CN109642327A - The system and method that the preparation and maintenance for the treatment of compositions are formed by processing bath by it - Google Patents

Abstract

Disclosed by the invention is a kind of method for manufacturing treatment compositions.Lithium cation and carbon dioxide are merged in water-bearing media the treatment compositions that this includes lithium carbonate are formed in situ.It is also disclosed that a kind of system and method for maintaining to be formed by processing bath by the treatment compositions containing lithium carbonate.Carbon dioxide and/or lithium salts are supplied to the bath with such amount, the pH that the amount is enough to bathe the processing maintains 9.5-12.5, the amount that lithium amount maintains 5ppm-5500ppm (calculating as lithium cation) and carbonate is maintained into 15ppm-25000ppm (calculating as carbonate), the total weight based on processing bath.Also disclose the substrate handled with the composition, system and method.

Description

The system and method that the preparation and maintenance for the treatment of compositions are formed by processing bath by it

The cross reference of related application

The interim Shen in the U.S. submitted this application claims on August 12nd, 2016 with entitled " Sealing Composition " It please submit and entitled " Preparation of Treatment on June 29th, No.62/374188 and 2017 Composition and System and Method of Maintaining a Treatment Bath Formed The priority of the U.S. Provisional Application No.62/526382 of Therefrom ", the two are incorporated by reference herein in its entirety.

Invention field

The present invention relates to the treatment compositions for handling substrate such as metallic substrates, such as are related to for shape on the surface At the treatment compositions of protective coating, and it is related to the preparation of such composition and maintains by such treatment compositions institute The system and method for the processing bath of formation.

Background of invention

Corrosion resistance is improved using protective coating on the metal surface and paint adhesion characteristics are metal lump gorget domain public affairs Know.Conventional technique include with containing phosphate and chromium treatment compositions handle metallic substrates, come promote corrosion resistance and Coating is formed by for the adhesion of substrate surface by the treatment compositions.But use such phosphate-containing and/or chromium The composition of hydrochlorate results in environment and health problem.As a result, having developed the processing group of chromate-free and/or phosphate free Close object.

Certain ingredient examples in typical processing method, when treatment compositions contact substrate, in the treatment compositions Such as metal ion deposition is integrated on the substrate surface to form protective layer.As a result, in the composition those ions it is dense Degree may reduce during the method, this can negatively affect the substrate that is continuously coated in identical coating composition it Between coating characteristic and reproducibility.It is desirable, therefore, to provide such treatment compositions, not generation environment and health Problem, and can be used for being formed the protective coating with effective corrosion protection and adhesion characteristics on the surface of the substrate, and Mean that avoiding or at least alleviate the such composition of continuous use changes and to handle composition when substrate for coating The relevant adverse effect of characteristic and reproducibility.So target of the present invention is to provide treatment compositions, be Environmental security and Healthy and beneficial, it can be produced with cost effective manner by the resource being easy to get, and still can form such protection Property layer, assign effective corrosion protection and on the surface of the substrate have with the composition of phosphate-containing and/or chromate it is comparable Suitable adhesion.

Another the goal is to provide a kind of method and systems, and the processing formed by such composition can be used continuously Bath to handle substrate, this produced in a manner of reproducible with it is desirable that characteristic coating, and without influencing corrosion or attached Performance composition variation.

Summary of the invention

These targets are by processing group in greater detail in dependent claims defined and following specification It closes object and its manufacturing method and solves for maintaining the method and system of processing bath.

Process described herein composition generally comprises carbon dioxide source, lithium cation (it may be at lithium salt form) and Water-bearing media.

The treatment compositions may include lithium carbonate, and wherein the lithium carbonate can contained by carbon dioxide and lithium cation Reaction is in aqueous medium to be formed in situ.

Present invention is accordingly directed to it is a kind of manufacture treatment compositions method, it includes: in water-bearing media merge lithium sun from Son and carbon dioxide form treatment compositions, it includes lithium amount be 5ppm-5500ppm (being calculated as lithium cation), base It is 15ppm-25000ppm (being calculated as carbonate) in the total weight and carbonate amount of the treatment compositions, is based at this Manage the total weight of composition.

The present invention additionally relates to System, which includes: lithium salts；And/or carbon dioxide；With optional hydroxide source.

Another part of the invention is a kind of for maintaining to be formed by processing bath by the treatment compositions comprising lithium carbonate Method, this method includes: with the bath handle substrate during and/or after, by at least one of carbon dioxide and lithium salts It is supplied to the bath with such amount, the pH which is enough to bathe the processing maintains 9.5-12.5, and the amount of lithium is 5ppm- 5500ppm (is calculated) as lithium cation, and the amount of total weight and carbonate based on processing bath is 15ppm-25000ppm (being calculated as carbonate), the total weight based on processing bath.

The present invention additionally relates to the substrate handled with such composition and the processing bath maintained.With not in this way The mode substrate of compositions-treated that is formed or maintained on be formed by the coating characteristic of coating and compared with reproducibility, with The coating characteristic and reproducibility of the coating formed in substrate handled by such composition and the processing bath maintained are continuously being located There is bigger consistency in the substrate of reason.Therefore, it is formed by by composition according to the present invention and maintained processing bath Protective coating is reproducible and shows suitable corrosive nature and adhesion on the surface of the substrate.

Detailed description of the invention

Fig. 1 shows a flow chart, details to be used to prepare and contains the processing group used in embodiment D to J Close the sequential steps of the processing bath of object.

Fig. 2 shows a flow chart, details the processing bath for being used to prepare composition used in embodiment L to O Sequential steps.

Fig. 3 shows a schematic diagram, and which show the thickness degree of the treatment compositions on the surface of the substrate.

Specific embodiment

For the purpose being explained in detail below, it should be understood that the present invention can show the change programme of different alternative selections And order of steps, in addition to there is specific opposite regulations place.In addition, in addition to any operation embodiment or place indicated otherwise Outside, all digital such as expression value, amount, percentage, range, those of subrange and score can be interpreted as " big with word It is about " modified, even if the term does not occur clearly.Therefore, unless the contrary indication, otherwise below specification and additional Claim in the digital parameters that illustrate be approximation, the desired performance that can be obtained according to the present invention and become Change.At least, and be not intended to limit the scope of the claims using doctrine of equivalents, each digital parameters should at least according to It the numerical value for the effective digital reported and rounds up technology by using common and explains.Closing is being described herein or is opening When the digital scope put, be in or be contained in the digital scope all number, be worth, amount, percentage, subrange and point Number is considered being specifically included in and belonging to the original disclosure of the application, just as these numbers, is worth, amount, percentage, sub- model It encloses as being write out with the clear entirety with them of score.

Although the digital scope and parameter that illustrate the wide range of the present invention are approximations, described in a particular embodiment Numerical value be reported as precisely as possible to report.But any numerical value is substantially contained by existing in their own test measurement Certain errors for necessarily being formed of standard deviation.

As used in this article, unless otherwise directed, otherwise plural term may include its single counterpart, otherwise also So, unless otherwise directed.Although such as refer to "an" lithium salts herein, "an" hydroxide and "one" treatment compositions, But the combination (i.e. multiple) of these components can be used.In addition in this application, "and/or" is indicated using "or", unless It is otherwise expressly specified, even if "and/or" can be used clearly in some cases.

As used in this article, " comprising ", "comprising" and similar terms are understood to be in the present context and " contain " synonymous and so be open, and do not exclude the presence of the other element not described and/or do not describe, material, ingredient And/or method and step.As used in this article, " by ... form " being understood to exclusion in the present context, there is appoint What unspecified element, ingredient and/or method and step.As used in this article, "consisting essentially of" is above and below the application Element illustrated by being understood to include in text, material, ingredient and/or method and step " and it is described for basic and novel Characteristic those of have no substantial effect ".

As used in this article, term " on it ", " to thereon ", " being applied to thereon ", " applying above it ", " shape At thereon ", " deposited thereon ", " being deposited on " indicates to be formed, and covering deposits and/or is provided on surface, but need not It need to be contacted with surface.Such as coating " is formed in " other that one or more identical or different compositions are not excluded the presence of in substrate It is inserted into coating, is located at and is formed by between coating and substrate.

Unless disclose otherwise herein, otherwise term " there is no " is when being related to coming there is no specific material in use, table If showing that such material exists entirely in composition, the bath containing the composition and/or formed by the composition and comprising this When in the layer of composition, only exist with 5ppm or lower trace, based on the total weight of the composition, bath and/or layer, Depending on according to circumstances.Unless disclose otherwise herein, otherwise term " not having substantially " when be related to coming there is no specific material using When, if indicating that such material exists entirely in composition, the bath containing the composition and/or formed by the composition and wrapped When in the layer containing the composition, only exist with 1ppm or lower trace, the gross weight based on the composition, bath and/or layer Meter, according to circumstances depending on.Unless disclose otherwise herein, otherwise term " absolutely not " makes when being related to that there is no specific materials Used time, if indicate such material exist entirely in composition, the bath containing the composition and/or formed by the composition and When in the layer comprising the composition, be not present in the composition, the bath containing the composition and/or formed by it and comprising its (that is, the composition, the bath containing the composition and/or being formed by the composition and the layer comprising the composition includes in layer Such material of 0ppm).It is formed when composition, the bath containing composition and/or by it and be there is no comprising its layer, Substantially not or absolutely not specific material when, this indicates such material by from wherein excluding, unless the material can Using as example from processing bath first in process pipelines, municipal water sources, the residue of substrate and/or device dissolution As a result exist.

As used in this article, " salt " refers to ionic compound, is made of metal cation and metalloid anion, And there is the charge for being on the whole zero.Salt can be hydration or anhydrous.

As used in this article, " Aquo-composition " refers to solution or dispersion in the medium mainly comprising water Body.Such as the water that the water-bearing media may include is greater than 50wt%, is either greater than 70wt% or is greater than 80wt% or big In 90wt% or it is greater than 95wt%, is based on the medium total weight.The water-bearing media can be for example substantially made of water.

As used in this article, term " oxidant " is when the component for being related to sealing compositions in use, referring to such Chemicals can aoxidize following at least one: being present in substrate and contact the metal of sealing compositions, and/or be present in Metal chelating agent in the sealing compositions.As being related to used in " oxidant ", word " can aoxidize " indicates can be from In atom present in substrate or sealing compositions or molecule remove de-electromation, according to circumstances depending on, thus reduce electron number.

As used in this article, term " group ia metal " refers to such element, is in the CAS editions periodic table of elements Group ia in, such as Handbook of Chemistry and Physics, shown in the 63rd edition (1983), correspond to practical 1st race of IUPAC number.

As used in this article, term " group ia metal compound " refers to such compound comprising is in CAS At least one of the group ia of version periodic table of elements element.

As used in this article, term " group iia metal " refers to such element, is in CAS editions period of element In the group iia of table, such as Handbook of Chemis try and Phys ics, shown in the 63rd edition (1983), correspond to real 2nd race of border IUPAC number.

As used in this article, term " group iia metallic compound " refers to such compound comprising is in At least one of the group iia of CAS editions periodic table of elements element.

As used in this article, term " Group IIIB metal " refers to the yttrium and scandium of the CAS editions periodic table of elements, such as Handbook of Chemistry and Physics, the 63rd edition (1983) shown, the 3rd corresponding to practical IUPAC number Race.For the sake of brevity, " Group IIIB metal " clearly excludes lanthanide series.

As used in this article, term " Group IIIB metallic compound " refers to such compound comprising as above At least one of the defined Group IIIB in CAS editions periodic table of elements element.

As used in this article, term " group ivb metal " refers to such element, is in CAS editions period of element In the group ivb of table, such as Handbook of Chemistry and Physics, shown in the 63rd edition (1983), correspond to practical 4th race of IUPAC number.

As used in this article, term " group ivb metallic compound " refers to such compound comprising is in At least one of the group ivb of CAS editions periodic table of elements element.

As used in this article, term " Group VB metal " refers to such element, is in the CAS editions periodic table of elements Group VB in, such as Handbook of Chemistry and Physics, shown in the 63rd edition (1983), correspond to practical 5th race of IUPAC number.

As used in this article, term " Group VB metallic compound " refers to such compound comprising is in CAS At least one of the Group VB of version periodic table of elements element.

As used in this article, term " vib metals " refers to such element, is in CAS editions period of element In the group VIB of table, such as Handbook of Chemistry and Physics, shown in the 63rd edition (1983), correspond to practical 6th race of IUPAC number.

As used in this article, term " vib metals compound " refers to such compound comprising is in At least one of the group VIB of CAS editions periodic table of elements element.

As used in this article, term " V Group IIB metal " refers to such element, is in CAS editions period of element In the group ia of table, such as Handbook of Chemistry and Physics, shown in the 63rd edition (1983), correspond to practical 7th race of IUPAC number.

As used in this article, term " V Group IIB metallic compound " refers to such compound comprising is in At least one of the V Group IIB of CAS editions periodic table of elements element.

As used in this article, term " X II race metal " refers to such element, is in CAS editions period of element In the group ia of table, such as Handbook of Chemistry and Physics, shown in the 63rd edition (1983), correspond to practical 12nd race of IUPAC number.

As used in this article, term " X II race metallic compound " refers to such compound comprising is in At least one of the X II race of CAS editions periodic table of elements element.

As used in this article, term " lanthanide series " refers to the element 57-71 of the CAS editions periodic table of elements, and wraps Include the simple substance form of lanthanide series.According to the present invention, lanthanide series can be that with both+3 and+4 common oxidation states A bit, hereinafter referred to as+3/+4 oxidation state.

As used in this article, term " lanthanide compound " refers to such compound comprising CAS editions elements At least one element 57-71 of periodic table.

As used in this article, " sealing compositions " refer to composition such as solution or dispersion, with such Mode influences the material of substrate surface or deposition on the surface of the substrate, makes it possible to change physics and/or the change of substrate surface It learns performance (such as the composition provide corrosion protections).

As used in this article, " conversion composition " refers to composition such as solution or dispersion, can be with base Bottom surface reaction and to its chemical modification and be bonded thereto with formed provide corrosion protection film.

As used in this article, what " processing bath " referred to being formed by initial treatment composition contains water-bath.Processing bath can To be the by-product of substrate Yu the treatment compositions contact process comprising such component.

As used in this article, the processing bath that " maintenance " is formed by treatment compositions refers to keeping the certain of processing bath Parameter, including maintaining the concentration of certain ingredients and/or pH in the desired range.This can by from respective source by a kind of or Multiple material is online and/or processing bath is added offline to realize, as described in more detail below.As used in this article, " online (on-shift) " indicates that product to be processed is present in processing bath.As used in this article, " offline (off- Shift) " indicate will the product of compositions-treated through this process be not present in processing bath, but do not indicate that the processing is bathed It must be removed from processing line.

Pit corrosion is the corrosion being partially formed, and generates chamber or hole in the substrate by it.As used in this article, Term " pit " refers to such chamber or hole, be corroded to be formed by pit, and be characterized in that (1) when perpendicular to Test panel surface is round, elongation or irregular appearance when observing, " the comet tail " that (2) are dissipated from pit chamber, directly Line perhaps " halo " (that is, surface discolouration) and (3) inside pit or close to around pit there are corrosion by-products (such as White, light grey perhaps black is granular powdered or amorphous materials).The surface chamber of observation or hole necessarily exhibit At least two it is above-mentioned be considered as corrosion pit characteristic.Show the surface chamber or hole of only one of these characteristics It may require that other analysis before being classified as corrosion pit.When corrosion by-products are that naked eyes are invisible, amplified using 10X The microscopical visual inspection of multiplying power is used for determining the presence of corrosion by-products.

Unless disclose otherwise herein, otherwise as used in this article, term " total composition weight ", " always bathing weight ", " group Close object total weight ", " processing bath total weight " either similar terms refer to being present in it is complete in respective composition or bath foam The total weight of portion's ingredient, including any carrier and solvent.

As described above, according to the present invention, disclosing a kind for the treatment of compositions comprising lithium carbonate.The lithium carbonate can be outstanding It is reacted for example in water-bearing media by carbon dioxide and lithium cation (it may be at lithium salt form) to be formed in situ.It should Treatment compositions can be sealing compositions, conversion composition etc..

Treatment compositions of the invention are typically alkalinity.According to the present invention, the pH of the treatment compositions can be to Lack 9.5, for example, at least 10, for example, at least 11 and 12.5 can be not more than in some cases, such as no more than 12, such as less In 11.5.According to the present invention, the pH of the treatment compositions can be 9.5-12.5, such as 10-12, such as 11-11.5.According to this The pH of invention, the treatment compositions can be adjusted by including acid material, including carbon dioxide, and water-soluble and/or water can Dispersed acid such as nitric acid, sulfuric acid and/or phosphoric acid.According to the present invention, the pH of the treatment compositions can be by including alkaline material Material is to adjust, including water-soluble and/or water-dispersible alkali, including carbonate, such as group i carbonate, group ii carbonate, Hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonium hydroxide, ammonia and/or amine such as triethylamine, methyl second Base amine or its mixture.

According to the present invention, the carbon dioxide for being used to form treatment compositions of the invention can be gas, and solid is (that is, dry Ice) or a combination thereof.

According to the present invention, the lithium salts for being used to form treatment compositions of the invention may include inorganic lithium salt, organic lithium salt Or a combination thereof.According to the present invention, the anion of the lithium salts and cation are both soluble in water.According to the present invention, the lithium salts In 25 DEG C of (K of temperature；25 DEG C) solubility constant in water can be at least 1x10^-11, for example, at least 1x10^-4With in some feelings 5x10 can be not more than in condition⁺².According to the present invention, the lithium salts is in 25 DEG C of (K of temperature；25 DEG C) solubility constant in water can be with It is 1x10^-11To 5x10⁺², such as 1x10^-4To 5x10⁺².As used in this article, " solubility constant " is indicated in respective lithium salts The product of saturated aqueous solution intermediate ion equilibrium concentration.Each concentration is increased to the power of respective ion coefficient in equilibrium equation.No Solubility constant with salt can be found in Handbook of Chemistry and Physics.The example of suitable lithium salts Son is lithium carbonate, lithium hydroxide, lithium phosphate, lithium sulfate and lithium tetraborate.

Optionally, which can also include hydroxide, such as alkali metal hydroxide, alkaline-earth metal hydrogen-oxygen Compound or a combination thereof.According to the present invention, which can be one or more group i hydroxide, ammonium hydroxide or Its mixture of person.The hydroxide with any amount if it is present can exist, such as maintain the pH of the treatment compositions In the amount of 9.5-12.5.The not limiting example of group i hydroxide includes sodium hydroxide, potassium hydroxide, lithium hydroxide or Its mixture.Therefore, which if you are using, then can be used as lithium salts component and provides to be used to form the processing group Object or part of it are closed, such as lithium hydroxide, is optionally combined with other lithium salts such as lithium carbonate.But the processing Composition also may include one or more such as sodium hydroxides of the hydroxide different from lithium salts, potassium hydroxide or its group It closes.

Treatment compositions of the invention generally comprise water-bearing media as carrier.Therefore the composition may be at lithium salts and exist The form of solution or dispersion in carrier.

According to the present invention, lithium carbonate is formed by merging carbon dioxide and lithium cation in aqueous carrier medium , wherein equilibrium carbon dioxide and lithium cation have it with such amount, that is, so that lithium depositing in the treatment compositions It is 5ppm-5500ppm (being calculated as lithium cation) in amount, the total weight based on the treatment compositions, carbonate is at this Amount in reason composition is 15ppm-25000ppm (calculating as carbonate), the total weight based on the treatment compositions Meter.As described above, optionally by for example one or more acid materials of another or a variety of pH adjusting agents and/or one kind or For example one or more hydroxide of a variety of basic matterials are added in the aqueous carrier medium, wherein optional pH tune can be balanced The amount for saving agent, carbon dioxide and lithium salts, so that the pH of the treatment compositions is 9.5-12.5.

According to the present invention, which can further include the group ia metal cation of at least one non-lithium, Group VB metal cation and/or vib metals cation.According to the present invention, the group ia metal of at least one non-lithium Cation, Group VB metal cation and/or vib metals cation may be at the form of salt, and cation is respectively Amount in the treatment compositions can be at least 5ppm, for example, at least 50ppm, for example, at least 150ppm, for example, at least 250ppm (is calculated) as metal cation, the total weight based on the treatment compositions, and amount can in some cases To be not more than 5500ppm, such as no more than 1200ppm, for example no more than 1000ppm, for example no more than 500ppm (as metal Cation calculates), the total weight based on the treatment compositions.In some cases, according to the present invention, lithium metal is in the processing Amount in composition can be 5ppm-5500ppm, such as 50ppm-1000ppm (calculating as metal cation), be based on The total weight of the treatment compositions, such as 150ppm-500ppm.

It is suitable for and lithium cation, the group ia cation of non-lithium, Group VB cation and/or group VIB cation are formed The not limiting example of the anion of salt includes carbonate, hydroxyl, nitrate anion, halogen, sulfate radical, phosphate radical and silicate (such as positive silicate and metasilicic acid root), so that the metal salt may include carbonate, hydroxide, nitrate, halide, Sulfate, phosphate, silicate (such as orthosilicate or metasilicate), permanganate, chromate, vanadate, molybdate And/or perchlorate.

According to the present invention, metal salt (i.e. lithium salts, the group ia metal of non-lithium, the Group VB and/or of the treatment compositions Group vib) amount in each comfortable treatment compositions can be at least 25ppm, for example, at least 150ppm, for example, at least 500ppm (is calculated) as total compound, the total weight based on the treatment compositions, and is not more than in some cases 30000ppm, such as (calculated as total compound) no more than 2000ppm, for example no more than 1500ppm, it is combined based on the processing The total weight of object.According to the present invention, the amount in each comfortable treatment compositions of the metal salt can be 25ppm- 30000ppm, such as 150ppm-2000ppm, such as 500ppm-1500 (calculating as total compound), are combined based on the processing The total weight of object.

According to the present invention, sealing compositions of the invention may include oxidant, such as hydrogen peroxide, and persulfate is high Chlorate sprays oxygen, bromate, perbenzoic acid salt, ozone etc. or a combination thereof.Such as the sealing compositions can wrap Oxidant containing 0.1wt%-15wt%, the total weight based on the sealing compositions, such as 2wt%-10wt%, such as 6wt%-8wt%.Alternatively, according to the present invention, which can be there is no or in some cases substantially Not or in some cases absolutely not oxidant.

According to the present invention, which can not include chromium or containing chromium compound.As used in this article, term " contain chromium compound " refer to include Cr VI material.The not limiting example of such material includes chromic acid, chromium trioxide, Chromic anhybride, bichromate such as ammonium dichromate, sodium dichromate, potassium bichromate and calcium bichromate, barium, magnesium, zinc, cadmium and strontium.Work as place Reason composition and/or bath or the coating formed by it or layer there is no, substantially not or absolutely not chromium when, This includes any type of chromium, chromyl compound such as, but not limited to listed above.

Therefore optionally, according to the present invention, the painting that treatment compositions of the invention and/or processing are bathed and/or formed by it Material perhaps layer can there is no can substantially without and/or can absolutely not any element or change listed by leading portion Close the one or more of object.It there is no chromium or the treatment compositions containing chromium compound and/or bath and/or formed by it Coating or layer indicate chromium or are not intended that addition containing chromium compound, but can exist with trace, such as due to from ring The impurity in border or inevitably pollution.In other words, the amount of the material is small in this way, so that it does not influence processing combination Object and/or bath and/or performance by its coating or layer that are formed；In the case where chromium, this can further comprise the element Either its compound can not cause environment in the treatment compositions and/or bath and/or the coating or layer that are formed by it with it The horizontal of burden exists.Therefore term " there is no " for example can indicate the treatment compositions and/or bath and/or by its shape At coating or layer include to be based on the combination less than any or whole elements or compound listed by the leading portion of 10ppm Object, bath, coating or layer total weight, according to circumstances depending on, if present.Term " not having substantially " indicates at this Reason composition and/or bath and/or the coating formed as it or layer include be less than it is any or whole listed by the leading portion of 1ppm Element perhaps total weight of the compound based on the composition, bath, coating or layer, according to circumstances depending on, if there is Words.Term " absolutely not " indicates the treatment compositions and/or bath and/or the coating formed by it or layer includes to be less than 1ppb Leading portion listed by any or whole elements perhaps total weight of the compound based on the composition, bath, coating or layer, Depending on according to circumstances, if present.

According to the present invention, treatment compositions of the invention and/or processing bath and/or the coating or layer that are formed by it are one The compound of phosphate anion or phosphorous acid group can be excluded in a little situations and/or forms slurry, such as aluminum phosphate, ferric phosphate And/or trbasic zinc phosphate, it is, for example, to be formed in the case where using the inorganic agent based on trbasic zinc phosphate.As used in this article, " contain The compound of phosphate radical " includes such as orthophosphates of the compound containing element phosphor, pyrophosphate, metaphosphate, tripolyphosphate Salt, organic phosphonate etc., and can include but is not limited to unit price, divalent or Tricationic for example: sodium, potassium, calcium, zinc, Nickel, manganese, aluminium and/or iron.When treatment compositions and/or bath and/or the coating formed by it or layer there is no, substantially Not perhaps absolutely not phosphate when this includes any type of phosphate anion or the compound containing phosphate radical.

Therefore according to the present invention, treatment compositions disclosed herein and/or bath and/or the coating formed by it or layer can With there is no perhaps can not have substantially in some cases or in some cases can it is absolutely not a kind of or Any ion or compound listed by a variety of leading portions.It there is no phosphatic treatment compositions and/or bath and/or by it The coating or layer of formation indicate that phosphate ion or the compound containing phosphate radical are not intended that addition, but can be with trace In the presence of, such as due to the impurity from environment or inevitably pollution.In other words, the amount of the material is small in this way, with The treatment compositions and/or bath and/or the performance by its coating or layer that are formed are not influenced as it；This can further be wrapped Phosphate is included in the treatment compositions and/or bath and/or the coating or layer that are formed by it not to cause the water of environmental pressure It is flat to exist.Term " there is no " can specifically indicate the treatment compositions and/or bath and/or the coating that is formed by it or Layer includes any or whole phosphate anions or compound listed by the leading portion less than 5ppm, based on the composition, bath, The total weight of coating or layer, according to circumstances depending on, if present.Term " not having substantially " indicates that the processing is combined Object and/or bath and/or the coating formed as it or layer include less than any or whole phosphate listed by the leading portion of 1ppm Anion perhaps total weight of the compound based on the composition, bath, coating or layer, according to circumstances depending on, if there is Words.Term " absolutely not " indicates the treatment compositions and/or bath and/or the coating formed by it or layer includes to be less than 1ppb Leading portion listed by any or whole phosphate anions perhaps compound based on the total of the composition, bath, coating or layer Poidometer, according to circumstances depending on, if present.

According to the present invention, sealing compositions can exclude the chemical combination of group iia metal cation or the metal containing group iia Object, including but not limited to calcium.The not limiting example of such material includes group iia metal hydroxides, group iia metal Nitrate, group iia metal halide, group iia metal aminosulfonate, group iia metal sulfate, group iia carbonic acid Salt and/or group iia metal carboxylate.The coating or layer formed when sealing compositions and/or respectively by it there is no, Substantially not or absolutely not group iia metal cation when, this includes any type of group iia metal cation, The compound of the metal such as, but not limited to listed above containing group iia.

According to the present invention, sealing compositions can exclude fluoride or fluoride source in some cases.As herein It uses, " fluoride source " includes single fluoride, difluoride, fluoride complex and generation fluorine ion known to it Mixture.When composition and/or comprising its layer, perhaps coating there is no substantially not or absolutely not fluoride When, this includes any type of fluoride ion or fluoride source, but does not include unintentionally fluoride, be can be used as following Result and be present in bath foam: for example come in process pipelines first processing bath, municipal water sources (such as: will be fluorinated Object, which is added in water supply, prevents tooth deterioration), from the residue of the fluoride of precondition substrate etc..That is, there is no, It substantially not or the bath foam of absolutely not fluoride can have unintentionally fluoride, can be outside these Source, that is, be used in manufacture the composition of the bath there is no before for process pipelines, substantially without or completely There is no fluoride.

Such as sealing compositions can there is no any fluoride source, such as ammonium and alkali metal fluoride, acid fluorination Object, fluoboric acid, fluosilicic acid, fluotitanic acid and fluorine zirconic acid and their ammonium and alkali metal salt and other inorganic fluorides, it is non exhaustive Example be: zinc fluoride is fluorinated zinc-aluminium, titanium fluoride, zirconium fluoride, nickel fluoride, ammonium fluoride, sodium fluoride, potassium fluoride and hydrofluoric acid, with And other similar material well known by persons skilled in the art.

Be present in the sealing compositions fluoride (it is not bonded to metal ion such as group ivb metal ion, or Person's hydrogen ion is defined herein as " Free Fluoride ") such as desk-top instrument of Orion Dual Star two-way can be used as close The operating parameter measurement in composition bath is sealed, the desk-top instrument is equipped with to be selected obtained from the fluoride ion of Thermoscientific Selecting property electrode (" ISE "), what VWR International was providedFluoride ion selective compound electrode, Or similar electrode.See, for example, Light and Cappuccino, Determination of fluoride in Toothpaste using an ion-selective electrode, J.Chem.Educ., 52:4,247-250,1975 years 4 Month.Fluoride ISE can be by immersing the electrode in the solution of known fluoride concentration, and records millivolt reading, so These millivolts of readings are corrected with logarithmic chart drawing afterwards.The millivolt reading of unknown sample then can be with this correction chart Compare, and determines fluoride concentration.Alternatively, fluoride ISE can be used together with such instrument, internal school will be carried out The positive concentration calculated and unknown sample therefore can be read directly after calibration.

Fluorine radical ion is a kind of small anion with high charge density, therefore in aqueous solution, it often with have The metal ion of high positive charge density such as group ivb complexing of metal ion, or be complexed with hydrogen ion.Fluorine root yin in solution Ion (its ion or being covalently bonded on metal cation or hydrogen ion) is defined herein as " the fluorine root of bonding ".Therefore The fluorine radical ion of complexing be it is immeasurablel with fluoride ISE, unless their solution for being contained therein with from such complexing The ion concentration that fluorine radical ion is discharged in object adjusts buffer (such as: Citrate anions or EDTA) and is mixed.At that A moment, (whole) fluorine radical ion can be measured by fluoride ISE, and the measurement is referred to as " total fluoride ". Alternatively, total fluoride can by by the weight of fluoride provided in encapsulant composition compared with the total weight of composition To calculate.

According to the present invention, which can there is no in some cases, or in some cases originally Do not have in matter, either absolutely not cobalt ions or cobalt compound in some cases.As used in this article, " contain cobalt Close object " it include the compound containing element cobalt, complex compound or salt such as cobaltous sulfate, cobalt nitrate, cobalt carbonate and cobalt acetate.Work as group Close object and/or comprising its layer perhaps coating there is no substantially not or absolutely not cobalt when, this includes any shape The cobalt ions or cobalt compound of formula.

According to the present invention, which can there is no in some cases, or in some cases originally Do not have in matter, either absolutely not vanadium ion or vanadium-containing compound in some cases.As used in this article, " contain vanadium Close object " include the compound containing elemental vanadium, complex compound or salt such as vanadate and decavanadate comprising alkali metal or Ammonium cation counter ion counterionsl gegenions, including such as ten sodium vanadate ammoniums.When composition and/or layer comprising it or coating do not have substantially Have, substantially not perhaps absolutely not vanadium when this includes any type of vanadium ion or the compound containing vanadium.

According to the present invention, which can optionally further include indicator compound, this is indicated due to it Such as the presence of chemical substance such as metal ion, pH of composition etc. and gain the name.As used in this article, " indicator ", " refers to Show immunomodulator compounds " and similar terms refer to such compound, can change colour to respond some outside stimulus, parameter or item Part, such as the presence of metal ion either respond specific pH pH range.

Indicator compound used in accordance with the present invention can be any indicator known in the art, indicate substance Presence, especially pH etc..Such as suitable indicator can be and form metal ion complex with specific metal ion It is metachroic that.The Metal ion indicator is usually the organic compound of high conjugation.As used in this article and such as this Field the skilled person will understand that, " conjugated compound " refers to such compound, have two separated by singly-bound it is double Key, such as two carbon-to-carbon double bonds and single carbon-carbon bond between them.Any conjugated compound can be used for the present invention.

Similarly, the indicator compound can be when changing pH and change colour that；Such as the compound can be It is a kind of color when acid or neutral pH, and changes colour in alkaline pH, vice versa.Such indicator be it is well known and It is commercially widely used." discoloration when being converted to two pH from the first pH " is (that is, from the first pH to greater or lesser acidity Or the 2nd pH of alkalinity) indicator therefore there is when being exposed to a pH the first color (or colourless) and be converted to the (that is, pH that acid or alkalinity is more than or less than the first pH) becomes the second color (or from colourless to coloured) when two pH.Such as The indicator of " being converted to bigger alkaline pH (or smaller acid pH) Shi Bianse " when pH becomes alkalinity from acidity/neutrality from First color/colourless becomes the second color/coloured.Such as " when becoming bigger acid pH (or smaller alkaline pH) Shi Bianse " Indicator becomes the second color/coloured from the first color/colourless when pH becomes acidity from alkalinity/neutrality.

The not limiting example of such indicator compound includes methyl orange, xylenol orange, catechol violet, bromophenol Indigo plant, green and purple, eriochrome black T, celestine blue, hematoxylin, calmagite, Gallocyanine and combinations thereof.Optionally, the indicator compound It may include organic indicator compound, be Metal ion indicator.The not limiting example of indicator compound includes table 1 In it is those of listed.Fluorescence indicator (it will shine in certain conditions) can be used for the present invention, although can also clearly arrange Except using fluorescence indicator.That is, selectively, clearly excluding the conjugated compound for showing fluorescence.As used in this article, " fluorescence indicator " and similar terms refer to such compound, molecule, pigment and/or dyestuff, will fluoresce or Color is shown when being exposed to ultraviolet light or visible light." fluorescing " will be understood as absorb compared with short wavelength light or other It shines after electromagnetic radiation.The example (often referred to as " marking ") of such indicator includes acridine, anthraquinone, cumarin, hexichol Methylmethane, diphenyl naphthyl methane, quinoline, stilbene, triphenyl methane, anthracene and/or molecule containing any of these parts and/or appoint What these derivative such as rhodamine, phenanthridines, oxazines, fluorone, anthocyanidin and/or acridine.

Table 1

According to the present invention, the conjugated compound that can be used as indicator can be for example comprising catechol violet, as shown in table 1.Youngster Tea phenol violet (CV) is a kind of sulfone phthalein dyestuff, is manufactured by the adjacent iodo-benzoic acid acid anhydride of the pyrocatechol and 1mol that are condensed 2mol.? It is found that CV is with indicator properties and when being introduced into the composition with metal ion, it forms complex compound, this makes Obtaining it may be used as complexing dosage facility.Because the composition containing CV is chelated with the metal ion from metallic substrates (there is divalent or more those of high price), therefore it is generally observed the color that blue arrives bluish violet.

As shown in table 1, xylenol orange can be equally used for composition according to the present invention.Have been found that xylenol orange With metal ion (i.e. those of high price with divalent or more) indicator properties and the group with metal ion ought be introduced into When closing object, it forms complex compound, this makes it may be used as complexing dosage facility.When this contains the composition chelating of xylenol orange When metal ion, xylenol orange solution becomes the color of usual blue from red.

According to the present invention, amount of the indicator compound in treatment compositions can be at least 0.01g/1000g Treatment compositions, for example, at least 0.05g/1000g treatment compositions, and in some cases no more than 3g/1000g processing combination Object, such as no more than 0.3g/1000g treatment compositions.According to the present invention, the indicator compound is in the treatment compositions Amount can be 0.01g/1000g treatment compositions to 3g/1000g treatment compositions, such as 0.05g/1000g processing combination Object is to 0.3g/1000g treatment compositions.

According to the present invention, the indicator compound for responding certain outside stimulus and changing colour is provided when using treatment compositions Benefit, is visually indicated with what the composition was handled because it can for example serve as substrate.Such as comprising when exposure The metal ion being exposed in the presence of substrate and the treatment compositions of indicator that change colour with the metal ion in that substrate Change colour when complexing；This allows user's understanding substrate to be contacted with the composition.Similar benefit can be by by alkali Property or acidic layer are deposited in substrate and contact the substrate with composition of the invention to realize, the composition of the invention The discoloration when being exposed to alkalinity or acid pH.

Optionally, treatment compositions of the invention can further include nitrogen-containing heterocycle compound.The nitrogen-containing heterocycle chemical combination Object may include the cyclic compounds such as pyrroles with 1 nitrogen-atoms, and the azoles chemical combination with 2 or more nitrogen-atoms Object such as pyrazoles, imidazoles, triazole, tetrazolium and pentazole, azole compounds such as oxazole with 1 nitrogen-atoms and 1 oxygen atom and Isoxazole, or azole compounds such as thiazole and isothiazole with 1 nitrogen-atoms and 1 sulphur atom.Suitable azole compounds Not limiting example include 2,5- dimercapto-1,3,4-thiadiazole (CAS:l072-71-5), 1H- benzotriazole (CAS:95- 14-7), 1H-1,2,3- triazoles (CAS:288-36-8), 2- amino -5- sulfydryl -1,3,4- thiadiazoles (CAS:2349-67-9), Also referred to as 5- amido-1,3,4-thiadiazoles -2- mercaptan and 2- amido-1,3,4-thiadiazoles (CAS:4005-51-0).Some In embodiment, such as the azole compounds include 2,5- dimercapto-1,3,4-thiadiazole.Furthermore according to the present invention, the nitrogen-containing hetero Cycle compound may be at the form of salt such as sodium salt.

The nitrogen-containing heterocycle compound in the treatment compositions there are concentration can be at least 0.0005g/L composition, For example, at least 0.0008g/L composition, for example, at least 0.002g/L composition and in some cases in the treatment compositions Amount can be not more than 3g/L composition, such as no more than 0.2g/L composition, such as no more than 0.1g/L composition.Root According to the present invention, the nitrogen-containing heterocycle compound in the treatment compositions there are concentration (if any) can be 0.0005g/ L composition is arrived to 3g/L composition, such as 0.0008g/L composition to 0.2g/L composition, such as 0.002g/L composition 0.1g/L composition.

As described above, treatment compositions of the invention include water-bearing media as carrier.The aqueous carrier can be optionally Include for example, at least a kind of organic solvent of other materials.The not limiting example of suitable solvent includes propylene glycol, and ethylene glycol is sweet Oil, low-molecular-weight alcohol (i.e. C1-C12 alcohol) etc..When it is present, even if having, presence of the organic solvent in the treatment compositions Amount can be at least 1g solvent/L treatment compositions, for example, at least about 2g solvent/L treatment compositions and deposit in some cases 40g solvent/L treatment compositions can be not more than in amount, such as no more than 20g solvent/L treatment compositions.According to the present invention, should Organic solvent can be 1g solvent/L treatment compositions at 40g solvent/L in the amount (even if having) in the treatment compositions Composition, such as 2g solvent/L treatment compositions are managed to 20g solvent/L treatment compositions.

As described above, the treatment compositions of aforementioned present invention can be prepared by such method, it includes containing water ballast Merge lithium salts and carbon dioxide in body medium to form the treatment compositions, it includes lithium amount be 5ppm-5500ppm (as Lithium cation calculates), the amount of total weight and carbonate based on the treatment compositions is 15ppm-25000ppm (as carbon Hydrochlorate calculates), the total weight based on the treatment compositions.The amount of suitable lithium salts and lithium is institute as above in the treatment compositions It states.Such as the lithium salts being used to form in the method for the treatment compositions may include lithium carbonate, lithium hydroxide or a combination thereof. Furthermore the method for preparing treatment compositions of the invention can be at least 9.5 comprising adjusting the pH of the treatment compositions to pH, It for example, at least 10, for example, at least 11 and adjusts to pH be not more than 12.5 in some cases, such as no more than 12, such as no more than 11.5.According to the present invention, it is 9.5-12.5, such as 10-12, such as 11-11.5 that therefore which, which can adjust pH,. The pH of the treatment compositions can measure and can according to need according to any following methods using for example any sour and/or alkali come It adjusts, as described above.

According to the present invention, the method for manufacturing the treatment compositions, which is included in water-bearing media, merges carbon dioxide and lithium salts. According to the present invention, which can be supplied to aqueous carrier medium in the form of gas, solid or a combination thereof.As herein Used in, " supply " is when being related to carbon dioxide in use, referring to that carbon dioxide is introduced the combination using the source of non-atmosphere Object.The amount that carbon dioxide is supplied to water-bearing media is enough to form such treatment compositions, it includes carbonate (as carbonic acid Salt calculates) amount be at least 15ppm, the total weight based on the treatment compositions, for example, at least 50ppm, for example, at least 200ppm and in some cases be not more than 25000ppm, the total weight based on the treatment compositions, for example, no more than 15000ppm, such as no more than 2400ppm.In some cases, according to the present invention, carbon dioxide can be formed with water with being enough The amount of such treatment compositions merges, so that the amount for the carbonate (calculating as carbonate) that the composition includes is 15ppm-25000ppm, the total weight based on the treatment compositions, such as 50ppm-15000ppm, such as 200ppm- 2400ppm。

As described above, the method for manufacturing treatment compositions according to the present invention can also be comprising being added hydroxide such as the I race hydroxide, ammonium hydroxide or its mixture.The hydroxide source with any amount if it exists, can exist, example The pH of the treatment compositions is such as made to be in the amount of 9.5-12.5 range.The not limiting example of group i hydroxide includes hydrogen Sodium oxide molybdena, potassium hydroxide, lithium hydroxide or its mixture.

As described above, according to the present invention, it is also disclosed that a kind of system and method, for maintaining the processing by lithium carbonate containing Composition is formed by processing bath.The treatment compositions can be above-mentioned treatment compositions and can be according to side described on this Method is manufactured or can be manufactured by any method known to those skilled in the art.In one example, according to the present invention, " processing bath " is also referred to containing water-bath, by the initial treatment composition such as above-mentioned composition of lithium carbonate containing, in processing one It is formed when kind or a variety of substrates.As used, " maintenance " is formed by processing bath (regardless of being somebody's turn to do by the treatment compositions of lithium carbonate containing How lithium carbonate composition is formed) certain parameters for referring to maintaining the processing to bathe, including by the concentration and pH of lithium and carbonate It maintains in the desired range for example above for range those of described in treatment compositions according to the present invention.This can pass through by One or more materials from respective source are online and/or processing bath is added offline to realize, as described in more detail below 's.

According to the present invention, the maintenance system or method may include (i) and add material into is formed by the treatment compositions Processing bath in, the material is different from material for preparing the treatment compositions, and/or (ii) is added material by this The processing bath that composition is formed is managed, the material is identical as preparing those for the treatment of compositions material.Although such as should The method for maintaining the processing bath containing the treatment compositions may include carbon dioxide addition processing bath, but the processing group Closing object can be used carbonate to prepare.

According to the present invention, the maintenance system or method may include to add material into and be formed by the treatment compositions Reason bath, the material are identical as preparing the material of the treatment compositions.Such as titanium dioxide can be used in the treatment compositions Carbon (as described above) is prepared, and the method for the maintenance processing bath that contains the treatment compositions may include titanium dioxide Processing bath is added in carbon.

System or method of the invention is not related to being simply added into more treatment compositions into processing bath to maintain The bath.But as described above, the system and method for the invention be related to by carbon dioxide and/or lithium salts and/or hydroxide with Processing bath is added in such amount, which is enough the pH of processing bath maintaining 9.5-12.5, and lithium amount maintains 5ppm- 5500ppm (is calculated) as lithium cation, and total weight and carbonate amount based on processing bath maintain 15ppm- 25000ppm (is calculated) as carbonate, the total weight based on processing bath.The supply can carry out online or offline.

As described above, according to the present invention, disclose the processing bath for maintaining to be formed by the treatment compositions of lithium carbonate containing is System.According to the present invention, which may include lithium salts and/or carbon dioxide, optional hydroxide or any group above-mentioned It closes.The lithium salts may include one or more above-mentioned any lithium salts, such as lithium carbonate, lithium hydroxide or a combination thereof.Dioxy Changing carbon may include the carbon dioxide as gas, solid or a combination thereof.The hydroxide may include one or more What above-mentioned hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide or a combination thereof.Above-mentioned lithium salts, carbon dioxide And/or hydroxide can include individually or in any combination within the system, and can from the system they are each From source be added formed by the treatment compositions processing bath in, come realize will processing bath maintain above-mentioned pH and lithium and carbon The amount of hydrochlorate.

As described above, according to the present invention, it is also disclosed that a kind of maintenance was formed by the treatment compositions of lithium carbonate containing The method for managing bath.According to the present invention, this method be included in the bath processing substrate during and/or after, by carbon dioxide with At least one of lithium salts and optional hydroxide are added the processing with such amount and bathe, which is enough that the pH dimension of bath will be handled It holds in 9.5-12.5, lithium amount maintains 5ppm to 5500ppm (calculating as lithium cation), the total weight based on processing bath The amount of meter and carbonate maintains 15ppm to 25000ppm (calculating as carbonate), the total weight based on processing bath. Above-mentioned lithium salts, carbon dioxide and hydroxide can be added in the processing bath formed by treatment compositions, to realize processing bath Maintain the amount of pH and lithium and carbonate in greater detail in treatment compositions context according to the present invention above.Such as According to the present invention, which may include for carbon dioxide to be added with such amount and be bathed by the processing that treatment compositions are formed In, i.e., so that the pH of processing bath is maintained at less than 12.5, and/or processing bath is added with such amount in hydroxide, even if The pH for obtaining processing bath is maintained above 9.5.In the example shown, according to the present invention, carbon dioxide can slowly be bubbled into processing bath In or can be added by falling into dry ice piecewise.According to the present invention, pH can periodically or continuously monitor (following institute State) and/or hydroxide can be introduced, as previously discussed, to the processing bath in pH is maintained 9.5-12.5.

According to the present invention, as described above, after having supplied carbon dioxide and/or lithium salts and/or hydroxide, lithium (is made For lithium cation calculating) amount in the treatment compositions can be at least 5ppm, for example, at least 50ppm, for example, at least 150ppm, for example, at least 250ppm bathe total weight based on the processing, and amount can be not more than in some cases 5500ppm, such as no more than 1200ppm, such as no more than 1000ppm, such as no more than 500ppm, gross weight is bathed based on the processing Meter.In some cases, according to the present invention, after supply carbon dioxide and/or lithium salts, lithium (calculates) as lithium cation Amount in processing bath can be 5ppm-5500ppm, bathe total weight, such as 50ppm- based on the processing 1200ppm, such as 150ppm-1000ppm, such as 250ppm-500ppm.

According to the present invention, after having supplied carbon dioxide and/or lithium salts and/or hydroxide, carbonate is (as carbonic acid Salt calculate) the processing bath in amount can be at least 15ppm, based on the processing bathe total weight, for example, at least 50ppm, for example, at least 200ppm and in some cases amount can be not more than 25000ppm, bathe total weight based on the processing Meter, such as no more than 15000ppm, such as no more than 2400ppm.In some cases, according to the present invention, dioxy is being supplied After changing carbon and/or lithium salts and/or hydroxide, amount of the carbonate (calculating as carbonate) in processing bath can be with It is 15ppm-25000ppm, total weight, such as 50ppm-15000ppm, such as 200ppm-2400ppm is bathed based on the processing.

According to the present invention, after having supplied carbon dioxide and/or lithium salts and/or hydroxide, the pH of processing bath can Be at least 9.5, for example, at least 10, for example, at least 11 and in some cases pH can no more than 12.5, such as no more than 12, Such as no more than 11.5.According to the present invention, after having supplied carbon dioxide and/or lithium salts and/or hydroxide, processing bath PH can be 9.5-12.5, such as 10-12, such as 11-11.5.

According to the present invention, the method for maintenance processing bath can further include the pH for adjusting processing bath, such as pass through root It is adjusted according to needing to be added any acid and/or alkali.According to the present invention, processing bath can be maintained by including acid material, Including water-soluble and/or water dispersible acid such as nitric acid, sulfuric acid and/or phosphoric acid.According to the present invention, the pH of processing bath can lead to It crosses including basic matterial and maintains, including water-soluble and/or water dispersible alkali, such as group i carbonate, group ii carbonate, Hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, ammonia, amine such as triethylamine, methyl ethylamine or its Mixture.

The method of maintenance processing bath of the invention can be further included using suitable for being combined by the processing comprising lithium carbonate Object formed bath foam size pH meter and probe come monitor the processing bath pH.One example of suitable pH meter and probe includes But it is not limited to Accumet AB15 (being obtained from Fisher Scientific) and single connection electrode (Ag/AgCl reference electrode； Fisher Scientific)。

The method of maintenance processing bath of the invention can be further included through any side well known by persons skilled in the art Lithium in method monitoring processing bath, the amount of carbonate or lithium carbonate.Such as according to the present invention, the method for the monitoring lithium may include Such as using luminescence spectrometer or equivalent instrument and using the lithium with normal concentration standard sample (such as in provision wavelengths The known concentration reference substance (such as Li reference substance of 500ppm, be diluted to the Li of 5ppm) of (such as 670.784nm) calculates The concentration of lithium (metal cation) in processing bath.The method of maintenance processing bath of the invention, which can further include, passes through this Any method known to the technical staff of field monitors the amount of carbonate in processing bath, including for example using titration by hand or automatically Titration method.

It has been surprisingly found that carbon dioxide and/or lithium salts and optional hydroxide can be used for maintaining by containing The processing bath that the treatment compositions of lithium carbonate are formed, so that pH and lithium cation concentration and/or lithium cation concentration and carbonic acid Salt (anion) concentration can be according to the manipulation of bath conditional sampling or adjusting, this is contrasted with the bath with such as lithium carbonate, Here pH, lithium concentration and carbonate concentration change all through bath foam is added in lithium carbonate (that is, for each such Independent control is not present in parameter).Such as carbon dioxide and/or lithium salts and optional hydroxide can be used for maintaining by containing The processing bath that the treatment compositions of lithium carbonate are formed, so that the pH of processing bath is 9.5 to 12.5, lithium concentration is that 5ppm is arrived 5500ppm (is calculated) as lithium cation, is 15ppm to 25000ppm based on processing bath total weight and carbonate concentration (calculating as carbonate) bathes total weight based on the processing.

As described above, the treatment compositions or the bath formed by it include water-bearing media as carrier.Therefore, the combination Object or bath may be at the form of solution or dispersion of the lithium salts in the carrier.According to the present invention, the solution or point Granular media can be contacted with the composition or the substrate of bath processing by any a variety of known technologies, such as be impregnated Or submergence, spraying, intermittent spray, subsequent spraying is impregnated, then dipping, brushing or roller coating are sprayed.According to the present invention, this is molten Liquid or dispersion may be at 40 °F of (5 DEG C)-about 160 °F (71 DEG C) when being applied to substrate, such as 60 °F (16 DEG C)- The temperature of 110 °F (43 DEG C).For example, the process that treatment compositions or bath are contacted with substrate can be in environment temperature or room temperature Such as 23 DEG C of progress, unless otherwise directed.Time of contact is often 1 second to 2 hours, such as 5 minutes to 60 minutes.

According to the present invention, the thickness of the layer formed by the treatment compositions for example high can arrive 550nm, such as 5nm- 550nm, such as 10nm-400nm, such as 25nm-250nm.The thickness degree that composition is formed through this process can be used Analytical technology measures, including but not limited to XPS (x-ray photoelectron spectroscopy) depth profile or TEM (transmission electron microscope).Such as It is used herein, " thickness " when be related to by layer that treatment compositions of the invention are formed and in use, referring to (a) initial Air/substrate interface layer formed above, (b) is formed by modified layer below pretreatment/substrate interface, or is (c) (a) (b) combination, as shown in Figure 3.Although modified layer (b) is shown extend to pretreatment/substrate interface in Fig. 3, insertion Layer can reside between modified layer (b) and pretreatment/substrate interface.Equally, (c), the combination of (a) and (b) is not limited to continuous Layer and it may include multiple layers and there is insert layer in-between, and the measurement of the thickness of layer (c) can exclude the insertion Layer.

Can be used for suitable substrate of the invention includes metallic substrates, metal alloy base, and/or metallized Substrate such as nickel plated plastic.According to the present invention, the metal or metal alloy may include either steel, aluminium, zinc, nickel and/or Magnesium.Such as steel base can be with cold-rolled steel, hot-rolled steel, galvinized steel and/or hot dipping galvinized steel.1XXX, 2XXX, 3XXX, 4XXX, It 5XXX, 6XXX or 7XXX series alloys and covers aluminium alloy and is also used as substrate.Aluminium alloy may include 0.01 weight The copper of % is measured to the copper of 10 weight %.Processed aluminium alloy can also include cast body such as 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X or 9XX.X (such as: A356.0).AZ31B, AZ91C, AM60B or EV31A series magnesium alloy is also used as substrate.Substrate used in the present invention can also include titanium and/or titanium alloy, zinc and/or zinc Alloy and/or nickel and/or nickel alloy.According to the present invention, the substrate may include vehicle a part such as car body (such as but It is not limited to door, body panels, standby boxboard lid, top plate, hood, roof and/or the support strip on aircraft, rivet, rise and fall portion Part and/or face component) and/or vehicle frame.As used in this article, " vehicle " or its variant it is including but not limited to civilian, Commercial and military aircraft and/or land vehicle such as car, motorcycle and/or truck.

According to the present invention, before at least part of substrate surface is contacted with above-mentioned treatment compositions or bath, at least A part the substrate surface can by it is known in the art it is any cleaning or metal pretreated substrate conventional means come Cleaning and/or oxide removal and/or pretreatment, to remove degreasing, foul and/or other foreign matters.At least part of substrate Surface can be cleaned by physically and/or chemically means, for example, the mechanical lapping surface and/or with it is commercially available alkalinity or Acidic cleaning come clean/degreasing described in surface, this is well known to those skilled in the art.It is suitable for the invention alkaline clean The example of agent includes Chemkleen -166tlP, 166m/c, 177,490MX, 2010LP and Surface Prep 1 (SP 1), Ultrax 32, Ultrax 97, Ultrax 29 and 92D, each of which available commercially from PPG Industries, Inc. (Cleveland, OH) and any DFM series, 1002 detergent of RECC 1001 and 88X, available commercially from PRC-DeSoto International, Sylmar, CA) and Turco 4215-NCLT and Ridolene (available commercially from Henkel Technologies, Madison Heights, MI).Such detergent often water rinse for example with tap water, distilled water or a combination thereof rinse before or Later.

As described above, according to the present invention, at least part of clean substrate surface can mechanically and/or chemically carry out deoxidation Compound.As used in this article, term " oxide removal " indicate remove substrate surface existing for oxide skin(coating) come promote conversion or Attachment on the uniform deposition of person's pretreatment compositions and the such composition coating to substrate surface of promotion.Suitable deoxidation Compound agent will be well known to those skilled in the art.A kind of typical mechanical oxide removal mode can be for example using wiping or Person's cleaning pad comes so that substrate surface even roughness.Typical chemistry deoxygenated agent includes such as acidic group deoxygenated agent example As phosphoric acid, nitric acid, fluoboric acid, sulfuric acid, chromic acid, hydrofluoric acid and fluoram or 7/17 deoxygenated agent of Amchem (are obtained from Henkel Technologies, Madison Heights, MI), OAKITE DEOXIDIZER LNC (available commercially from Chemetall), TURCO DEOXIDIZER 6 (available commercially from Henkel) or a combination thereof.In general, the chemistry deoxygenated agent packet Containing carrier, often water-bearing media, so that the deoxygenated agent may be at the shape of solution or dispersion in the carrier Formula, the solution or dispersion can be contacted by any a variety of known technologies with substrate in this case, such as be soaked Stain or submergence, spraying, intermittent spray impregnate subsequent spraying, spray then dipping, brushing or roller coating.According to the present invention, when When being applied to metallic substrates, those skilled in the art can select the temperature model of the solution or dispersion based on etch-rate It encloses, such as 50 °F -150 °F (10 DEG C -66 DEG C), such as 70 °F -130 °F (21 DEG C -54 DEG C), such as 80 °F -120 °F (27 DEG C -49 DEG C) temperature.The time of contact can be -20 minutes 30 seconds, such as -15 minutes 1 minute, such as -12 minutes 90 seconds, such as 3 - 9 minutes minutes.

After cleaning and/or desoxidation step, which can optionally use tap water, deionized water and/or flushing The aqueous solution of agent rinses to remove any residue.According to the present invention, wet basis bottom surface can protect field technology by substrate The pretreatment of any method known to personnel, such as with conversion composition anodization or processing, and/or above-mentioned processing group can be used Closing the processing of one of object or the substrate can dry before handling substrate surface, such as be air-dried, such as use air knife It is dry, by substrate it is of short duration be exposed to such as 15 DEG C -100 DEG C of high temperature, such as 20 DEG C -90 DEG C flash away water, or heating Such as infrared heating is used in device assembly, such as is carried out 10 minutes at 70 DEG C, or substrate is passed through between rubber rollers.According to this Invention, the conversion composition may include such as lanthanide series, Group IIIB metal and/or group ivb metal, and can be into One step includes group iia metal, Group VB metal, vib metals, V Group IIB metal and/or X II race.According to this hair Bright, which can be for example comprising cerium, praseodymium, terbium or a combination thereof；The group iia metal may include magnesium；Section III B Race's metal may include yttrium, scandium or a combination thereof；The group ivb metal may include zirconium, titanium, hafnium or a combination thereof；V B Race's metal may include vanadium；The vib metals may include trivalent or Cr VI and/or molybdenum；The V Group IIB metal can To include manganese；It may include zinc with X II race metal.

According to the present invention, after substrate is contacted with the treatment compositions, the coating composition comprising film-forming resin can sink In product at least part surface of substrate, which is contacted with the treatment compositions.Any suitable technology can be with It for such coating composition to be deposited to substrate, including for example brushes, dip-coating, flow coat, spraying etc..But in some feelings In condition, as described in more detail below, the such deposition of coating composition may include electropaining step, and wherein electrodepositable combines Object is deposited in metallic substrates by electro-deposition.In other certain situations, as described in more detail below, coating group Closing the such deposition of object includes powder coating step.In other situations still, which can be liquid coating Composition.

According to the present invention, which may include thermosetting film-forming resin or thermoplastic film-forming resin.Such as this Used herein, term " film-forming resin " refers to such resin, can be any in the presence of removing the composition When diluent or carrier or when being to solidify at a temperature of environment temperature or raising, on at least horizontal surface of substrate Form self-supporting continuous film.The conventional film-forming resin that can be used includes but is not limited to be commonly used in automotive OEM Coating material composition Object, automobile ornamenting coating composition, industrial coating composition, architectural coating compositions, coil coating composition and aerospace coatings Those of in composition etc..As used in this article, term " thermosetting property " refers to such resin, by solidification or hands over Join and irreversibly " solidify ", wherein the polymer chain of the polymers compositions is combined by covalently bonded.This property Can be usually related to the cross-linking reaction of composition components, often for example by heating or radiating come caused by.Solidification or Person's cross-linking reaction can also carry out at ambient conditions.Once solidification or crosslinking, then thermosetting resin will not when applying heat Melt and do not dissolve in solvent.As used in this article, term " thermoplasticity " refers to such resin, and it includes such polymerizations Object component: it is not by Covalent bonding together, and it is possible thereby to experience liquid flowing when heated, and dissolves in molten Agent.

As it appears from the above, according to the present invention, the electrodepositable of film-forming resin dispersible comprising water, containing ionic salt group applies Feed composition can be deposited in substrate by electropaining step, and wherein the electrodepositable coating composition is heavy by electricity It accumulates and deposits in metallic substrates.The film forming polymer containing ionic salt group may include to be applied for cationic electrodepositable The film forming polymer containing cationic salts group in feed composition.As used in this article, term " cation salt groups Film forming polymer " refers to such polymer comprising the cation group at least partly neutralized, such as assign positive charge Sulfonium group and ammonium group.The film forming polymer of cation salt groups may include active hydrogen functional group, including such as hydroxyl, Primary or secondary amine group and thiol group.The film forming polymer of cation salt groups comprising active hydrogen functional group can claim Make containing reactive hydrogen, the film forming polymer of cation salt groups.It is suitable as the film forming polymer of cation salt groups The example of polymer includes but is not limited to alkyd polymer, acrylate copolymer, polyepoxide, polyamide, polyurethane, Polyureas, polyethers and polyester etc..The film forming polymer of the cation salt groups is in cationic electrodepositable coatings composition Amount can be 40%-90% weight, such as 50%-80% weight, such as 60%-75% weight, be based on the electrodepositable The total weight of the resin solid of coating composition.As used in this article, " resin solid " include containing ionic salt group at Membrane polymer, curing agent, and any other water being present in the electrodepositable coating composition are dispersible uncoloured Component.

Alternatively, the film forming polymer for containing ionic salt group may include the film forming polymer containing anionic salt groups to use In anionic electrodepositable coating composition.As used in this article, term " film forming polymer containing anionic salt groups " refers to Be such anionic polymer, it includes the anionic functional group at least partly neutralized, such as assign the carboxylic of negative electrical charge Acid and phosphate group.The film forming polymer containing anionic salt groups may include active hydrogen functional group.Include reactive hydrogen function The film forming polymer containing anionic salt groups of group can be referred to as film forming polymers containing reactive hydrogen, containing anionic salt groups. The film forming polymer containing anionic salt groups may include alkali solubilising, carboxy-containing acid group film forming polymer such as drying oil The either reaction product or addition product of semi-drying fatty acid ester and dicarboxylic acids or acid anhydrides；And aliphatic ester, unsaturated acids or The reaction product of person's acid anhydrides and any other unsaturated modified material, further with polyol reaction.It also suitable is not At least partly neutralizing for the hydroxy alkyl ester of saturated carboxylic acid, unsaturated carboxylic acid and other at least one ethylenically unsaturated monomers is mutual Polymers.Still another suitable anionic electrodepositable resin includes alkyd resin-aminoplast vehicle, that is, contains alkyd tree The carrier of rouge resin and amine-aldehyde resins.Another suitable anionic electrodepositable resin combination includes the mixed of resinous polyol Close ester.The polyepoxide of the polymer such as phosphorylation of other sour functions or the acroleic acid polymerization of phosphorylation can also be used Object.The polyepoxide of exemplary phosphorylation is disclosed in [0004]-of U.S. Patent Application Publication No.2009-0045071 [0015] and in [0014]-[0040] of US Pat Appl Ser No.13/232093, reference portion is incorporated herein by With reference to.Amount of the film forming polymer containing anionic salt groups in the anionic electrodepositable coating composition can be 50%-90%, such as 55%-80%, such as 60%-75%, based in the electrodepositable coating composition resin solid it is total Poidometer.

The electrodepositable coating composition can further include curing agent.The curing agent can contain ionic salt group with this Film forming polymer reactive group for example active hydrogen group react, to complete the solidification of coating composition to form coating. The not limiting example of suitable curing agent is at least partly closed polyisocyanates, amino resin and phenola plastics tree Rouge, such as phenolic condensation compound, including its allyl ether derivative.The curing agent is in cationic electrodepositable coatings composition Amount can be 10%-60% weight, such as 20%-50% weight, such as 25%-40% weight, be based on the electrodepositable The total weight of the resin solid of coating composition.Alternatively, presence of the curing agent in anionic electrodepositable coating composition Amount can be 10%-50% weight, such as 20%-45% weight, such as 25%-40% weight, be based on the electrodepositable coating The total weight of the resin solid of composition.

Electrodepositable coating composition can further include other optional compositions, such as color compositions and such as fruiting period If prestige, different additives such as filler, plasticizer, antioxidant, biocide, UV light absorber and stabilizer, by Hinder amine light stabilizer, defoaming agent, fungicide, dispersing aid, flow control agent, surfactant, wetting agent or a combination thereof. The electrodepositable coating composition can wrap aqueous and/or one or more organic solvents.Water can be for example with 40%-90% weight Amount, such as the amount of 50%-75% weight exist, the total weight based on the electrodepositable coating composition.If used, this has The typical amount of solvent can be, for example, less than 5 weight %, based on the electrodepositable coating composition less than 10 weight % Total weight.Electrodepositable coating composition can be provided specifically with aqueous dispersion form.Electrodepositable coating composition Total solids content can be 1%-50% weight, such as 5%-40% weight, such as 5%-20% weight, be based on the electrodepositable The total weight of coating composition.As used in this article, " total solid " refers to the non-volatile of electrodepositable coating composition Property content, that is, be heated to 110 DEG C continue 15 minutes when nonvolatile material.

The cationic electrodepositable coatings composition can deposit in conductive substrates as got off: by composition and conduction yin Pole and conductive anode contact are placed, and the surface to be coated is cathode.Alternatively, the anionic electrodepositable coating composition can It is deposited in conductive substrates with such as getting off: the composition is contacted into placement with conductive cathode and conductive anode, and to be coated Surface is anode.When applying enough voltage between the electrodes, the adhesive film of the electrodepositable coating composition is with substantially Continuous mode is respectively deposited on cathode or anode.The voltage applied can be variation, and can be for example as low as 1 volt It is lied prostrate to height to several kilovolts of such as 50-500.Current density is usually 1.0 amperes -15 amperes/square feet (10.8-161.5 peaces Training/square metre) and tend to rapid decrease during electro-deposition method, this suggests the formation of continuous self-insulating film.

Once the cation or anionic electrodepositable coating composition are electrodeposited at least part of conductive substrates On, then coated substrate can be heated to certain temperature and continue for some time, and the electro-deposition being enough in cured substrate applies Layer.For cationic electrodeposition, coated substrate can be heated to 250 °F -450 °F (121.1 DEG C -232.2 DEG C), such as 275 °F -400 °F (135 DEG C -204.4 DEG C), such as the temperature of 300 °F -360 °F (149 DEG C -180 DEG C).It is heavy for anionic electrodeposition Product, coated substrate can be heated to 200 °F -450 °F (93 DEG C -232.2 DEG C), such as 275 °F -400 °F (135 DEG C - 204.4 DEG C), such as 300 °F -360 °F (149 DEG C -180 DEG C), such as the temperature of 200 °F -210.2 °F (93 DEG C -99 DEG C).Solidification Time can depend on solidification temperature and its dependent variable, such as the film thickness of electrodeposited coating, catalyst present in composition Horizontal and type etc..Such as curing time can be -60 minutes 10 minutes, such as 20-40 minutes.It is heavy to be formed by cured electricity The thickness of product coating can be 2-50 microns.

Alternatively, as described above, according to the present invention, after substrate is contacted with the treatment compositions, powder coating composition Object can be subsequently deposited on at least part of surface of substrate, be contacted with the treatment compositions.As herein It uses, " powder paint compositions " refer to the coating composition of absolutely not water and/or solvent.Therefore, disclosed herein Powder paint compositions and known in the art water base and/or solvent-based coating composition are not synonymous.According to the present invention, should Powder paint compositions may include the film forming polymer that (a) has reactive functional groups；(b) have with the functional group and react The curing agent of property.The example that can be used for powder paint compositions of the invention includes that polyester base ENVIROCRON Series powder applies Feed composition (available commercially from PPG Industries, Inc.) or epoxy-polyester heterozygosis powder paint compositions.It can be used for this The alternative example of the powder paint compositions of invention includes low-temperature setting powdered thermosetting compositions for coatings, and it includes (a) At least one tertiary amino carbamide compound, at least one tertiary amino urethane compound or its mixture, and (b) at least one film forming The resin of the resin and/or at least one silicone-containing containing epoxy (such as that in United States Patent (USP) No.7470752 is described A bit, belong to PPG Industries, Inc. and be hereby incorporated by reference)；Curable powder paint compositions usually wrap Containing (a) at least one tertiary amino carbamide compound, at least one tertiary amino urethane compound or its mixture, and (b) at least one Kind film forming containing epoxy resin and/or at least one silicone-containing resin (such as description in United States Patent (USP) No.7432333 Those, belong to PPG Industries, Inc. and be hereby incorporated by reference)；With comprising with T_gBe at least 30 DEG C containing anti- Those of solids mixture of the polymer of answering property group (such as describe those of in United States Patent (USP) No.6797387, Belong to PPG Industries, Inc. and be hereby incorporated by reference).

After powder paint compositions deposition, the coating is often heated to cure deposited composition.It should add Heat or curing operation are often at 150 DEG C -200 DEG C, such as 170 DEG C -190 DEG C of temperature carries out 10-20 minutes time.According to The present invention, the thickness for being formed by film is 50 microns -125 microns.

As described above, according to the present invention, which can be liquid coating composition.As used in this article, " liquid coating composition " refers to the coating composition of the water comprising a part and/or solvent.Therefore, liquid disclosed herein Coating composition is synonymous with known in the art water base and/or solvent-based coating composition.According to the present invention, which applies Feed composition may include for example (a) film forming polymer with reactive functional groups；(b) have with the functional group reactive Curing agent.In other examples, which, which may include, can react with the oxygen in air or with dampening and/or molten The evaporation of agent and the film forming polymer of film coalescence.These membrane formation mechanisms, which may require that or pass through, applies heat or some type of Such as ultraviolet light or infrared light are radiated to accelerate.The example that can be used for liquid coating composition of the invention includesThe solvent-based coating composition of series,Series water base paint compositions andThe UV coating material solidified (all available commercially from PPG Industries, Inc.) of series.It can be used for liquid of the invention Suitable film forming polymer in body coating composition may include (poly-) ester, alkyd resin, (poly-) urethane, chlorinated isocyanurates, (poly-) urea, (poly-) epoxy, acid anhydrides, acrylic resin, (poly-) ether, (poly-) thioether, (poly-) amine, (poly-) amide, (poly-) vinyl chloride, (poly-) alkene, (poly-) vinylidene, (poly-) siloxanes or a combination thereof.

According to the present invention, the substrate contacted with process described herein composition can also with paint base composition and/ Or top coat composition contact.The primer base can be the priming paint and high-performance top coat material of such as chromate-based.According to the present invention, The primer base can be the primer base of conventional chromate-based, such as (produce obtained from PPG Industries, those of Inc. Product code 44GN072) or non-chrome primer for example obtained from those of PPG (DESOPRIME CA 7502, DESOPRIME CA 7521, Deft 02GN 083, Deft 02GN 084).Alternatively, the primer base can be the primer base of chromate-free, example As described in US Pat Appl Ser No.10/758973, entitled " CORROSION RESISTANT COATINGS CONTAINING CARBON " and US Pat Appl Ser No.10/758972 and 10/758972, the two is entitled Coating composition in " CORROSION RESISTANT COATINGS ", whole are hereby incorporated by reference, and the present invention Other non-chrome primers known in the art can also be used, and it can pass through MIL-PRF-85582N class or MIL-PRF- The military requirements of 23377N class.

As described above, substrate of the invention can also include top coat material.As used in this article, term " top coat material " refers to It is binder, can be the mixture of organic or inorganic based polymer or polymer, typically at least one pigment is mixed Object is closed, and can be optionally comprising at least one solvent or solvent mixture, and can optionally include at least one solid Agent.Top coating is typically single layer and is perhaps exposed to atmosphere or environment in its outer surface of the coating of multilayer coating system, and And its inner surface is contacted with another coating or polymeric substrates.The example of suitable top coat material includes meeting MIL-PRF- Those of 85285D, such as obtained from those of PPG (Deft 03W 127A and Deft 03GY 292).According to the present invention, the top Coating can be high-performance top coat material, for example, obtained from those of PPG (ELT.TM.99GY 001 and 99W 009).But other top coat material and high-performance top coat material can be used for the present invention, such as refer to those skilled in the art of the invention As member will be understood that.

According to the present invention, the metallic substrates can also comprising from bottoming top coat material, or enhancing from bottoming top coat material.Art Language " from bottoming top coat material " is also referred to as the coating of " directly contact substrate " or " directly contact metal ", refers to binder (its mixture that can be organic or inorganic based polymer or polymer), the mixture of typical at least one pigment, Can be optionally comprising at least one solvent or solvent mixture, and can optionally include at least one curing agent.Term " enhancing from bottoming top coat material " is also referred to as " the direct contact base coating of enhancing ", refers to functionalized fluorinated binder Such as fluoroethylene-alkyl vinyl base ether is all or partly (it can be organic or inorganic base and polymerize with other binders Object or polymeric blends) mixture, typical at least one pigment, can optionally comprising at least one solvent or Solvent mixture, and can be optionally comprising at least one curing agent.It include meeting TT-P- from the example of bottoming top coat material Those of 2756A.It include oneself being obtained from those of PPG (03W 169 and 03GY 369), and enhance from the example of bottoming top coat material The example of bottoming top coat material includesELT^TM/ ESPT and product code 97GY 121, available from PPG.But Other can be used for coating system according to the present invention, such as art technology from bottoming top coat material with what is enhanced from bottoming top coat material Personnel are with reference to as understanding the present invention.

According to the present invention, from the substrate that can be directly applied to sealing from bottoming top coat material of bottoming top coat material and enhancing On.This can optionally be applied to organic or inorganic polymer coatings example from bottoming top coat material with what is enhanced from bottoming top coat material On priming paint or paint film.This from the bottoming top coat bed of material and enhancing from bottoming top coat material be typically single layer or laminated coating Coating in system, the outer surface of floating coat be exposed to the inner surface of atmosphere or environment and coating typically with substrate or Person optional polymer coating or primer source.

According to the present invention, the top coat material, can be with wet or " not from bottoming top coat material from bottoming top coat material and enhancing It is sufficiently cured " condition is applied in the substrate of sealing, and it is dry at any time or solidify, that is, solvent evaporation and/or presenceization Learn reaction.The coating can be naturally or by acceleration means such as UV curing system drying or solidification, to be formed Film or " cured " paint.The coating with semi-solid preparation or can also be fully cured state and apply, such as adhesive.

In addition, colorant and if it is desire to different additives such as surfactant, wetting agent or catalyst can To be included in the coating composition (electrodepositable, powder or liquid coating composition).As used in this article, term " colorant " indicates any such substance, assigns color and/or other opacity and/or other views for the composition Feel effect.The example of colorant includes pigment, dyestuff and toner, such as paint industry and/or is listed in Dry Color Those of in Manufacturers Association (DCMA) and special effect composition.In general, colorant is in coating Amount in composition can be any amount for being enough to assign desired vision and/or colour effect.The colorant can account for 1-65 weight %, such as 3-40 weight % or 5-35 weight %, total weight of the weight percent based on composition.

Aspect

In view of foregoing teachings, therefore the application is specifically related to following aspect 1-24, but be not limited to these:

A kind of 1 composition, it includes the carbon dioxide and lithium cation in water-bearing media.

2. wherein carbon dioxide includes gas, solid or a combination thereof according to the composition of aspect 1.

3. wherein the amount of lithium cation is that 5ppm-5500ppm (makees according to the composition of any one of aspect 1 or 2 For lithium cation calculating), the total weight based on the treatment compositions.

4. wherein pH is 9.5-12.5 according to the composition in terms of aforementioned any one.

5. further including hydroxide according to the composition in terms of aforementioned any one.

6. according to the composition in terms of aforementioned any one, wherein the amount of carbonate be 15ppm-25000ppm (as Carbonate calculates), the total weight based on the treatment compositions.

7. a kind of method for manufacturing treatment compositions, it includes:

Merge lithium cation and carbon dioxide in water-bearing media treatment compositions are formed in situ, wherein the processing is combined The lithium amount that object includes is 5ppm-5500ppm (calculating as lithium cation), total weight and carbon based on the treatment compositions Hydrochlorate amount is 15ppm-25000ppm (calculating as carbonate), the total weight based on the treatment compositions.

8. according to the method for the manufacture treatment compositions of aspect 7, wherein lithium cation be as lithium carbonate, lithium hydroxide or Person's a combination thereof and it is existing.

9. according to the method for the manufacture treatment compositions of aspect 7 or any one of 8, wherein carbon dioxide be as gas, Solid or a combination thereof is supplied in water-bearing media.

10. aqueous it includes this is added in hydroxide according to the method for the manufacture treatment compositions of any one of aspect 7-9 Medium.

11. wherein the hydroxide includes lithium hydroxide, hydroxide according to the method for the manufacture treatment compositions of aspect 10 Sodium, potassium hydroxide or a combination thereof.

12. wherein this method includes by the processing group according to the method for the manufacture treatment compositions of any one of aspect 7-11 The pH for closing object is adjusted to 9.5-12.5.

13. a kind for the treatment of compositions are obtained according to the method for any one of aspect 7-12.

14. a kind of method for the processing bath for maintaining to be formed by the treatment compositions comprising lithium carbonate, this method includes:

During and/or after handling substrate with bath, carbon dioxide and at least one of lithium salts are supplied with such amount To the bath, which is enough to maintain the pH of the bath foam into 9.5-12.5, lithium amount maintain 5ppm-5500ppm (as lithium sun from Son calculates), 15ppm-25000ppm (calculating as carbonate) is maintained based on processing bath total weight and carbonate amount, Total weight is bathed based on the processing.

15. wherein lithium salts includes lithium carbonate, lithium hydroxide or its group according to the method for the maintenance processing bath of aspect 14 It closes.

16. according to the method for the maintenance processing bath of aspect 14 or any one of 15, wherein carbon dioxide be as gas, Gu Body or a combination thereof is supplied to the bath.

17. it includes hydroxide is supplied to the bath according to the method for the maintenance processing bath of any one of aspect 14-16.

18. wherein hydroxide includes lithium hydroxide, sodium hydroxide, hydrogen according to the method for the maintenance processing bath of aspect 17 Potassium oxide or a combination thereof.

19. further including according to the method for the maintenance processing bath of any one of aspect 14-18 and monitoring processing bath PH, the amount of carbonate in processing bath, the lithium amount or a combination thereof in processing bath.

20. a kind of substrate is with the treatment compositions of any one of aspect 1-6 or 13 or with according to aspect 14-19 The maintained processing of the method for any one bathes to handle.

21. a kind of system for the processing bath for maintaining to be formed by the treatment compositions comprising lithium carbonate, which includes:

Lithium salts source；And/or

Carbon dioxide source；With

Optional hydroxide source.

22. according to aspect 21 maintenance processing bath system, wherein the lithium salts source include lithium carbonate, lithium hydroxide or its Combination.

23. wherein the carbon dioxide source includes conduct according to the system of the maintenance processing bath of any one of aspect 21 or 22 The carbon dioxide of gas, solid or a combination thereof.

24. according to the system of the maintenance processing bath of any one of aspect 21-23, wherein the system includes hydroxide source, Include lithium hydroxide, sodium hydroxide, potassium hydroxide or a combination thereof.

Although specific features of the invention have been described for purpose of explanation above, those skilled in the art are come Saying obviously can be to the thin for the treatment of compositions disclosed herein and the bath formed by it and preparation or the method for maintaining it Section carries out many changes, without departing from the range of appended claims.

The following examples illustrate the present invention, are not considered as limiting the invention to their details.Embodiment with And whole parts and percentages in entire application documents are unit of weights, unless otherwise directed.

Embodiment

2 material of table

* according to the analytical proof material of supplier

Table 3- detergent/deoxygenated agent composition (embodiment A)

	Weight (g)
		Sodium hydroxide pellets, 98%	0.016
Sodium phosphate decahydrate, 97%	0.063
		Polyvinylpyrrolidone (PVP), 8000 molecular weight	0.002
Allantoin, 98%	0.003
		2,5- dimercapto-1,3,4-thiadiazoles (DMTD), 98%	0.100
Carbowet GA100	0.410
		Deionized water	98.7

Table 3 provides the detergent/deoxygenated agent composition ingredient for being used to prepare embodiment A and theirs opposite Amount.Sodium hydroxide and sodium phosphate is completely molten under the appropriate mechanical stirring using agitating plate (VWR, 7x7 CER HOT/STIR) Solution is in deionized water.Then, once sodium hydroxide and sodium phosphate are completely dissolved, then PVP is stirred until dissolution, and then added Enter allantoin and stirring until dissolution, DMTD and stirring is then added until dissolution.After DMTD is completely dissolved, by Carbowet GA100 is stirred under appropriate mechanical stirring as above.

Table 4- conversion composition (embodiment B)

	Quality (g)
		Yttrium nitrate solution	12.48
Cerous nitrate solution	10.40
		Solution of cerium chloride by oxidation	0.04
Hydrogenperoxide steam generator	1.04
		Deionized water	1953

The component and their amount for being used to prepare the conversion coating compositions solution of embodiment B provide in table 4.By nitric acid Cerium, yttrium nitrate and solution of cerium chloride by oxidation are weighed in each cup.Then 500g deionized water is used, it is in the case where being slightly agitated for that this is molten Liquid is transferred in the container containing 1000g deionized water.Remaining 453g water is added and the solution is stirred 10 minutes to ensure The uniformity before hydrogen peroxide is added.Final solution is being stirred into minimum 30 minutes using preceding.

Table 5- sealing compositions (embodiment C-O)

In the preparation of sealing compositions, the pH of each embodiment C-J is using pH meter (Accumet AB15, Fisher ) and single connection electrode (Ag/AgCl reference electrode Scientific；Fisher Scientific) measurement, and each implementation The pH of example K-O is using pH meter (Mettler Toledo, Seven2Go, S2 type) and double open connection electrode (Mettler Toledo,Polymer reference electrode) come what is measured.

Sealing compositions embodiment C and embodiment K is each using ingredient shown in table 5, by stating agitating plate in use Lithium carbonate is dissolved into deionized water under being slightly agitated for of (VWR, 7x7CER HOT/STIR) to prepare.Embodiment C's is final PH is 11.52.Embodiment C is used to handle the panel (being described below) in comparative example 1.The final pH of embodiment K is 11.14.It is real A K is applied for handling the panel (being described below) in comparative example 9.

Sealing compositions embodiment D and embodiment L is each using ingredient shown in table 5, by stating agitating plate in use It is slightly agitated for lower lithium hydroxide is dissolved into deionized water to prepare.The final ph of embodiment D is 12.69.Embodiment D is used Panel (being described below) in processing comparative example 2.The final ph of embodiment L is 12.17.Embodiment L is for handling comparison Panel (being described below) in example 10.

In the bath for having used the composition containing embodiment D come after handling the panel according to comparative example 2, by by dioxy Change carbon gas sparging and prepares sealing compositions until obtaining final ph 11.42 into the bath of the composition containing embodiment D Embodiment E.Referring to Fig. 1 and table 5.Embodiment E is for the panel (being described below) in Processing Example 3.

In the bath for having used the composition containing embodiment E come after handling the panel according to embodiment 3, by will in addition Carbon dioxide gas be bubbled into the composition of embodiment E until obtain final ph 10.54 come prepare sealing compositions reality Apply a F.Referring to Fig. 1 and table 5.Embodiment F is for the panel (being described below) in Processing Example 4.

In the bath for having used the composition containing embodiment F come after handling the panel according to embodiment 4, by will in addition Carbon dioxide gas be bubbled into the composition of embodiment F until obtain final ph 9.47 come prepare sealing compositions implement Example G.Referring to Fig. 1 and table 5.Embodiment G is for the panel (being described below) in Processing Example 5.

In the bath for having used the composition containing embodiment G come after handling the panel according to embodiment 5, by by 5% Lithium hydroxide solution, which is added in the composition of embodiment G, to be implemented until obtaining final ph 10.47 to prepare sealing compositions Example H.Referring to Fig. 1 and table 5.Embodiment H is for the panel (being described below) in Processing Example 6.

After the bath for having used the composition containing embodiment H according to embodiment 6, by by 5% lithium hydroxide solution It is added in the composition of embodiment H and prepares sealing compositions embodiment I until obtaining final ph 11.48.Referring to Fig. 1 and Table 5.Embodiment I is for the panel (being described below) in Processing Example 7.

After the bath for having used the composition containing embodiment I according to embodiment 7, by by 5% lithium hydroxide solution It is added in the composition of embodiment I and prepares sealing compositions embodiment J until obtaining final ph 12.47.Referring to Fig. 1 and Table 5.Embodiment J is for the panel (being described below) in Processing Example 8.

In the bath for having used the composition containing embodiment L come after handling the panel according to comparative example 10, by by two Carbon oxide gas, which is bubbled into the bath of the composition containing embodiment L, prepares seal combination until obtaining final ph 11.37 Object embodiment M.Referring to fig. 2 with table 5.Embodiment M is for the panel (being described below) in Processing Example 11.

In the bath for having used the composition containing embodiment M come after handling the panel according to embodiment 11, by will be another Outer carbon dioxide gas is bubbled into the composition of embodiment M real to prepare sealing compositions until obtaining final ph 9.5 Apply a N.Referring to fig. 2 with table 5.Embodiment N is for the panel (being described below) in Processing Example 12.

After the bath for having used the composition containing embodiment N according to embodiment 12, by by 5% lithium hydroxide solution It is added in the composition of embodiment N and prepares sealing compositions embodiment O until obtaining final ph 11.37.Referring to fig. 2 and table 5.Embodiment O is for the panel (being described below) in Processing Example 13.

Panel preparation

Comparative example 1

The aluminium 2024T3 bare substrate that size is 3 " x5 " x0.032 " (is obtained from Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In environment temperature and The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes under intermittent stirring.The panel is then immersed in During two subsequent deionized waters are rinsed, each 2 minutes, the two was all under environment temperature and intermittent stirring.It is rinsed second Later, which rinse within 10 seconds with cascade deionized water flushing.Then the panel immerses conversion combination in environment temperature 5 minutes in object embodiment B, without stirring.Then, the panel passes through immersion deionized water under environment temperature and intermittent stirring In 2 minutes, be followed by 10 seconds cascade deionized waters and rinse to rinse.Then the panel immerses under environment temperature and intermittent stirring 2 minutes in sealing compositions embodiment C.The panel is air-dried a whole night in environmental condition, is then corroded as described below Test.

Comparative example 2

The aluminium 2024T3 bare substrate that size is 3 " x5 " x0.032 " (is obtained from Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In environment temperature and The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes under intermittent stirring.The panel is then immersed in During two subsequent deionized waters are rinsed, each 2 minutes, the two was all under environment temperature and intermittent stirring.It is rinsed second Later, which rinse within 10 seconds with cascade deionized water flushing.Then the panel immerses conversion combination in environment temperature 5 minutes in object embodiment B, without stirring.Then, the panel passes through immersion deionized water under environment temperature and intermittent stirring In 2 minutes, be followed by 10 seconds cascade deionized waters and rinse to rinse.Then the panel immerses under environment temperature and intermittent stirring 2 minutes in sealing compositions embodiment D.The panel is air-dried a whole night in environmental condition, is then corroded as described below Test.

Embodiment 3

Comparative example 2 panel by the processing of the sealing solution of embodiment D after, the pH of the bath foam is by by carbon dioxide Gas sparging is into the bath until pH 11.42 is adjusted (that is, formed above-described embodiment E).Referring to Fig. 1.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which rinse within 10 seconds with cascade deionized water flushing.Then the panel is immersed in environment temperature 5 minutes in conversion composition embodiment B, without stirring.Then, the panel passes through immersion under environment temperature and intermittent stirring 2 minutes in deionized water, it is followed by 10 seconds cascade deionized waters and rinses to rinse.Then the panel is stirred in environment temperature and interval It mixes in lower immersion sealing compositions embodiment E 2 minutes.The panel is air-dried a whole night in environmental condition, then as described below Carry out corrosion test.

Embodiment 4

After panel is by the sealing solution processing of embodiment E, the pH of the bath foam is by the way that carbon dioxide gas to be bubbled Into the bath until pH 10.54 is adjusted (that is, formed above-described embodiment F).Referring to Fig. 1.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which rinse within 10 seconds with cascade deionized water flushing.Then the panel is immersed in environment temperature 5 minutes in conversion composition embodiment B, without stirring.Then, the panel passes through immersion under environment temperature and intermittent stirring 2 minutes in deionized water, it is followed by 10 seconds cascade deionized waters and rinses to rinse.Then the panel is stirred in environment temperature and interval It mixes in lower immersion sealing compositions embodiment F 2 minutes.The panel is air-dried a whole night in environmental condition, then as described below Carry out corrosion test.

Embodiment 5

After panel is by the sealing solution processing of embodiment F, the pH of the bath foam is by the way that carbon dioxide gas to be bubbled Into the bath until pH 9.47 is adjusted (that is, formed above-described embodiment G).Referring to Fig. 1.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which rinse within 10 seconds with cascade deionized water flushing.Then the panel is immersed in environment temperature 5 minutes in conversion composition embodiment B, without stirring.Then, the panel passes through immersion under environment temperature and intermittent stirring 2 minutes in deionized water, it is followed by 10 seconds cascade deionized waters and rinses to rinse.Then the panel is stirred in environment temperature and interval It mixes in lower immersion sealing compositions embodiment G 2 minutes.The panel is air-dried a whole night in environmental condition, then as described below Carry out corrosion test.

Embodiment 6

After panel is by the sealing solution processing of embodiment G, the pH of the bath foam uses lithium hydroxide solution institute as above It states to adjust (that is, forming above-described embodiment H).Referring to Fig. 1.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which rinse within 10 seconds with cascade deionized water flushing.Then the panel is immersed in environment temperature 5 minutes in conversion composition embodiment B, without stirring.Then, the panel passes through immersion under environment temperature and intermittent stirring 2 minutes in deionized water, it is followed by 10 seconds cascade deionized waters and rinses to rinse.Then the panel is stirred in environment temperature and interval It mixes in lower immersion sealing compositions embodiment H 2 minutes.The panel is air-dried a whole night in environmental condition, then as described below Carry out corrosion test.

Embodiment 7

After panel is by the sealing solution processing of embodiment H, the pH of the bath foam uses lithium hydroxide solution institute as above It states to adjust (that is, forming above-described embodiment I).Referring to Fig. 1.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which rinse within 10 seconds with cascade deionized water flushing.Then the panel is immersed in environment temperature 5 minutes in conversion composition embodiment B, without stirring.Then, the panel passes through immersion under environment temperature and intermittent stirring 2 minutes in deionized water, it is followed by 10 seconds cascade deionized waters and rinses to rinse.Then the panel is stirred in environment temperature and interval It mixes in lower immersion sealing compositions embodiment I 2 minutes.The panel is air-dried a whole night in environmental condition, then as described below Carry out corrosion test.

Embodiment 8

After panel is by the sealing solution processing of embodiment I, the pH of the bath foam uses lithium hydroxide solution institute as above It states to adjust (that is, forming above-described embodiment I).Referring to Fig. 1.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which is received into cascade deionized water and is rinsed 10 seconds.Then the panel immerses conversion group in environment temperature It closes in object embodiment B 5 minutes, without stirring.Then, the panel passes through immersion deionization under environment temperature and intermittent stirring 2 minutes in water, it is followed by 10 seconds cascade deionized waters and rinses to rinse.Then the panel soaks under environment temperature and intermittent stirring Enter in sealing compositions embodiment J 2 minutes.The panel is air-dried a whole night in environmental condition, then as described below to carry out corruption Erosion test.

Comparative example 9

The aluminium 2024T3 bare substrate that size is 3 " x5 " x0.032 " (is obtained from Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In environment temperature and The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes under intermittent stirring.The panel is then immersed in During two subsequent deionized waters are rinsed, each 2 minutes, the two was all under environment temperature and intermittent stirring.It is rinsed second Later, which was rinsed by cascade deionized water flushing in 10 seconds.Then the panel immerses conversion group in environment temperature It closes in object embodiment B 5 minutes, without stirring.Then, the panel passes through immersion deionization under environment temperature and intermittent stirring 2 minutes in water, it is followed by 10 seconds cascade deionized waters and rinses to rinse.Then the panel soaks under environment temperature and intermittent stirring Enter in sealing compositions embodiment K 2 minutes.The panel is air-dried a whole night in environmental condition, then as described below to carry out corruption Erosion test.

Comparative example 10

The aluminium 2024T3 bare substrate that size is 3 " x5 " x0.032 " (is obtained from Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In environment temperature and The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes under intermittent stirring.The panel is then immersed in During two subsequent deionized waters are rinsed, each 2 minutes, the two was all under environment temperature and intermittent stirring.It is rinsed second Later, which was rinsed by cascade deionized water flushing in 10 seconds.Then the panel immerses conversion group in environment temperature It closes in object embodiment B 5 minutes, without stirring.Then, the panel passes through immersion deionization under environment temperature and intermittent stirring 2 minutes in water, it is followed by 10 seconds cascade deionized waters and rinses to rinse.Then the panel soaks under environment temperature and intermittent stirring Enter in sealing compositions embodiment L 2 minutes.The panel is air-dried a whole night at ambient conditions, then as described below to carry out Corrosion test.

Embodiment 11

Comparative example 10 panel by the processing of the sealing solution of embodiment L after, the pH of the bath foam is by by titanium dioxide Carbon gas sparging is into the bath until pH 11.37 adjusts (that is, formed above-described embodiment M).Referring to fig. 2.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which was rinsed by cascade deionized water flushing in 10 seconds.Then the panel is soaked in environment temperature Enter in conversion composition embodiment B 5 minutes, without stirring.Then, the panel passes through leaching under environment temperature and intermittent stirring Enter in deionized water 2 minutes, is followed by 10 seconds cascade deionized waters and rinses to rinse.The panel is then in environment temperature and interval Stirring is lower to immerse in sealing compositions embodiment M 2 minutes.The panel is air-dried a whole night in environmental condition, then following institute State carry out corrosion test.

Embodiment 12

After panel is by the sealing solution processing of embodiment M, the pH of the bath foam is by the way that carbon dioxide gas to be bubbled Into the bath until pH 9.50 adjusts (that is, formed above-described embodiment N).Referring to fig. 2.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which was rinsed by cascade deionized water flushing in 10 seconds.The panel then at ambient temperature It immerses in conversion composition embodiment B 5 minutes, without stirring.Then, the panel passes through under environment temperature and intermittent stirring It immerses in deionized water 2 minutes, is followed by 10 seconds cascade deionized waters and rinses to rinse.The panel then environment temperature and It has a rest and stirs in lower immersion sealing compositions embodiment N 2 minutes.The panel is air-dried a whole night at ambient conditions, then such as Under the carry out corrosion test.

Embodiment 13

It is after panel is by the sealing solution processing of embodiment N, the pH of the bath foam is as above using lithium hydroxide solution It is described that (that is, forming above-described embodiment O) is adjusted.Referring to fig. 2.

Then, by size be 3 " x5 " x0.032 " other aluminium 2024T3 bare substrate (Priority Metals, Orange County, CA) it is wiped by hand with methyl ethyl ketone and disposable cloth and is air-dried it before chemically cleaning.In ring The panel is immersed in detergent-deoxygenated agent composition embodiment A 3.5 minutes at border temperature and intermittent stirring.The panel It is then immersed in two subsequent deionized waters flushings, each 2 minutes, the two was all under environment temperature and intermittent stirring.? After second rinses, which was rinsed by cascade deionized water flushing in 10 seconds.The panel then at ambient temperature It immerses in conversion composition embodiment B 5 minutes, without stirring.Then, the panel passes through under environment temperature and intermittent stirring It immerses in deionized water 2 minutes, is followed by 10 seconds cascade deionized waters and rinses to rinse.The panel then environment temperature and It has a rest and stirs in lower immersion sealing compositions embodiment O 2 minutes.The panel is air-dried a whole night at ambient conditions, then such as Under the carry out corrosion test.

Corrosion test

The panel of embodiment 1-8 is placed in the neutral salt spray cabin according to ASTM B117 operation and is exposed to the open air 7 days.Corrosive nature It is to be assessed by after the 7 day exposure, counting the visible pit number of naked eye on the panel.Before testing on edge Existing pit is formed by pit from the counting by scraping and excludes.Corrosive nature data report is in table 6.

Use autotitrating method (Metrohm 799 GPT Titrino, Tiamo 2.3 software) evaluation embodiment 9-13 Bath foam carbonic acid lithium content.%Li₂CO₃And %CO₃It is to be calculated using following formula:

%Li₂CO₃₌[(volume of the volume-EP2 of EP3) x MW Li₂CO₃X HCl concentration x 100]/(SW x 1000) With

%CO₃₌[(condition of the volume-EP2 of EP3) x MW CO₃X HCl concentration x 100]/(SW x 1000),

Wherein EP2 is the second terminal and EP3 is third terminal.HCl concentration (N) is 0.1012.

These values are used to calculate the amount of carbonate in the bath foam of the sealing compositions containing embodiment 9-13, such as 6 institute of table Report.

6. Corrosion results of table and carbonate measured value

Comparative example 1 and 9 shows that the processing containing the composition made of lithium carbonate is bathed.These embodiments show that containing The pH of such processing bath of the composition made of lithium carbonate, and comparative example 9 also shows lithium carbonate and carbon in processing bath The amount of hydrochlorate.The pH of the processing bath of comparative example 1 is 11.52, and recessed there are 5 on handled panel after salt fog exposes to the open air Hole.The pH of the processing bath of comparative example 9 is 11.14, and includes 0.154% lithium carbonate and 1248ppm carbonate.

Comparative example 2 and 10 shows that the processing containing the composition made of lithium hydroxide is bathed.It is apparent that embodiment D (is used In manufacture comparative example 2) lithium amount it is identical as the lithium amount in embodiment C (for manufacturing comparative example 1) (0.081mol lithium).Comparative example The pH of 2 processing bath is 12.69, and exists on handled panel after salt fog exposes to the open air and be greater than 100 pits.Comparative example 10 processing bath pH be 12.17 and only comprising 48ppm carbonate.While not wishing to theory is limited to, it is assumed that right Carbonate present in the processing bath of ratio 10 is CO₂It is converted to CO^3-Result.Enough carbon is not present in these data confirm thats When hydrochlorate, lithium cannot provide corrosion protection to bathe processed metallic substrates with the processing.

Embodiment 3 is confirmed by by CO₂It is bubbled into processing bath, pH can be reduced to comparable with comparative example 1 Range, while the pit number on the panel of processing is reduced to 6.As embodiment 11 is confirmed, CO₂It can be also used for forming bath CO is being added in lithium carbonate in liquid, the bath foam₂Before only with the lithium carbonate of trace.

Embodiment 4,5 and 12 is also demonstrated the CO of additional amount₂Being bubbled into processing bath reduces pH, but these realities Apply example show with processing bath pH reduce, with comparative example 1 (its pH be 11.52 and on the panel of processing have 5 it is recessed Hole) compare and with embodiment 3 (its pH be 11.42 and on the panel of processing have 6 pits) compared with, after salt fog exposes to the open air Have the tendency of the corrosion pit gradually increased (that is, the panel handled in embodiment 4 and 5 is in pH 10.54 on processing panel 10 and 18 pits are respectively provided under with 9.47).As embodiment 12 is confirmed, there are the carbonic acid of 1960ppm in processing bath Salt.For these data confirm thats in the bath foam comprising lithium carbonate, pH is crucial for corrosive nature.

Embodiment 6,7 and 13 confirms that LiOH, which is added, increases respectively to 10.47 and 11.48 for pH, this leads to corrosivity It can improve, because the panel as handled by embodiment 6 has 14 pits, and it is recessed with 3 those of handled by embodiment 7 Hole.

Embodiment 8 confirms that pH, which is increased to 12.5, weakens corrosive nature, is also even if carbonate level is enough In this way, and handle panel have 39 corrosion sites, this compared to comparative example 2 (its do not include any lithium carbonate and its tool Have and be not added in the bath greater than 100 pits and lithium carbonate) it is improved.

The embodiment confirms the interaction of pH, lithium concentration and carbonate concentration and corrosion resistance.

Claims (28)

1. a kind of composition comprising lithium carbonate, wherein the lithium carbonate is by carbon dioxide source and lithium cation in water-bearing media It is middle to react to be formed in situ.

2. the composition of claim 1, wherein the carbon dioxide source includes gas, solid or a combination thereof.

3. the composition of claim 1, wherein the amount of the lithium cation is that 5ppm to 5500ppm (comes as lithium cation Calculate), the total weight based on the composition.

4. the composition of claim 1, wherein pH is 9.5-12.5.

5. the composition of claim 1, further includes hydroxide source.

6. the composition of claim 1, wherein the amount of carbonate is that 15ppm to 25000ppm (is counted as carbonate Calculate), the total weight based on the treatment compositions.

7. a kind of substrate is handled with the composition of claim 1.

8. a kind of method for manufacturing treatment compositions, it includes:

Merge lithium cation and carbon dioxide source in water-bearing media to form treatment compositions, wherein the treatment compositions include Lithium cation amount be 5ppm to 5500ppm (as lithium cation calculate), the total weight based on the treatment compositions, and The amount of carbonate is 15ppm to 25000ppm (calculating as carbonate), the total weight based on the treatment compositions.

9. method for claim 8, wherein the pH of the treatment compositions is 9.5-12.5.

10. method for claim 8 further includes the acid of the not carbon dioxide treatment compositions is added.

11. method for claim 8, wherein lithium cation be as the salt comprising lithium carbonate, lithium hydroxide or a combination thereof and It is existing.

12. method for claim 8 further includes and hydroxide source is added in water-bearing media.

13. method for claim 8, wherein hydroxide source includes lithium hydroxide, sodium hydroxide, potassium hydroxide or its group It closes.

14. method for claim 8, wherein carbon dioxide source includes gas, solid or a combination thereof.

15. a kind of substrate is handled with method for claim 8.

16. a kind of system for maintaining the carbonate level in the processing bath containing treatment compositions, it includes:

Lithium cation；And/or

Carbon dioxide source；With

Optional hydroxide source.

17. the system of claim 16, wherein lithium cation includes lithium carbonate, lithium hydroxide or a combination thereof.

18. the system of claim 16, wherein carbon dioxide source includes gas, solid or a combination thereof.

19. the system of claim 16, wherein hydroxide source includes lithium hydroxide, sodium hydroxide, potassium hydroxide or its group It closes.

20. a kind of substrate is in the maintained bath of system according to claim 16 with processing compositions-treated.

21. a kind of method for maintaining the carbonate level in the processing bath containing treatment compositions, it includes:

At least one of carbon dioxide source and lithium source is supplied to bath with such amount, which is enough the pH of the treatment compositions 9.5-12.5 is maintained, lithium amount maintains 5ppm-5500ppm (calculating as lithium cation), is based on the treatment compositions gross weight Meter and carbonate amount maintain 15ppm-25000ppm (calculating as carbonate), are based on the treatment compositions total weight.

22. the method for claim 21, wherein carbon dioxide source includes gas, solid or a combination thereof.

23. the method for claim 21, wherein lithium source includes lithium carbonate, lithium hydroxide or a combination thereof.

24. the method for claim 21 further includes to the bath and supplies hydroxide source.

25. the method for claim 21, wherein after supply, in processing bath the amount of lithium carbonate be 25ppm-30000ppm (as Total compound calculates), the total weight based on the treatment compositions.

26. the method for claim 21 further includes the pH of monitoring processing bath, handles the amount of carbonate in bath, processing bath The amount or a combination thereof of middle lithium.

27. the method for claim 21, further including will differ from the acid of carbon dioxide processing bath is added.

28. a kind of substrate is that the treatment compositions in the bath maintained with method according to claim 21 are handled.