current potential of 12V in slot by 5 minutes.After the time, slot is dismantled to and poured out excess solution, is only left steel fibre.While agitating, hot-air is blown on steel grit to be dried.

Salt spray test is carried out to these fibers according to ASTMB117.The visual measurement result of ASTMB117 test is listed in following table.

Table K

The red rust coverage of the first time breaking-out 5% of processing corrosion

Uncoated 5 hours 1 hour

Electrolysis 24 hours 60

Example 16-24

The process of the invention verified in example 16-24 uses 1 liter of beaker as described in Example 2 and DC power supply.It has had adjusted the silicate concentration in bath, the current potential applied and bath temperature and has listed these parameters in table L-A.

Table L-A

Technique silicate concentration current potential temperature-time

A 1wt.% 6V 25C 30 minutes

10% 12V 75C of B 30 minutes

15% 12V 25C of C 30 minutes

15% 12V 75C of D 30 minutes

Example 16

For the effect for the metal ion tested in electrolyte, iron chloride is added in bath solution with concentration listed in following table.Since iron is easy and silicate is compound or forms ferric hydroxide precipitate, therefore, it is difficult to iron is introduced into the solution.Since the Acidity of iron cation can destroy dissolubility of the silica in alkaline solution, the addition of iron is also restricted.However it has been found that the iron chloride (< 0.5%) of limited amount low concentration can be added in 20% N- grade silicate solutions, FeCl₃Concentration in the silicate solutions of 10wt.% is less than 0.025wt%.Table L shows the truth table for comparing electrolyte and keeping other conditions constant.Using inert anode, the solution efficacy of more no any anion dissolution.

L-B table

The concentration anode first time red rust failure of technique silicate concentration iron

(%) (%) (5% red rust)

B 10% 0 Pt 3 hours 2 hours

10 0.0025 Pt of B 3 hours 2 hours

10 0.025 Pt of B 7 hours 3 hours

10 0 Fe of B 7 hours 3 hours

10 0.0025 Fe of B 4 hours 2 hours

10 0.025 Fe of B 8 hours 3 hours

Control group N/A N/A N/A 1 hour 1 hour

The result of table L-B shows in 10% silicate solutions the process of the invention carried out at 12V in 75C 30 minutes.Anode used, which both can be platinum guaze, can also be iron plate.The solution is 10% silicate solutions with 0-0.0025% ferric chloride solution.Corrosive nature is measured in ASTM B117 exposure duration.

The trend show effect caused by the amount for the iron being doped in bath foam using inertia platinum electrode increase with without doping iron, it is similar using the bath of iron anode.This example confirmation enhances corrosion resistance by the iron that steel anode introduces, this can be reappeared by introducing iron salt solutions.

Example 17

Without combining any theoretical or explanation, it is believed that mineralising reaction mechanism includes condensation reaction.Researches show that the presence of condensation reaction out for rinsing, in this study rinse test plate after the processing of the electrolysis shown in table M-A.Table M-A shows that etching time also increases when rinsing time increase.It is believed that easily the layer mineral can be removed in water rinsing if layer mineral irrelevantly crosslinks or polymerize in layer mineral.On the contrary, corrosion failure time is improved when the breadboard dry quite a long time, indicates form fully crosslinked or polymerization layer mineral whereby.This further implies that there may be the further stage of reaction such as cross-linking reactions.

By heating, the corrosion resistance of layer mineral can be enhanced.Table M-B indicates the effect of heating on corrosion performance.The performance starts weak after about 600F.Without combining any theoretical or explanation, it is believed that heating can initially improve crosslinking, and the laser heating at high temperature can lead to cross-linked layer degradation.

Table M-A

Rinsing time failure time

It is carried out immediately 1 hour when also wet after the process

It is carried out immediately 2 hours after plate is dry

It is carried out 5 hours after plate is 1 hour dry

It is carried out 7 hours after plate is 24 hours dry

Table M-A indicates the corrosion failure time (ASTMB117) with the steel breadboard after CEM silicic acid salt treatment, processing after different time is rinsed.

Table M-B

Technique heating is damaged

B 72F 2 hours

B 200F 4 hours

B 300F 4 hours

B 400F 4 hours

B 500F 4 hours

B 600F 4 hours

B 700F 2 hours

B 800F 1 hour

D 72F 3 hours

D 200F 5 hours

D 300F 6 hours

D 400F 7 hours

D 500F 7 hours

B 600F 7 hours

B 700F 4 hours

B 800F 2 hours

Table M-B- handles the CEM of steel base.Technique B refers to the mineralising processing of 12V, 30 minutes cations in 10% silicate solutions.Technique C refers to the mineralising processing of 18V, 30 minutes cations in 15% silicate solutions.Breakage refers to the time for occurring 5% red rust coverage in ASTMB117 salt mist environment.

Example 18

The combination energy of the layer mineral formed on stainless steel is analyzed in this example.Stainless steel is 304 alloy of ANSI.Solvent washing is carried out to sample and is handled using technique B (doped with 10% silicate solutions of iron chloride, 75C, 12V, 30 minutes).ESCA conventionally is implemented to these processed samples.The result of ESCA indicates that the Si (2p) of 103.4eV combines energy.

The layer mineral can also be analyzed using automatic force microscope (AFM).Crystallization shown by surface is about 0.1-0.5 μm wide.

Example 19

Conventionally, the layer mineral of the method B formation according to example 18 is analyzed using auger electrons energy praseodymium (AES).Based on silicon, metal and oxygen is about 5000 angstroms (500nm) containing the approximate thickness of the silicate layer is measured.The thickness for measuring silicon dioxide layer based on the tenor relative to silicon and the amount of oxygen is less than about 500 angstroms (50nm).

The layer mineral formed according to the method B of example 16 is applied in the stainless steel base of ANSI304.The layer mineral is analyzed according to conventional test method, using automatic force microscope (AFM).AFM, which discloses being grown in around crystal grain boundary for metal silicate crystals (about 0.5 micron), to be assembled.

Example 20

This example indicates influence of the concentration of silicate to present invention process method.The concentration of electrolyte can consume silicate after implementing process of the invention.The number for the technique being subjected in the prebath for reducing the efficiency bathed is tested using 1 liter of 10% sodium silicate solution in an experiment.Bath utilizes exposure 15in using after 30 times²Breadboard, the corrosive nature of processed plate obviously reduces.

Sodium metasilicate, which is exposed in acid or metal, can be aggregated the silicate for keeping its insoluble.If a certain Cmin of silicate be it is useful, acid or the addition of metal salt will be settled out gel.If the solution consumption silicate or no enough amounts, not will form precipitating.Various acid and metal salt are added in the electrobath of equal part.After process of the invention carries out 40 wheels in same bath, which will not provide the protection of phase same level.This shows that the efficiency of silicate bath can be tested using iron chloride and zinc chloride.

Table N

Solution		0 wheel	10 wheels	20 wheels	30 wheels	40 wheels
Solution		0 wheel	10 wheels	20 wheels	30 wheels	40 wheels	0.1% FeCl₃	2 drops	-	-	-	-	-
10 drops	+	Trace	Trace	Trace	Trace			2 drops	-	-	-	-	-
10 drops	+	Trace	Trace	Trace	Trace	1mL		+	+	+	+	Trace
10% FeCl₃	2 drops	+	+	+	+	1mL		+	+	+	+	Trace	+
	2 drops	+	+	+	+	10 drops	It is thick	It is thick	It is thick	It is not bery thick	It is not bery thick		+
	0.05% ZnSO₄	2 drops	-	-	-	10 drops	It is thick	It is thick	It is thick	It is not bery thick	It is not bery thick	-	-
10 drops		2 drops	-	-	-	-	-	-	-	-		-	-
10 drops		5%ZnSO₄	2 drops	+	+	-	-	-	-	-	+	+	+
10 drops	+		2 drops	+	+	+	+	+	Finely		+	+	+
10 drops	+		0.1% ZnCl₂	2 drops	+	+	+	+	Finely	+	+	+	-
10 drops	+	+		2 drops	+	+	+	It is not bery thick		+	+	+	-
10 drops	+	+		10%ZnCl₂	2 drops	+	+	It is not bery thick	+	+	+	+	Finely
10 drops	+	+	+		2 drops	+	+		+	+	+	+	Finely

0.1%HCl	2 drops	-	-	-	-	-
	2 drops	-	-	-	-	-	10 drops	-	-	-	-	-
	10%HCl	2 drops	-	-	-	-	10 drops	-	-	-	-	-	-
10 drops		2 drops	-	-	-	-	-	-	-	-	-		-
10 drops		0.1% K₃Fe(CN)₆	2 drops	-	-	-	-	-	-	-	-	-	-
10 drops	-		2 drops	-	-	-	-	-	-	-		-	-
10 drops	-		10% K₃Fe(CN)₆	2 drops	-	-	-	-	-	-	-	-	-
10 drops	-	-		2 drops	-	-	-	-	-		-	-	-

Each 5th wheel of table N- takes out the bath foam sample of 50mL and is tested with ppt test."-" indicates to be formed without precipitating."+" indicates that precipitating is formed.

Example 21

The corrosion resistance of the layer mineral formed on the surface containing zinc and on the surface containing iron (steel) according to example 16 is compared by this example.Table O shows the truth table for comparing iron (cold-rolled steel-CRS) and zinc (electrogalvanizing-EZG) as the lattice building materials in cold rolled steel substrate and electrozinc galvanized substrate.The result for comparing rinsing is also included in table O.The sample only rinsed can get stronger corrosion resistance by using different anode materials.Technique B is carried out on the steel plate using iron anion compared with using Zinc material, provides the resistance to saltfog of enhancing.

Table O

Substrate	Anode	Processing	Rinsing	First time white rust	First time red rust	It is damaged
Substrate	Anode	Processing	Rinsing	First time white rust	First time red rust	It is damaged	CRS CRS CRS CRS EZG EZG EZG EZG CRS EZG	Fe Fe Zn Zn Zn Zn Fe Fe control control	B B B B B B B B control control	Without DI without DI without DI without DI without nothing	1 1 1 24 3	1 3 1 2 240 312 312 312 2 168	2 24 1 5 582 1080 579 864 2 192

The result of table O shows to establish the Corrosion results of mineral lattice ASTM B117 obtained from different anode material cathodic mineralization processing cold-rolled steels and plated steel sheet.

Example 22

This example elaborates on layer mineral using the second layer in order to provide further corrosion resistance (second layer generally comprise have can be with the compound of the hydrophilic composition in conjunction with layer mineral).

Make to contact according to the motor shaft of 10 mineralising of example with second coating.Both coating used in the coating of axis are 4- ethyl-orthosilicate (TEOS) or organofunctional silane (VS).Table P-A and P-B also list the influence of heating second coating.Table P-A and P-B show the effect of TEOS and vinyl silanes to B technique of the invention.

Table P-A

It handles ED time dry rinsing TEOS dipping 150C and heats first time red rust failure

B 10 minutes without without without without 5 hours 3 hours

B 10 minutes is without without without being 10 hours 7 hours

B 30 minutes without without without without 5 hours 3 hours

B 30 minutes is without without without being 11 hours 6 hours

B 10 minutes are that nothing is without 3 hours 3 hours

B 30 minutes are that nothing is 4 hours 3 hours

1 hour 10 minutes nothing of B is without 3 hours 1 hour

1 hour 10 minutes nothing of B is 15 hours 7 hours

B 1 hour 10 minutes is without 6 hours 5 hours

B 1 hour 10 minutes is 4 hours 3 hours

1 day 10 minutes nothing of B is without 10 hours 3 hours

1 day 10 minutes nothing of B is 17 hours 3 hours

B 1 day 10 minutes is without 6 hours 4 hours

B 1 day 10 minutes is 7 hours 3 hours

1 hour 30 minutes nothing of B is without 13 hours 6 hours

1 hour 30 minutes nothing of B is 15 hours 6 hours

B 1 hour 30 minutes is without 7 hours 3 hours

B 1 hour 30 minutes is 6 hours 2 hours

1 day 30 minutes nothing of B is without 10 hours 6 hours

1 day 30 minutes nothing of B is 18 hours 6 hours

B 1 day 30 minutes is without 6 hours 6 hours

B 1 day 30 minutes is 7 hours 4 hours

Control group 00 is without without without 5 hours 5 hours

Table P-A shows TEOS and heat and acts on the performance of B technique.

Table P-B

Processing rinsing baking test first time red rust failure

B DI salt-free 3 10

B DI 150c salt 36

B A151 salt-free 4 10

B A151 150c salt 2 10

B A186 salt-free 4 12

B A186 150c salt 17

B A187 salt-free 2 16

B A187 150c salt 2 16

Control group is without salt-free 11

DI=deionized water

A151=vinyltriethoxysilane (Witco)

A186=β-(3,4- epoxycyclohexyl) ethyl trimethyl silane (Witco)

A187=γ-glycidyl-trimethoxy silane (Witco)

Table P-B shows the effect that vinyl silanes handle ElishaB.

Table P-A shows that heat treatment improves corrosion resistance.These results also show if sedimentation time can be shortened by being used in combination with TEOS.The application of TEOS and heating has 100% improvement than the technique B of standard.The use of vinyl silanes shows that the performance of technique B can be improved.The additional benefit of organic coating first is that, table can be obviously reduced can be able to and repel water.

Example 23

This example describes the assessment when substituting possible phosphate with E- coat system to the present invention process method for forming coating on naked and galvinized steel.The assessment includes four classes: applying E- coating on mineral surfaces；The bonding of E- coating；Mineral/E- coat system erosion test；And the elemental analysis of mineral coating.Four mineral coatings (technique A, B, C, D) is assessed as reference material using phosphate.E- coating includes the blocked isocyanate coating that cathode applies.

Table Q

Technique SiO₃Concentration potential temperature-time

1% 6V 25C of A 30 minutes

10% 12V 75C of B 30 minutes

15% 12V 25C of C 30 minutes

15% 18V 75C of D 30 minutes

It has been found that E- coating can be evenly applied on the mineral surfaces formed by technique A-D and best application occurs on the mineral formed with technique A and B.It has also been found that surface A and B bathe E- coating or do not have apparent illeffects to E- curing of coatings technique.The adhesive test shows that surface A, B and D can improve the adhesiveness of E- coating compared with phosphate.Similar result can also see that in the surface C and D on galvinized steel.Surface B and D, which are usually shown, has bigger corrosion resistance than other evaluated modifications.

In order to understand the relationship between coating and performance, elemental analysis is carried out.It showing, the depth section of coating B and D are very big, and 5000 angstroms of >.

Example 24

This example demonstrates the effect of process of the invention to stress corrosion cracking.These tests are carried out to check that electrolysis of the invention handles the influence for the sensibility split to AISI304 stainless steel probe tube to stress.The pitting resistance that the test discloses the sample after implementation technique of the invention makes moderate progress.Four AISI304 Corrosion of Stainless Steel probe tubes are used in the test procedure.A sample is tested without surface treatment.Another sample is tested after the electrolysis process of the method B of embodiment 16.

According to method A (iron chloride pitting test) exposure test sample of ASTM G48.These tests include exposing 72 hours in ferric chloride solution (by weight about 6%) at room temperature.

Table R gives the result of erosion test.The end grain attack that untreated probe tube is subjected to mainly is subject to the probe tube of electrolysis processing.

The result of table R-ASTM G48 spot corrosion test

Maximum pitting penetration (mil)	Spot corrosion seepage velocity (mpy)	Comment
Maximum pitting penetration (mil)	Spot corrosion seepage velocity (mpy)	Comment	3.94	479	Spot corrosion on edge is maximum.Spot corrosion on surface is minimum.

ASTM G48,304 are exposed in iron chloride, and 72 hours, ambient temperature

Initial weight T (g)	Weight (g) after test	Weight (g) after test cleaning	Claim counterweight (g)	Weight loss (g)^*	Surface area (inch²)	Time (hour)	Density (gg/cc)	Corrosion rate (mpy)
Initial weight T (g)	Weight (g) after test	Weight (g) after test cleaning	Claim counterweight (g)	Weight loss (g)^*	Surface area (inch²)	Time (hour)	Density (gg/cc)	Corrosion rate (mpy)	28.7378	28.2803	28.2702	-0.4575	0.4676	4.75	72.0	7.80	93.663

Example 25

This example, which demonstrates the process of the invention when pre-processing to paint top layer, can improve adhesiveness and corrosion resistance.A layer mineral is formed on the steel plate according to the technique B of example 16.Processed plate is immersed in double-the 1 of 5%, it in 2- (trimethoxy silylation) ethane (BSTE-Witco) and is dried, is then immersed in 2% vinyltriethoxysilane (Witco) or 2% γ-glycidyl-trimethoxy silane (Witco) solution.In order to be compared, preparation is only with BSTE, then with the steel plate of the vinyl silanes steel plate handled and trbasic zinc phosphate processing.All plates are carried out with thermoset epoxy paint (Corvel 10-1002by Morton) powder coated, thickness is up to 2 mils.These plates are drawn with carbonization point tool and make its exposure 500 hour in ASTM B117 salt fog.It after exposure, takes out plate and rinses, then dry 1 hour.Scratch is scraped off with scraper, removes any paint vehicle due to incision, and measure remaining gap.Compare the average gap size that the plate that the trbasic zinc phosphate implemented and BSTE are handled shows 23mm.It is shown other than scratch with the mineralized plate that silane post-processes without measurable gap.The mineralization process implemented in conjunction with silane treatment is shown to improve to some extent than individually implementing silane treatment.This example confirms that the layer mineral provides the surface or thin layer that BSTE layers can more preferably bond.

Example 26

This example, which describes the layer mineral of the invention formed on containing metallic surface, can be used as electrical insulator.The insulating property (properties) of the steel plate of mineral coating is assessed using Miller hand-held point welding machine (model #AASW 1510M/110V input value/4450 Secondary amp outputs).Also assess control board, that is, cold-rolled steel (CRS) and 60g galvanized steel.All plate thickness are .032 ".Using tip and the time of holding about 5.0 seconds.Check associativity, discolouration and the weld size of completed spot welding.CRS and galvanized sheet show preferable associativity and the dark solder joint with about .25 " diameter.The steel plate of mineral coating does not have enough electricity to generate solder joint and have the circle of the .06 " diameter to change colour slightly.

Example 27

This example, which is described, forms thin layer of the invention on the zinc surface obtained using the sherardising process commercially bought.

It include in mineralizing solution 2 liters of glass beakers of injection of 10wt.%N sodium silicate solution (PQ Corp) and 0.001wt.% iron chloride by 1900mL.Solution is heated to 75C on stirring hot plate.One block of observation glass is put into the top of beaker so that evaporation loss is minimum and solution is heated simultaneously.It is used as anode for two (3 inches × 6 inches × 0.032 inch) of standard ACT cold roll steel (100008) breadboard and hangs the copper strip contacts to hang down from the copper rod of 3/16 inch diameter.Cathode be diameter be 1.1875 inches, with a thickness of 0.125 inch and have one 0.5 inch centre bore Sherardized washer.Washer and steel anode are connected on power supply by the electric wire pressed from both sides with stainless steel cover support.Power supply is Hull Cell rectifier (3- electronic circuit).In 2.5 volts of constant (1 amperes/inch of ∽²Current density) voltage under electrolysis processing washer 15 minutes.Washer is dried under external environmental condition after taking out in CM bath.Implement postorder salt spray test (ASTM B117) and is compared with untreated control washer, as a result as follows:

Sample	There is the time of first time red rust	Red rust reaches for 5% time
Sample	There is the time of first time red rust	Red rust reaches for 5% time	Compare washer	144	192
Mineralising washer	360	1416	Compare washer	144	192

Example 28

This example demonstrates using aftertreatment technology the property for improving thin layer of the present invention.

The slot of the mineralizing solution including 10wt.%N sodium silicate solution (PQ Corp) and 0.001wt.% iron chloride containing 25 gallons is heated to 75C using immersion heater.It is used as anode for six (3 inches × 6 inches × 0.032 inch) of standard ACT cold roll steel (100008) breadboard and hangs the copper strip contacts to hang down from the copper rod of 3/16 inch diameter.3/16 inch of copper rod contacts 0.5 inch of copper anode bus, which is connected with rectifier.Three standard ACT Electrogalvanized steel test panels (03 inch × 06 inch × .030 inches of 2 face ACT E60 EZG) are suspended between two rows of three steel anodes, distance of these anodes apart from Electrogalvanized steel test panels is about 3 inches.Plated steel sheet is set to be connected with negative busbar.It is handled electrogalvanizing breadboard 15 minutes under 12 volts of constant pressure.Electric current is initially about 40 amperes, and exposure falls to approximately 25 amperes after 15 minutes.These plates are post-processed in aqueous solution below.

Sample #	It rinses immediately	It is dry	Treatment fluid
Sample #	It rinses immediately	It is dry	Treatment fluid	1	No	It is	Zirconyl carbonate ammonia (1: 4 diluted Bacote20)
2	It is	No	Zirconyl carbonate ammonia (1: 4 diluted Bacote20)	1	No	It is	Zirconyl carbonate ammonia (1: 4 diluted Bacote20)
2	It is	No	Zirconyl carbonate ammonia (1: 4 diluted Bacote20)	3	No	It is	Zirconyl carbonate ammonia (1: 4 diluted Bacote20)
4	No	It is	The phosphoric acid of 20% (by volume)	3	No	It is	Zirconyl carbonate ammonia (1: 4 diluted Bacote20)
4	No	It is	The phosphoric acid of 20% (by volume)	5	It is	No	The phosphoric acid of 20% (by volume)
6	No	It is	Nothing	5	It is	No	The phosphoric acid of 20% (by volume)
6	No	It is	Nothing	7	No	It is	The phosphoric acid of 2.5% (by volume)
8	It is	No	The phosphoric acid of 2.5% (by volume)	7	No	It is	The phosphoric acid of 2.5% (by volume)
8	It is	No	The phosphoric acid of 2.5% (by volume)	9	No	It is	Nothing
10	No	It is	The iron chloride of 1.0wt.%	9	No	It is	Nothing
10	No	It is	The iron chloride of 1.0wt.%	11	It is	No	The iron chloride of 1.0wt.%
12	No	It is	The iron chloride of 1.0wt.%	11	It is	No	The iron chloride of 1.0wt.%

As it appears from the above, being rinsed to some samples, handle, some samples are dried immediately after first, is then handled with shown aqueous solution.After drying, sample 3,6,7 and 10 is sprayed with two layers flat non-zinc-plated (7776) high-quality ruthenium osmiridium protection enamel.0.00145 inch of final dry film coating thickness average out to.It is under external environmental condition that the breadboard applied is 24 hours dry, it is secondly placed in wet exposure (ASTM-D2247) 24 hours, it is then 24 hours dry under external environmental condition before carrying out bonding test.As follows, salt spray test (ASTM-B117) or paint adhesion test (ASTM D-3359) are carried out to processed plate.

Sample #	The loss of % adhesion of coatings	There is the time (hour) of first time B117 red rust	There is the time (hour) of 5%B117 red rust
Sample #	The loss of % adhesion of coatings	There is the time (hour) of first time B117 red rust	There is the time (hour) of 5%B117 red rust	1	-	288	456
2	-	168	216	1	-	288	456
2	-	168	216	3	0	-	-
4	-	144	216	3	0	-	-
4	-	144	216	5	-	96	120
6	100	-	-	5	-	96	120
6	100	-	-	7	15-35	-	-
8	-	72	96	7	15-35	-	-
8	-	72	96	9	-	192	288
10	15-35	-	-	9	-	192	288
10	15-35	-	-	11	-	168	168
12	-	72	96	11	-	168	168

The above results show that zirconyl carbonate ammonia has advantageous effect to the improvement of the adhesiveness of postorder coating and the corrosion resistance on uncoated surface.Salt spray results show that corrosion resistance can be weakened by rinsing and being exposed in strong phosphoric acid immediately.

Example 29

This example demonstrates the effect of process of the invention to stress corrosion cracking.These tests are carried out to check that electrolysis of the invention handles the influence for the sensibility split to AISI304 and 316 stainless steel probe tubes to stress.The pitting resistance that the test discloses the sample after implementation technique of the invention makes moderate progress.It include three corrosion coupons steel in each test group.Mineralising sample is tested after the electrolysis processing (15 minutes) of the method B of embodiment 16.

Table R gives the result of corrosion test.The end grain attack that untreated probe tube is subjected to mainly is subject to the probe tube of electrolysis processing.

Material	Mineralising processing	The average maximum (μM) of pitting penetration	The average value (μM) of 10 deepest points erosion	Pitting density (spot corrosion/cm²)	Average quality loses (g/cm²)
Material	Mineralising processing	The average maximum (μM) of pitting penetration	The average value (μM) of 10 deepest points erosion	Pitting density (spot corrosion/cm²)	Average quality loses (g/cm²)	AISI304	It is no	2847	1310	4.1	0.034
AISI304	It is	2950	1503	0.2	0.020	AISI304	It is no	2847	1310	4.1	0.034
AISI304	It is	2950	1503	0.2	0.020	AISI316L	It is no	2083	1049	2.5	0.013
AISI316L	It is	2720	760	0.3	0.005	AISI316L	It is no	2083	1049	2.5	0.013

Mineralising processing of the invention effectively reduces the number of occurred spot corrosion.

Example 30

This example demonstrates the effect of method of the invention to the resistance to rupture for improving following substrate.Before mineral processing of the application as described in the method B (5 and 15 minutes) of example 16, heat-sensing is carried out at 1200F to the curved stress corrosion sample of 9 U-shapeds made of AISI304 stainless steel and handles 8 hours.Each test group includes 8 inches long, 2 inches wide and 1/16 inch three samples.After being handled using mineral, sample is put on stainless steel tube section and is squeezed.Exposure sequence is identical as described in ASTM C692, and including applying foam gas thermal insulation around the U-Bemd sample being consistent with its shape.A kind of combined 2.473g/L NaCl solution is introduced continuously into the tensile surface of sample by the hole in insulator.Flow velocity is adjusted so as to wet/dry condition in the part for obtaining sample.Internal heating is carried out to the section of pipe using cartridge heater and heat-transfer fluid and controls test temperature in 160F.The test carries out 100 hours, then visually inspects test sample, as a result as follows:

Material	Mineral processing	Mineral handle time (minute)	The average number of rupture	Average total rupture length (inch)
Material	Mineral processing	Mineral handle time (minute)	The average number of rupture	Average total rupture length (inch)	AISI304	It is no	0	8.7	1.373
AISI304	It is	5	2.7	0.516	AISI304	It is no	0	8.7	1.373
AISI304	It is	5	2.7	0.516	AISI304	It is	15	4.3	1.330

Mineralising processing of the invention efficiently reduces number and length that rupture occurs.

Example 31

This example describes the improved heat resistance and corrosion resistance of the zinc plated parking brake line end fitting sleeves handled compared with conventional chromate 1 is handled according to the present invention.

The hourage and corrosion resistance (exposure of ASTM B-117 salt fog) of heat exposure

		Extraneous (70F)			200F/15 minutes			400F/15 minutes			600F/1 5 minutes			700F/15 minutes
		Extraneous (70F)			200F/15 minutes			400F/15 minutes			600F/1 5 minutes			700F/15 minutes					White rust for the first time	Red rust for the first time	Damaged red rust	White rust for the first time	Red rust for the first time	Damaged red rust	White rust for the first time	Red rust for the first time	Damaged red rust	White rust for the first time	Red rust for the first time	Damaged red rust	White rust for the first time	Red rust for the first time	Damaged red rust
Zinc-plated control group	Average value	24	136	212	24	204	276	24	123	187	24	119	204	24	60	162			White rust for the first time	Red rust for the first time	Damaged red rust	White rust for the first time	Red rust for the first time	Damaged red rust	White rust for the first time	Red rust for the first time	Damaged red rust	White rust for the first time	Red rust for the first time	Damaged red rust	White rust for the first time	Red rust for the first time	Damaged red rust
Zinc-plated control group	Average value	24	136	212	24	204	276	24	123	187	24	119	204	24	60	162	CM^*Zinc is without rinsing	Average value	72	520	1128	72	620	1148	72	430	464	72	220	448	48	99	264
CM^*Zinc technology (A) (silane)	Average value	72	736	1216	72	716	1320	72	295	1084	72	271	448	48	83	247	CM^*Zinc is without rinsing	Average value	72	520	1128	72	620	1148	72	430	464	72	220	448	48	99	264
CM^*Zinc technology (A) (silane)	Average value	72	736	1216	72	716	1320	72	295	1084	72	271	448	48	83	247	Zinc detergent chromate	Average value	48	128	239	48	127	262	24	84	181	24	84	153	24	52	278
Zinc chrome yellow acid	Average value	420	1652	2200	424	1360	1712	48	202	364	24	93	168	24	24	170	Zinc detergent chromate	Average value	48	128	239	48	127	262	24	84	181	24	84	153	24	52	278
Zinc chrome yellow acid	Average value	420	1652	2200	424	1360	1712	48	202	364	24	93	168	24	24	170	Zinc olive-drab chromate	Average value	312	1804	2336	294	1868	2644	48	331	576	36	97	168	24	76	236

^*Cathode treatment is carried out according to the present invention

+ each of the above value represents the average value of 6 single samples

It is about 1.5 inches by length, diameter is about that 0.50 inch of cylindrical galvanized wire end fitting sleeves are divided into six groups.One group without postorder surface treatment.One group is handled with the cleaning chromate conversion coatings commercially bought.One group is handled with chrome yellow hydrochlorate transformant, and one group is handled with olive-drab chromate conversion coatings.Two groups carry out cathode in the bath for including deionized water and about 10wt.%N sodium silicate solution under 12 volts (70-80 DEG C) and charge 15 minutes.One of cathode charging group is dried without being further processed.Another group is successively rinsed with following solution: deionized water has 2vol.%1 including 10wt.% denatured ethyl alcohol, the deionized water solution of 2 (double three ethoxies silicyls) ethane (commercially being provided by Aldrich), the deionized water solution with 2vol.% epoxy silane (commercially being provided by OSF Specialties, trade name Silquest A-186) including 10wt.% denatured ethyl alcohol

Each group in this six groups is finely divided again and is exposed in the following conditions: (A) does not heat up.(B) 200 °F 15 minutes.(C) 400 °F 15 minutes.(D) 600 °F 15 minutes.Or 700 °F of (E) 15 minutes, and in ASTM B-117 salt fog test until breakage.As a result as shown above.

Example 32

This example describes a kind of technique including process of the invention, is post-processed after technique of the invention.Post-processing includes contacting previously processed product with the water-bearing media containing water-soluble or dispersibility compound.

Process of the invention carries out in a kind of electrolyte, by being added to the N sodium silicate solution of 349.98g in the process tank of the deionized water containing 2.8L, to prepare the electrolyte.By solution mixing 5-10 minutes.The iron chloride of 0.1021g is mixed into the deionized water of 352.33g.It is internalized by both solution i.e. sodium metasilicate and iron chloride in process tank and merges stirring.A certain amount of deionized water, which is added in tank, makes final liquor capacity 3.5L.ACT zinc (plating) plate is impregnated in the electrolyte about 15 minutes as cathode.Anode includes the niobium sieve with platinum backpack cover.

Post-processing medium below is prepared by the way that the compound of listed amount to be add to deionized water:

A) zirconium acetate (200g/L)

B) zirconium oxychloride (100g/L)

C) calcirm-fluoride (8.75g/L)

D) aluminum nitrate (200g/L)

E) sulfuric acid is beautiful (100g/L)

F) tin fluoride (11) (12g/L)

G) zinc sulfate (100g/L)

H) titanium fluoride (5g/L)

I) zirconium fluoride (5g/L)

J) titanium chloride (150g/L)

K) stannic chloride (20g/L)

According to the corrosion resistance of the zine plate of ASTM B-117 test post-processing.It is listed below test result.

	There is the time (hour) of first time white rust	There is the time (hour) of first time white rust	It is damaged
	There is the time (hour) of first time white rust	There is the time (hour) of first time white rust	It is damaged	Zirconium acetate Zn	5	96	96
Basic zirconium chloride Zn	5	120	120	Zirconium acetate Zn	5	96	96
Basic zirconium chloride Zn	5	120	120	Calcirm-fluoride Zn	24	96	96

Aluminum nitrate Zn	24	144	240
Aluminum nitrate Zn	24	144	240	Magnesium sulfate Zn	24	264	456
Tin fluoride Zn	24	288	312	Magnesium sulfate Zn	24	264	456
Tin fluoride Zn	24	288	312	Zinc sulfate Zn	5	96	96
Titanium fluoride Zn	24	72	72	Zinc sulfate Zn	5	96	96
Titanium fluoride Zn	24	72	72	Zirconium fluoride Zn	24	144	264

Example 33

This example, which describes, is added to dopant in the electrolyte (or bath) of process for carrying out the present invention.In every an example below, semi-products include cathode, and anode includes the niobium sieve with platinum backpack cover.Electrolyte is prepared according to the method for example 32 and the dopant for the amount of showing is added.It will include that the ACT breadboard of zinc, iron or 304 stainless steels is impregnated into the electric current that in electrolyte and introducing is shown.

Dopant (zirconium acetate bath, 200/L)
Dopant (zirconium acetate bath, 200/L)							Plate	Zn	Zn	Fe	Fe	30455	30455
Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Plate	Zn	Zn	Fe	Fe	30455	30455
Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	0	13.1	13.3	12.9	12.4	12.0	11.8
15	13.2	130	121	116	11.1	111	0	13.1	13.3	12.9	12.4	12.0	11.8
15	13.2	130	121	116	11.1	111	Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76
Dopant (basic zirconium chloride bath, 00g/L)							Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76
Dopant (basic zirconium chloride bath, 00g/L)							Plate	Zn	Zn	Fe	Fe	30455	30455
Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Plate	Zn	Zn	Fe	Fe	30455	30455
Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	0	11.2	11.2	11.3	111	10.5	11.2
15	10.9	10.5	10.3	10.1	10.0	10.6	0	11.2	11.2	11.3	111	10.5	11.2
15	10.9	10.5	10.3	10.1	10.0	10.6	Bath temperature	77-76C	74-76	74-76	74-76	74-76	74-76
Dopant (calcirm-fluoride bath, 8.5g/L)							Bath temperature	77-76C	74-76	74-76	74-76	74-76	74-76
Dopant (calcirm-fluoride bath, 8.5g/L)							Plate	Zn	Zn	Fe	Fe	30455	30455
Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Plate	Zn	Zn	Fe	Fe	30455	30455
Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	0	11.2	11.0	110	10.7	9.2	121
15	11.0	10.8	10.4	9.7	9.0	11.5	0	11.2	11.0	110	10.7	9.2	121
15	11.0	10.8	10.4	9.7	9.0	11.5	Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76
Dopant (nitric acid aluminum bath, 200g/L)							Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76
Dopant (nitric acid aluminum bath, 200g/L)							Plate	Zn	Zn	Fe	Fe	30455	30455
Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Plate	Zn	Zn	Fe	Fe	30455	30455
Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	0	12	12.9	12.5	12.2	11.8	11.4
15	13.3	12.7	12	11.7	11.1	11	0	12	12.9	12.5	12.2	11.8	11.4

Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	Dopant (magnesium sulfate bath, 100g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Dopant (magnesium sulfate bath, 100g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11.1	10.6	10.2	10.8	11.3	11.8	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11.1	10.6	10.2	10.8	11.3	11.8	15	10.5	9.9	9.9	10.5	10.6	10.9
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	15	10.5	9.9	9.9	10.5	10.6	10.9
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	Dopant (fluorination tin bath, 12g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Dopant (fluorination tin bath, 12g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11	12.1	11.6	11.3	10.5	10.7	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11	12.1	11.6	11.3	10.5	10.7	15	11.1	11.4	10.8	10	9.4	9.4
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	15	11.1	11.4	10.8	10	9.4	9.4
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	Dopant (zinc sulfate bath, 100g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Dopant (zinc sulfate bath, 100g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11.3	10.9	9.9	9.3	8.5	9.3	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11.3	10.9	9.9	9.3	8.5	9.3	15	10.1	9.7	8.9	8.3	7.9	8
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	15	10.1	9.7	8.9	8.3	7.9	8
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	Dopant (titanium fluoride bath, 5g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Dopant (titanium fluoride bath, 5g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	12	12.8	12.1	13.3	12.9	12.7	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	12	12.8	12.1	13.3	12.9	12.7	15	12.4	12.4	11.6	12.9	12.1	11.8
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	15	12.4	12.4	11.6	12.9	12.1	11.8
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	Dopant (zirconium fluoride bath, 5g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Dopant (zirconium fluoride bath, 5g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11.3	11.9	12.1	12.1	11.7	11.4	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11.3	11.9	12.1	12.1	11.7	11.4	15	11.8	11.7	11.5	11.3	10.8	10.7
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	15	11.8	11.7	11.5	11.3	10.8	10.7
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	Dopant (titanium chloride (III) bath, 150g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Dopant (titanium chloride (III) bath, 150g/L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11.0	8.8	9.3	10.0	10.2	10.2	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	11.0	8.8	9.3	10.0	10.2	10.2	15	9.4	8.0	8.6	9.3	8.9	8.4

Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	Dopant (chlorination tin bath, 20g/1L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Dopant (chlorination tin bath, 20g/1L)
Plate	Zn	Zn	Fe	Fe	30455	30455	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	10.7	10.2	9.5	97	9.6	93	Minute	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)	Electric current (A)
0	10.7	10.2	9.5	97	9.6	93	15	9.3	9.1	8.8	86	8.3	79
Bath temperature	74-76C	74-76	74-76	74-76	74-76	74-76	15	9.3	9.1	8.8	86	8.3	79

Example 34

This example, which is described, activates mineralised surface with acidic rinse liquid before applying sealer (such as Enthonw (R) sealer).Make length be about 1.23 inches, diameter be about 5/8 inch zinc plated mild carbon steel cylindrical thread cutting mechanism the parsing of end connector sleeve, then the plating shield of lab size in again plating and mineralising zinc-plated to remove.Mineralized sleeves are subjected to dipping post-processing in citric acid (A group) or nitric acid (B group), and apply the sealer (Enthone (R) C-23) commercially bought.After 24 hours, the exposure test of ASTMB-117 salt fog is carried out to closed sleeve.A group is exposed to 144 hours in ASTMB-117 until observing white rust, and B group exposes about 120 hours before onset of white rust.

Mineralising is carried out on the processing line of lab size using following parameter:

Tankage size: 25 gallons

Orientation: 6 × 12 inch mini-barrel of Stirling

Anode: the niobium sieve of platinum plating

Work area: 736 square inches

Job category: zinc-plated line end fitting sleeves

Workload: 184

Runing time: 15 minutes

Working voltage: 12.0 volts

Ultimate current: AVG28 amperes

Running temperature: 78-79.5 DEG C

Electrolyte solution: the silicate solutions of deionized water, 10wt.% containing Fe2O3 doping agent

Power supply: Aldonex model T-224-7.5CR-CCV

Mineralization process post-processing is implemented as follows: being impregnated 5 seconds in the 20 zirconyl carbonate ammonia of Bacote (R) of 20wt.%, then spin is 30 seconds dry in New Holland Model K-11 spin drier under ambient temperature, wherein 15 seconds forward circulations, 15 seconds recycled backs.Time and the temperature of the every step process implemented in this example are listed in following table.

A group
A group			Processing step	Time (minute)	Temperature (DEG C)
Zinc is removed in 15vol.%HCl	5 minutes	20℃	Processing step	Time (minute)	Temperature (DEG C)
Zinc is removed in 15vol.%HCl	5 minutes	20℃	Deionized water rinsing	5 seconds	20℃
Deionized water rinsing	5 seconds	20℃	Deionized water rinsing	5 seconds	20℃
Deionized water rinsing	5 seconds	20℃	Alkaline zine plate (- 90A)	20 minutes	20℃
Stagnant H20 rinsing	30 seconds	20℃	Alkaline zine plate (- 90A)	20 minutes	20℃
Stagnant H20 rinsing	30 seconds	20℃	Deionized water rinsing	30 seconds	20℃
Mineralising -28A (12V)	15 minutes	78-79.5℃	Deionized water rinsing	30 seconds	20℃
Mineralising -28A (12V)	15 minutes	78-79.5℃	It spins dry (2)	60 seconds	Ambient temperature
B post-processes Bacote (R) 20	5 seconds	20℃	It spins dry (2)	60 seconds	Ambient temperature
B post-processes Bacote (R) 20	5 seconds	20℃	Spin drying	30 seconds	Ambient temperature
The w/.25% nitric acid of activation	5 seconds	20℃	Spin drying	30 seconds	Ambient temperature
The w/.25% nitric acid of activation	5 seconds	20℃	Spin drying	30 seconds	Ambient temperature
Close ethyl alcohol (R) C-23	90 seconds	55℃	Spin drying	30 seconds	Ambient temperature
Close ethyl alcohol (R) C-23	90 seconds	55℃	Spin drying	30 seconds	Ambient temperature
Furnace solidification	10 minutes	80℃	Spin drying	30 seconds	Ambient temperature

B group
B group			Processing step	Time (minute)	Temperature (DEG C)
Zinc is removed in 15vol.%HCl	5 minutes	20℃	Processing step	Time (minute)	Temperature (DEG C)
Zinc is removed in 15vol.%HCl	5 minutes	20℃	Deionized water rinsing	5 seconds	20℃
Deionized water rinsing	5 seconds	20℃	Deionized water rinsing	5 seconds	20℃
Deionized water rinsing	5 seconds	20℃	Alkaline zine plate (- 90A)	20 minutes	20℃
StagnantH20 rinsing	30 seconds	20℃	Alkaline zine plate (- 90A)	20 minutes	20℃
StagnantH20 rinsing	30 seconds	20℃	Deionized water rinsing	30 seconds	20℃
Mineralising -28A (12V)	15 minutes	78-79.5℃	Deionized water rinsing	30 seconds	20℃
Mineralising -28A (12V)	15 minutes	78-79.5℃	It spins dry (2)	60 seconds	Ambient temperature
Bacote (R) 20 is post-processed	5 seconds	20℃	It spins dry (2)	60 seconds	Ambient temperature
Bacote (R) 20 is post-processed	5 seconds	20℃	Spin drying	30 seconds	Ambient temperature
The w/5% citric acid of activation	5 seconds	20℃	Spin drying	30 seconds	Ambient temperature
The w/5% citric acid of activation	5 seconds	20℃	Spin drying	30 seconds	Ambient temperature

Close ethyl alcohol (R) C-23	90 seconds	55℃
Close ethyl alcohol (R) C-23	90 seconds	55℃	Spin drying	30 seconds	Ambient temperature
Furnace solidification	10 minutes	80℃	Spin drying	30 seconds	Ambient temperature

Example 35

This example, which describes, implements process of the invention, and Anodic includes niobium sieve.Cathode includes ACT electrolytic galvanized sheet.

By by the FeCl of the N sodium silicate solution of 349.98g, 0.1021g₃Merge with enough distilled water so that the total volume of solution reaches 3.5L, to prepare electrolyte.The every wheel of zine plate runs 15 minutes and begins to drying without rinsing.Before each round and after plate dried, zine plate is weighed to measure in electrochemical process by the weight pick-up caused by cathode.Start in experiment, also to weigh niobium sieve after 10 wheels, after 20 wheels and after 23 wheels.This allows to calculate the weight pick-up of anode.Voltage is set in 12.0V in all wheels.

The data of each round in 23 completed wheels can be found in following table.Following data shows that the electric current and voltage passed through between motor all keeps stablizing in all wheels.

Table: multiple circulations of niobium sieve anode and zinc cathode are utilized in sodium metasilicate electrolyte

Take turns the cathode of electric current (A) multimeter (V) weight change

# starts over (g)

1 12.7 13.9 8.40 6.88 0.014

2 13.5 13.3 10.32 10.15 0.037

3 13.1 13.2 10.58 10.14 0.032

4 12.6 12.8 10.30 9.91 0.016

5 12.7 13.2 10.04 10.04 0.016

6 13.5 14.0 9.68 9.63 0.037

7 13.3 13.8 9.03 9.72 0.038

8 13.4 13.7 9.38 9.44 0.035

9 13.3 13.6 9.76 8.96 0.038

10 9.0 9.2 10.45 10.34 0.035

11 11.0 11.7 10.06 9.96 0.027

12 10.8 11.8 9.97 9.60 0.033

13 11.2 11.9 10.13 9.87 0.014

14 11.7 12.0 9.96 10.09 0.029

15 11.4 12.0 9.60 9.44 0.030

16 11.7 12.1 10.15 9.94 0.030

17 12.1 12.4 9.82 10.10 0.028

18 12.1 12.4 10.33 10.26 0.031

19 11.7 12.2 10.77 10.28 0.030

20 11.9 12.3 10.37 10.16 0.029

21 8.4 9.4 8.85 9.10 0.002

22 9.7 9.9 10.53 10.57 0.022

23 9.4 10.0 10.39 10.52 0.022

Example 36A-36C shows to handle using process of the invention for component manufacturing of electric machines and component.

Example 36A

This example shows that the process processing using of the invention includes the assembling product of motor laminate component.

Under the direct current (average value of 9.75 amperes of 9-10 ampere) of 80C and 12V, 2.75 inch diameters × 0.40 inch motor laminate component is handled 15 minutes, which includes 13 and be individually casted into together and the laminated product including high si fe alloy.Implement the processing in the tank of the mineralizing solution of the iron chloride of the N sodium metasilicate (PQ Corp.) and 0.001wt.% including 10wt.% containing 25 gallons.Using the niobium sieve anode of the painting platinum of size constancy, and and being hung with copper hook, cathode connects the tinkertoy module, and the centre bore that the copper hook passes through tinkertoy module is inserted into.Processing complete after, by under ambient temperature in 6 inches of lab size of blue formula New Holland spin dry machine the tinkertoy module is 30 seconds positive, anti-30 seconds spinning cycles, excessive solution can be removed.Thereafter, (Gelest is come from bis- (triethoxysilyl) ethane including 2vol.%, Inc. CAS #16086-37-4) and 98vol.% ethyl alcohol (10vol.%) solution and deionized water (90vol.%) solution in by the tinkertoy module impregnate 5 seconds, then spin as previously described to remove excessive solution.Thereafter, tinkertoy module is immersed in the second solution of silane, the preparation of the solution is similar with the first solution of silane, only containing β-(3,4- epoxycyclohexyl) ethyl trimethyl silane (coming from Gelest, the CAS#3388-04-3 of Inc.).Tinkertoy module is spinning off excess solution and under ambient temperature after drying 1 hour certainly, the epoxy finish (B18-Magni Industries) filled according to following operation with metallic particles is coated: dipping is to be completely covered, fall excessive finishing coat drop, then spins in New Holland spin dry machine as described above.Make the curing of coatings in laboratory convection oven 10 minutes in 90C, then at 205C resolidification 20 minutes.Thereafter, by being placed in the tinkertoy module in salt fog exposure 500 hours in total using ASTM B-117 method, to assess the corrosion resistance of the component.When exposure 168 hours, the surface less than 5% is generated with red rust product.When exposure 500 hours, 25% surface has mainly from the edge and internal red rust of tinkertoy module, it is clear that does not have coating adhesion loss.

Example 36B

This example describes using the surface of process formation of the invention the bonding for reducing molten metal.

At (4.8-10.7 amperes of direct current of 75-77C and 12V；6.4 amperes of average value) under, the motor core laminates of 2.75 inch diameters containing high silicon steel are handled 15 minutes.Include containing 1.8L 10wt.% N sodium metasilicate (PQ Corp.) and 0.001wt.% iron chloride mineralizing solution beaker in implement the processing.It is fastened on copper wire and on the stainless steel cover support folder that is connected with the edge of laminates using two steel anodes (3 × 6 cold-rolled steel probe tubes of standard, the laboratory ACT), and by being suspended on laminates, and cathode connects the laminates of the cleaning.Processing complete after, by under ambient temperature in 6 inches of lab size of blue formula NewHolland spin dry machine the laminates are 30 seconds positive, anti-30 seconds spinning cycles, excessive solution can be removed.Thereafter, (Gelest is come from bis- (triethoxysilyl) ethane including 2vol.%, Inc. CAS#16086-37-4) and 98vol.% ethyl alcohol (10vol.%) solution and deionized water (90vol.%) solution in by the laminates impregnate 5 seconds, then spin as previously described to remove excessive solution.Thereafter, laminates are immersed in the second solution of silane, the preparation of the solution is similar with the first solution of silane, only containing β-(3,4- epoxycyclohexyl) ethyl trimethyl silane (coming from Gelest, the CAS#3388-04-3 of Inc.).Laminates are spinning off excess solution and under ambient temperature after drying 1 hour certainly, the high temperature topcoat system (B68/B70-Magni Industries) filled according to following operation with metallic particles is coated: dipping is to be completely covered, fall excessive finishing coat drop, then spins in New Holland spin dry machine as described above.Make the curing of coatings in laboratory convection oven 10 minutes in 90C, then at 288C resolidification 20 minutes.Thereafter, the resistance that the laminates are contacted with molten aluminum is assessed.Melt aluminium alloy (Alcanal 801737) in about 1500 ° of metallic crucible.The finishing coat overlapping piece midway is temporarily impregnated into molten aluminum, then takes out the laminates when observing no aluminium and adhering on laminates.When observing that aluminium has covered the edge of laminates and has been full of stacking slot along immersed edge, which is repeated 5 seconds.After the laminates are cooling, it can be observed manually to peel off aluminized coating from laminates edge and the face painting of the laminates do not revealed.This application confirms, a barrier is formed between steel layer overlapping piece and molten aluminum using the present invention.

Example 36C

This example demonstrates using process of the invention and partially handles assembling product.

At (6-7 amperes of direct current of 75-80C and 12V；6.75 amperes of average value) under, the long motor laminate core component in 2.75 inch diameter × 6 inch is handled 15 minutes, which includes multiple be individually casted into together and and the laminated product (high si fe alloy) that is assembled on simulation axis.Implement the processing in the tank of the mineralizing solution of the iron chloride of the N sodium metasilicate (PQ Corp.) and 0.001wt.% including 10wt.% containing 25 gallons.Using the niobium sieve anode of the painting platinum of size constancy.The position of manual rotation's component and component makes 0.5 inch of external side of only magnetic core in solution and impregnates on the bus of cathode connection, and component keeps rotation.Processing complete after, by under ambient temperature in 6 inches of lab size of blue formula New Holland spin dry machine the tinkertoy module is 30 seconds positive, anti-30 seconds spinning cycles, excessive solution can be removed.From the end of component, the outer surface of magnetic core (mineralised zones) is visually upper different from the center of magnetic core.

Example 37

This example it is visual using process of the invention is formed on rivet it is flexible, bond and corrosion resistant surface.

The zinc-plated rivet for being coated with 0.2-0.3 mil in advance with 150 pounds loads 18 inch diameters, 36 inches long of plating bucket.It is 1.05 inches that each rivet, which has the head of 0.75 inch diameter, the bar of 0.25 inch diameter and overall length,.Mineralising is carried out to rivet in 180 gallons of the solution at a temperature of 75C in rectangular tank to handle 30 minutes.The temperature is maintained using the outflow by Chromalox heater (NWHIS-18-075P-E4XX).Direct current and electric current are supplied in the range of 102-126 amperes (113 amperes of average values) in 12V conducive to AldonexUltimatic DC power supply (model T-412-20CFR-COV).Cathode connects the bucket, and anode is made of the niobium sieve that the platinum of the size constancy formed in the tank of paraboloidal is coated with, so that bucket is surround in side and bottom by anode part.After mineralising processing is completed, bucket is produced to 30 seconds to make excess solution drip-dry from solution, so that bucket is rotated 30 seconds in deionized water so as to drip-dry again and produced from solution.Then by rivet out of, the commercial size that standard is poured into bucket dipping-spin indigo plant, and excessive solution is spun off certainly in New HollandK-90 spin dry machine using direct circulation in 30 seconds and 30 seconds reacting cycles.Thereafter, (Gelest is come from bis- (triethoxysilyl) ethane including 2vol.%, Inc. CAS#16086-37-4) and 98vol.% ethyl alcohol (10vol.%) solution and deionized water (90vol.%) solution in by the rivet impregnate 5 seconds, then spin as previously described to remove excessive solution.Thereafter, rivet is immersed in the second solution of silane, the preparation of the solution is similar with the first solution of silane, only containing β-(3,4- epoxycyclohexyl) ethyl trimethyl silane (coming from Gelest, the CAS#3388-04-3 of Inc.).From spinning off excess solution and at 49-54C by rivet dry 5 minutes, while spinning.It impregnates-spins in machine in Ronci and be coated with rivet using dipping-spinning technology metallic particles filling epoxy finish (B17-Magni Industries).Make the curing of coatings 10 minutes in the commercial belt furnace for including 90C exposed region, then at 205C resolidification 20 minutes.Then, by the way that rivet (with or without B17 finishing coat) is exposed in salt fog using ASTM B-117 method, to assess the corrosion resistance of rivet.As a result as follows:

Only zinc plated rivets: mean hours number=124 red rusts of red rust are first appeared up to 5% mean hours number=288

Rivet w/ mineral & silane: mean hours number=416 red rusts of red rust are first appeared up to 5% mean hours number=728

Rivet w/ mineral, silane, B17 coating: mean hours number=1184 red rusts of red rust are first appeared up to 5% mean hours number=1336

Example 38

This example describes the adhesion characteristic of Dorriform (R) E (A31) and Dorritech (R) Silver (B17) on the galvanized sheet with mineralised surface of the invention.Between niobium anode by the platinum coating of the size constancy for two rectangles that each 4 " × 12 " plate is suspended in solution described in 25 gallons of examples 28, to implement mineralization process.It is carried out mineralising 15 minutes under the direct current of 70-80C and 12V.Electric current is in the range of 22-35 amperes (27 amperes of average values).Dorriform and Dorritech is the heat cured epoxy topcoatings commercially bought.Mineralised surface of the invention is post-processed by being rinsed according to example 36 with silane, the difference is that carrying out outside ambient air drying and being conducive to static suspension to replace New Holland spin dry machine.

Adhesiveness test is carried out at three dome heights (0.150,0.200,0.300 inch) on Timius Olsen machine and every Gerneral Motor GM6190M divides level-one.Also carry out the intersection adhesiveness grade of every Gerneral Motor GM6190M.Testing scheme GM6190M and GM907P are incorporated herein by reference herein.By applying and removing the 3M 610 of standard with the adhesiveness can be tested.

4 × 12 inches of plates are coated with epoxy coating, then carry out heat cure.These samples are swelled 0.150,0.200,0.300 inch and test the adhesiveness grade of every GM6190M.Sample all so intersects and every GM9071P values for being recorded just point level-one.

Every GM9071P of coating finished product shows do not have coating to be removed using coating system method for pretreating with the bonding grade of adhesiveness.The experiment represents the result without formation or curved film.

For Olsen cupping machine, the every GM6190M of plate of the stretching of domed form just point level-one will be received, to provide the photograph standard of paint loss.Corresponding coating finished product, adhesion test ratio GM9071P band adhesion test are tested tightened up.Based on these grades, using the mineralization process of the invention of silane rinse increase adhesiveness and meet more than identifying description.

Example 39

This example demonstrates flexibility, the patience of corrosion resistance and secondary processes on the surface that process according to the invention is formed.

6 inch diameters, 12 inches long of plating bucket are loaded with 200 zinc-plated parking brake line end fitting sleeves of 0.2-0.3 mil are coated in advance.The length that each cylindrical sleeve measures is about 1.5 inches, diameter is about 0.5 inch, and the surface area with about 4.0 square inches.Mineralising is carried out to sleeve in 25 gallons of the solution at a temperature of 75C in rectangular tank to handle 15 minutes.Direct current and electric current are supplied in the range of 20-32 amperes (24 amperes of average values) in 12V using Aldonex DC power supply.Cathode connects the bucket, and uses the niobium sieve anode of the platinum coating of size constancy.After mineralising processing is completed, bucket is produced to 30 seconds from solution to make excess solution drip-dry, then out of, 6 inch lab sizes are poured into bucket New Holland spin dry machine, and excessive solution is being spun off certainly using direct circulation in 30 seconds and 30 seconds reacting cycles.Thereafter, (Gelest is come from bis- (triethoxysilyl) ethane including 2vol.%, Inc. CAS#16086-37-4) and 98vol.% ethyl alcohol (10wt.%) solution and deionized water (90wt.%) solution in by the half sleeve impregnate 5 seconds, then spin as previously shown to remove excessive solution.Then, sleeve is immersed in the second solution of silane, the preparation of the solution is similar with the first solution of silane, only containing β-(3,4- epoxycyclohexyl) ethyl trimethyl silane (coming from Gelest, the CAS#3388-04-3 of Inc.).From spinning off excess solution and under ambient temperature by sleeve dry 5 minutes, while spinning.The other half sleeve is impregnated 5 seconds in Bacote20 (Magnesium Elektron) solution, the solution containing zirconyl carbonate ammonia of 20wt.%；Then spin drying is carried out as described above.Thereafter above-mentioned two groups of each group of sleeve is divided into Liang Ge group and is coated with every a small group: (A) clean substantially aqueous epoxy finish (W86-Magni Industries) with one of following finishing coat；And the substantially aqueous polyurethane finish containing 80.5wt.%Neorez R9637 (Zeneca Resins), 6.5wt.%N sodium metasilicate (PQ Corp.) and 13.0wt.% deionized water that (B) is clean.Coating is applied by dipping-spin using New Holland spin dry machine illustrated above.Make W86 curing of coatings in laboratory convection oven 10 minutes in 90C, then at 177C resolidification 30 minutes.Solidify polyurethane coating 10 minutes in 60C, then at 125C resolidification 30 minutes.In addition, preparation has the comparative group sleeve of silane rinse liquid disclosed above as described above, but the comparative group will be also crimped on spool to assess the ability that coating system restrains oneself manufacturing process.Two additional coatings: the epoxy finish (B18-Magni Industries) of (C) metallic particles filling are also tested under the conditions of following curling；(D) epoxy finish (B17-MagniIndustries) of metallic particles filling.Make B18 and B17 curing of coatings in laboratory convection oven 10 minutes in 90C, then at 205C resolidification 20 minutes.Then, by the way that sleeve (curling or not crimping) is exposed in salt fog using ASTMB-117 method, to assess the corrosion resistance of sleeve.

The test result of salt fog ASTMB-117

1) mineral+W86 is not crimped: mean hours number=312 for first appearing white rust first appear the mean hours number of red rust=1584 red rusts up to 5% mean hours number=2112 (silane)

2): mineral+W86 is not crimped: mean hours number=312 for first appearing white rust first appear the mean hours number of red rust=1244 red rusts up to 5% mean hours number=1744 (Bacote20)

3) mineral+W86 is not crimped: mean hours number=280 for first appearing white rust first appear 408 red rust of mean hours number > of red rust up to 5% mean hours number > 408 (silane)

4) mineral+PU is not crimped: mean hours number=312 for first appearing white rust first appear the mean hours number of red rust=1456 red rusts up to 5% mean hours number=1596 (silane)

5) mineral+PU is not crimped: mean hours number=320 for first appearing white rust first appear the mean hours number of red rust=1460 red rusts up to 5% mean hours number=1652 (Bacote20)

6) mineral+PU curling: mean hours number=320 for first appearing white rust first appear 408 red rust of mean hours number > of red rust up to 5% mean hours number > 408

7) mineral+B17 curling: the mean hours number > 408 for first appearing white rust first appears 408 red rust of mean hours number > of red rust up to 5% mean hours number > 408

8) mineral+B18 curling: the mean hours number > 408 for first appearing white rust first appears 408 red rust of mean hours number > of red rust up to 5% mean hours number > 408

Example 40

This example demonstrates flexibility, the patience of corrosion resistance and secondary processes on the surface that process according to the invention is formed when being applied with heat cured epoxy face.

6 inch diameters, 12 inches long of plating bucket are loaded with 15 pounds of zinc-plated rivets of 0.2-0.3 mil are coated in advance.It is 1.05 inches that each rivet, which has the head of 0.75 inch diameter, the bar of 0.25 inch diameter and overall length,.Mineralising is carried out to rivet in 25 gallons of the solution at a temperature of 70-75C in rectangular tank to handle 15 minutes.Direct current and electric current are supplied in the range of 22-28 amperes (24 amperes of average values) in 12V using Aldonex DC power supply.Cathode connects the bucket, and uses 4 inches × 12 inches of cold-rolled steel probe tube (laboratory ACT) of two standards as anode and be arranged in the two sides of tank.After mineralising processing is completed, bucket is produced to 30 seconds from solution to make excess solution drip-dry, 30 seconds and drip-dry again are then rotated in deionized water rinsing liquid, while rotating and coming out from solution.Then by rivet out of, 6 inch lab sizes are poured into bucket New Holland spin dry machine, and excessive solution is spun off certainly using direct circulation in 30 seconds and 30 seconds reacting cycles.Thereafter, (Gelest is come from bis- (triethoxysilyl) ethane including 2vol.%, Inc. CAS#16086-37-4) and 98vol.% ethyl alcohol (10wt.%) solution and deionized water (90wt.%) solution in by rivet impregnate 5 seconds, then carry out as previously shown it is white rotation to remove excessive solution.Then, rivet is immersed in the second solution of silane, the preparation of the solution is similar with the first solution of silane, only contains β-(3,4- epoxycyclohexyl) ethyl trimethyl silane (Silquest A-186, OSI Specialties).From spinning off excess solution and under ambient temperature by rivet dry 5 minutes, while spinning.It impregnates-spins in machine in Ronci and be coated with rivet using dipping-spinning technology metallic particles filling epoxy finish (B17-Magni Industries).Make the curing of coatings 10 minutes in the commercial belt furnace for including 90C exposed region, then at 205C resolidification 20 minutes.A comparative group rivet is prepared with same group of zinc plated rivets, but is coated with using the hexavalent chromate convection current of yellow come proxy mineral coating, is similarly coated with Magni B17 thereafter.Then, it is mounted on rivet as accumulation and non-stacking sample on papering.By the way that rivet is exposed in salt fog using ASTM B-117 method, to assess the corrosion resistance of rivet.As a result as follows: (exposed hourage)

Mineral+B17 does not accumulate: the mean hours number > 3240 for first appearing white rust first appears 4736 red rust of mean hours number > of red rust up to 5% mean hours number > 5400

Mineral+B17 accumulation: mean hours number=1680 for first appearing white rust first appear 5400 red rust of mean hours number > of red rust up to 5% mean hours number > 5400

Chromate+B17 does not accumulate: mean hours number=928 for first appearing white rust first appear the mean hours number of red rust=2360 red rusts up to 5% mean hours number=2856

Chromate+B17 accumulation: mean hours number=72 for first appearing white rust first appear the mean hours number of red rust=888 red rusts up to 5% mean hours number=1651

The hexavalent chromate that the above results show that mineral processing makes to be combined with 17 finishing coat of B has a superior performance, and as bulk property is revealed, mineral processing also has fairly good resist damage.

Example 41

This example, which describes, is applied to the fluoropolymer containing finishing coat on mineralised surface.Using 6 inch diameter of Sterling, 12 inches of miniature buckets of long rotation, mineralising processing is carried out to following five kinds of components in 25 Gallon Solutions at a temperature of 70-75C in rectangular tank.

4.25 inch is long, the zinc-plated B7 Alloy Studs (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 helix of 60mm long

The 8 six flange angle-style flat head screw of zinc-plated grade of 2.25 inches long, 3/8 inch diameter complete spiral

The 8 six flange angle-style flat head screw of zinc-plated grade of 2.25 inches long, 3/8 inch diameter part helix

C, D and E group are handled in same wheel, and handle A&B group in an independent wheel.For handling the same wheel of C, D&E group, direct current and electric current are supplied in the range of 25-30 amperes (27 amperes of average values) in 12V using Aldonex DC power supply.And it is used to handle the electric current of that wheel of A&B group in the range of 23-32 amperes (27 amperes of average values).Cathode connects the niobium sieve anode that this barrel and the platinum in that wheel for handling A&B group using size constancy are coated with.And 4 inches × 12 inches of the cold-rolled steel probe tube (laboratory ACT) in that wheel for handling C, D&E group using six standards is as anode.After mineralising processing is completed, bucket is produced to 30 seconds from solution so as to drip-dry excess solution, then out of, 6 inch lab sizes are poured into bucket New Holland spin dry machine, and spin off excessive solution certainly using direct circulation in 30 seconds and 30 seconds reacting cycles.Thereafter, (Gelest is come from bis- (triethoxysilyl) ethane including 2vol.%, Inc. CAS#16086-37-4) and 98vol.% ethyl alcohol (10wt.%) solution and deionized water (9wt.%) solution in by these components impregnate 5 seconds, then spin as previously shown to remove excessive solution.Then, these components are immersed in the second solution of silane, the preparation of the solution is similar with the first solution of silane, only containing β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane (coming from Gelest, the CAS#3388-04-3 of Inc.).From spinning off excess solution and under ambient temperature by component dry 5 minutes, while spinning.

The zinc-plated stud of 5/8 inch diameter of mineralising is simultaneously rinsed with above-mentioned solution of silane, is then coated with fluoropolymer finishing coat (Xylan (R) provided by Whitford).All flat head bolts receive two layers of 1424/524 finishing coat (viscositys: 49sec.#2Zahn, 72 °F), and one group of flat head bolt also receives epoxy (Magni B06J:49sec.#2Zahn, 72 °F) priming operation of metal filling under Xylan finishing coat.It is required that the color of two layers of Xylan is uniform.Standard nut is not incorporated on the flat head bolt being applied.It is listed below salt spray results.

Xylan 1424/524+ Kuang Wu &b silane on zine plate

Sample type	Occurs the hourage of white rust first	Occurs the hourage of red rust first	Hourage of the red rust up to 5%
Sample type	Occurs the hourage of white rust first	Occurs the hourage of red rust first	Hourage of the red rust up to 5%	C	240	624	1272
E	144	936	1752	C	240	624	1272
E	144	936	1752	D	528	1440	2064
D	168	1272	2520	D	528	1440	2064
D	168	1272	2520	E	144	1104	2064
E	336	1272	2064	E	144	1104	2064
E	336	1272	2064	Average value	260	1108	1956

Xylan 1424/524+ mineral, Gui Wan &Magni B06J priming paint on zine plate

Sample type	Occurs the hourage of white rust first	Occurs the hourage of red rust first	Hourage of the red rust up to 5%
Sample type	Occurs the hourage of white rust first	Occurs the hourage of red rust first	Hourage of the red rust up to 5%	E	624	3456	5376
E	480	3048	4728	E	624	3456	5376
E	480	3048	4728	E	480	3936	> 5616
D	144	3456	> 5616	E	480	3936	> 5616
D	144	3456	> 5616	D	144	1368	4008
D	480	2520	4536	D	144	1368	4008
D	480	2520	4536	Average value	392	2964	> 4980

^*Test is discontinuous in salt fog exposure in 5616 hours

Xylan (stud with nut)+mineral & silane on zinc-plated

Sample type	Occurs the hourage of white rust first	Occurs the hourage of red rust first	Hourage of the red rust up to 5%
Sample type	Occurs the hourage of white rust first	Occurs the hourage of red rust first	Hourage of the red rust up to 5%	AB	144^**	1056	3072
AB	144^**	1056	> 4008	AB	144^**	1056	3072

AB	48^**	1176	3072
AB	48^**	1176	3072	AB	288^**	1824	> 4008
AB	288^**	2712	> 4008	AB	288^**	1824	> 4008
AB	288^**	2712	> 4008	AB	360^**	2928	> 4008
Average value	212^**	1792	> 3696	AB	360^**	2928	> 4008

^*Test is discontinuous in salt fog exposure in 4008 hours

^**White rust occurs on the nut of the edge between surface

Claims

1. a kind of product including a conductive substrates, wherein at least a part of substrate has an inorganic, not chromate-containing surface, and at least one composition adheres on the surface.