CN105331959B

CN105331959B - Lug nickel strap Surface treatment passivation solution

Info

Publication number: CN105331959B
Application number: CN201510730679.4A
Authority: CN
Inventors: 沈明森
Original assignee: Maikaimen Electronic Technology (shanghai) Co Ltd
Current assignee: Maikaimen Electronic Technology (shanghai) Co Ltd
Priority date: 2015-11-02
Filing date: 2015-11-02
Publication date: 2018-02-16
Anticipated expiration: 2035-11-02
Also published as: CN105331959A

Abstract

The invention discloses a kind of lug nickel strap Surface treatment passivation solution and preparation method thereof, the composition includes water, chromium trioxide, inorganic acid and film forming accelerating, the present invention fine must can solve the problems, such as passivating film compactness it is low, with tab poor adhesion.

Description

Lug nickel strap Surface treatment passivation solution

Technical field

The present invention relates to new energy resource power battery lug piece field of surface treatment, especially, the present invention relates to nickel strap lug Piece Surface treatment passivation solution.

Background technology

Nickel and nickel alloy are because of the new energy power electric with good intensity, excellent electric conductivity, thermal conductivity and plasticity Pond lug piece field has a wide range of applications.However, nickel and nickel alloy are situated between in the moist, alkalescence containing industrial gasses, fuel gas etc. The destruction of the forms such as spot corrosion, crevice corrosion, stress corrosion and corrosion fatigue easily occurs when being used in matter and salt solution, it is therefore, right It is required technique that its surface, which carries out preservative treatment,.

Passivation Treatment is the effective means for preventing nickel lug piece to be corroded, and at present, conventional inactivating treatment liquid is because of easily production Raw noxious material and carcinogen, and cause the harm to the mankind and the pollution of the mankind.European Union formally implements on July 1st, 2006 《On prohibitting the use of some Hazardous Substances Directives in electric/electronic device》.Meanwhile processing passivation is carried out to nickel lug piece The passivating film of processing and the cohesive of tab are poor.

It is badly in need of at this stage by the improvement to formula, to obtain a kind of nontoxic, good passivation effect, the cohesive with tab It is relatively strong, and the passivating solution being safe from harm to air.

The content of the invention

In order to solve the above problems, the invention provides a kind of environment-friendly type, cohesive is strong, compactness is high and salt spray resistance Good passivating film.

One aspect of the present invention provides a kind of lug nickel strap Surface treatment passivation solution, including：

Water 100；

Chromium trioxide 0.01-0.3；

Inorganic acid 0.01-0.5；

Film forming accelerating 0.01-0.1.

As a kind of embodiment, the inorganic acid is in sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid, lactic acid, hydrofluoric acid, acetic acid One or more.

As a kind of embodiment, the film forming accelerating is ammonium vanadate, strontium chloride, hydrofluoric acid, malonic acid, oxalic acid, penta One or more in diacid, malic acid, maleic acid.

As a kind of embodiment, the lug nickel strap Surface treatment passivation solution also ring-type including 0.01-1 parts by weight is more The compound of ether compound and modified graphene, and the structural formula of the more ether compounds of the ring-type is：

Wherein, R is amino, carboxyl, methylol, phenyl, acyl group or alkoxy；

X is the one or more in O, S and N；

n=1-10。

As a kind of embodiment, the modified graphene is hydroxylating graphene, carboxylated graphene, sulfonic group fossil Black alkene or amination graphene.

As a kind of preferred embodiment, the modified graphene is sulfonic group graphite alkene or hydroxylating graphene.

As a kind of preferred embodiment, the ratio of S elements is 5-10 at% in the sulfonic group graphite alkene；The hydroxylating The ratio of O elements is 5-15 at% in graphene and carboxylated graphene；The ratio of N element is in the amination graphene 10-20 at%。

As a kind of embodiment, the mol ratio of the more ether compounds of the ring-type and modified graphene is 35-15：1.

Another aspect of the present invention provides a kind of using a kind of metal surface of lug nickel strap Surface treatment passivation solution Handling process, its step include：

（1）Using alkalescent liquid, the grease on lug nickel strap is removed；

（2）By step（1）Middle alkalescent liquid is cleaned up with distilled water；

（3）Distilled water cleaning step is used again（2）In product, and dry, it is blunt to be immersed in the lug nickel strap surface treatment Change in liquid；

（4）With distilled water cleaning step（3）Middle product, drying, cropping of products（3）.

In the present invention, the passivating solution still further comprises：

Organic phospho acid 0.01-0.05；

Phytic acid 0.01-0.05；

Cetyl trimethylammonium bromide 0.01-0.05；

BTA 0.01-0.05.

Embodiment

Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention The identical implication that art personnel are generally understood that.When contradiction be present, the definition in this specification is defined.

As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or Such a composition, step, method, product or the intrinsic key element of device.

Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme, It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.

Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope be intended to include its end value with All integers and fraction within the range.

In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.

Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this public affairs can be more easily understood Open content.A large amount of terms can be referred in description below and claims, these terms are defined as following meanings.

Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise.

" optional " or " optionally " refer to that the item that describes thereafter or event may or may not occur, and this is retouched State the situation that the situation occurred including event and event do not occur.

Approximate term in specification and claims is used for modifying quantity, and it is specific to represent that the present invention is not limited to this Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity. In some examples, approximate term likely corresponds to the precision of the instrument of measured value.In present specification and claims In, scope limits and can combine and/or exchange, and these scopes include all sub- models contained therebetween if not stated otherwise Enclose.

Water 100；

Chromium trioxide 0.01-0.3；

Inorganic acid 0.01-0.5；

Film forming accelerating 0.01-0.1.

Wherein, R is amino, carboxyl, methylol, phenyl, acyl group or alkoxy；

X is the one or more in O, S and N；

n=1-10。

（1）Using alkalescent liquid, the grease on lug nickel strap is removed；

The more ether compounds of ring-type

The structural formula of the heretofore described more ether compounds of ring-type is：

Wherein, R is amino, carboxyl, methylol, phenyl, acyl group or alkoxy

X is the one or more in O, N and S；

n=1-10。

Terminology used in the present invention " the more ether compounds of ring-type " refers to include (CH₂CH₂X)_nConstitutional repeating unit Cyclic compound, wherein X are represented as hetero atom.In the present invention, the one or more in X O, N and S.

When X is all O, the more ether compounds of ring-type are cyclic polyether.

When n is 2, the cyclic polyether is 12- crown ethers -4；When n is 4, the cyclic polyether is 18- crown ethers -6；When n is During 1-10, the like.

The cyclic polyether can be including highly dilute using any method well known by persons skilled in the art to be prepared Interpretation of the law, template synthesis method and stepwise condensation etc..

It is, for example, possible to use template prepares the more ether compounds of ring-type as follows：By dihydroxy compounds and multiethylene-glycol two Chloride or two p-methyl benzenesulfonic acid esters react in the basic conditions, then form two C-O keys and are cyclized circlewise polyether class Compound.

When X is O and N in the more ether compounds of ring-type, the more ether compounds of ring-type are Azacrown ether containing.When n is 2 When, O is 3, and when N is 1, the more ether compounds of ring-type are azepine -12- crown ethers -4；When n is 4, O is 4, and N is 2 When, the more ether compounds of ring-type are diaza -18- crown ethers -6.

(the m when n is 1-10, and O is m<N), when N is n-m, the like.

When X is all N, the more ether compounds of ring-type are cyclic polyamines.

When n is 4, the cyclic polyamines are macrocyclic tetraamines.

The Azacrown ether containing can be including highly dilute using any method well known by persons skilled in the art to be prepared Interpretation of the law, template synthesis method and stepwise condensation etc..

It is, for example, possible to use highly dilution method prepares compund of aza crown ether as follows：The chain that p-toluenesulfonyl is substituted Shape polyamines obtains Azacrown ether containing with the p-methyl benzenesulfonic acid ester condensation of multiethylene-glycol two, then sloughs p-toluenesulfonyl and obtain Azacrown ether containing.

When X is O and S in the more ether compounds of ring-type, the more ether compounds of ring-type are thia crown ether.

When n is 2, O is 3, and when S is 1, the more ether compounds of ring-type are thia -12- crown ethers -4；When n is 4, O is 4, and when S is 2, the more ether compounds of ring-type are dithia -18- crown ethers -6.

(the m when n is 1-10, and O is m<N), when N is n-m, the like.

When X is all S, the more ether compounds of ring-type are ring-type polythiaether.

The thia crown ether can be prepared using any method well known by persons skilled in the art.

For example, thia crown ether compound can be prepared as follows：Closed with vulcanized sodium under the conditions of ethanol Into thia crown ether compound.

When X is N and S in the more ether compounds of ring-type, the more ether compounds of ring-type are ring-type nitrogen thia ether.

When n is 2, N is 2, and when S is 2, the more ether compounds of ring-type are sulphur -4,10 diazacyclos of 1,7- bis- Dodecane.

(the m when n is 1-10, and S is m<N), when N is n-m, the like.

The ring-type nitrogen thia ether can be prepared using any method well known by persons skilled in the art：By ammonia second Base thioether and 2-[(the chloro- 2- oxoethyls of 2-) sulfenyl] excess acetyl chlorides generation sulphur-4,10 diazacyclos ten of 1,7- bis- Dioxane -3,11- diketone, then again through being reduced into sulphur -4, the 10 diazacyclo dodecanes of 1,7- bis-.

When X is N, O and S in the more ether compounds of ring-type, the more ether compounds of ring-type are Azacrown ether containing sulfur.

For example, as n=1, when O is 1, when N is 1, when S is 1, the Azacrown ether containing sulfur is 1- azepines -4- thia-crown ethers - 3

The ring-type nitrogen thia ether can be prepared using any method well known by persons skilled in the art：Will be to first Benzsulfamide and 2,2'- oxygen are double（Ethyltoluene sulfonic acid）Reaction generation sulphur -4, the 10 diazacyclo dodecanes -3,11- of 1,7- bis- Diketone, then again through being reduced into sulphur -4, the 10 diazacyclo dodecanes of 1,7- bis-.

It is also commercially available for can be used for the more ether compounds of ring-type of the present invention.

When R is methylol, the more ether compounds of ring-type are methylol-crown ether；When it is O that n, which is 4, X, the hydroxyl Methyl-crown ether is methylol -18- crown ethers -6.

When n is 1-10, during one or more in X O, N and S, the like.

When R is phenyl, the structural formula of the phenyl is as follows：

Wherein, R₁For amino, sulfonic group, carboxyl, acyl group, ester group or phosphate；Y is 1-3.

In one embodiment, the R₁For formoxyl, X O, when n is 3, the more ether compounds of ring-type are first Acyl phenyl -15- crown ethers -5.

Work as R₁For amino, sulfonic group, carboxyl, acyl group, ester group or phosphate, n 1-10, X O, N or one kind in S or When a variety of, by that analogy.

The X hetero atoms in the more ether compounds of ring-type in the present invention can be coordinated with nickel ion, form stabilization The complex compound of more yuan of rings, the more ether compounds of ring-type and nickel ion easily precipitates under certain pH value, forms certain conversion Film.Also, by the lot of experiment validation of the present inventor, unexpected discovery, as n=2, the more ethers of ring-type The salt spray resistance for the conversion film that compound/modified graphene is formed with nickel ion and the stability of conversion film are best.Inventor recognizes For may the reason for be due to that, as n=2, the more ether compounds of ring-type are 12- crown ether -4, and the more ether compounds of ring-type can To form stable planar shape structure with nickel ion.It is simultaneously compound in the more ether compounds of ring-type and modified graphene progress Afterwards, certain hydrophobicity can be presented in the modified graphene again, now formed before this on lug nickel strap surface one layer it is compound Film, while one layer of hydrophobic structure is formed on the surface of composite membrane, improve the salt spray resistance and corrosion resisting property of lug nickel strap.And And with tab intermolecular active force can occur for amino on the crown ether and carboxyl, and improve passivating film and tab Cohesive.

Modified graphene

For the application modified graphene can be hydroxylating graphene, carboxylated graphene, sulfonic group graphite alkene, Amination graphene.

Modified graphene for the application is not particularly limited, and can is commercially available, can also be obtained by synthesis.

For example, the hydroxylating graphene can be prepared by the method for low temperature（With reference to Chinese patent 201110093909.2）.

For example, the carboxylated graphene can be prepared by solwution method（With reference to Chinese patent CN104445163 A）.

For example, the sulfonic group graphite alkene can be prepared by reducing process（With reference to Chinese patent CN102706934 A）.

For example, the amination graphene can be prepared by reducing process（With reference to Chinese patent CN104140094 A）.

In the present invention, the ratio of element sulphur is 5-10 at% in the sulfonic group graphite alkene, it is preferable that the element sulphur Ratio is 6-9 at%；The ratio of oxygen element is 5-35 at% in the hydroxylating graphene and carboxylated graphene, it is preferable that The oxygen element is 10-20 at%；The ratio of N element is 10-20at% in the amination graphene, it is preferable that the nitrogen is first The ratio of element is 15-20 at%.

In the present invention, the mol ratio of the more ether compounds of the ring-type and modified graphene is 35-15：1, it is preferable that institute The mol ratio for stating the more ether compounds of ring-type and modified graphene is 30-20：1.

Organic phospho acid

Organic phospho acid is the unsubstituted compound that 2 hydroxyls are combined on phosphoric acid atom.Organic phospho acid can and metal Strong chelating, organic phosphine sorrel is self-assembly of in metal surface, and the organic phosphonate film on Ni substrate surface has Very strong hydrophobicity.Heretofore described organic phospho acid is：ATMP, 1-hydroxy ethylidene-1,1-diphosphonic acid, ethylenediamine tetramethyl Pitching phosphonic acids, two methene phosphonate group glycine, hydroxyl, oneself pitches base di 2 ethylhexyl phosphonic acid, 2- phosphates -1,2,4- butane tricarboxylates and hydroxyl Asia second One kind in base di 2 ethylhexyl phosphonic acid

The 3d unoccupied orbitals lone pair electrons of the organic phospho acid can form stable complex with metal ion.

ATMP, also known as nitrilo trimethylene tri methylene phosphonic acid, i.e. ATMP, that is, have the function that antisludging agent, Property is stable in water simultaneously, not facile hydrolysis.

Ethylene diamine tetra methylene phosphonic acid, also known as ethylenediaminetetramethylene phosphonic acids, i.e. EDTMPA, molecular formula are C₆H₂₀O₁₂N₂P₄.EDTMPA has the ability of very strong chelated metal ions, and sequestering power exceeds well over EDTA and DTPA.

Two methene phosphonate group glycine, the also known as methylenephosphonic acid of glycine two, i.e. GDMP, both have the function that antisludging agent, Also there is good corrosion mitigating effect simultaneously.

Oneself pitches base di 2 ethylhexyl phosphonic acid to hydroxyl, its polyhydroxy chelation, changes the corrosion potential of passivation film, is advantageous to improve The decay resistance of passivation film.

2- phosphates -1,2,4- butane tricarboxylates, referred to as：PBTCA, alias：1,2,4- tricarboxylic acids -2- phosphonic acid butanes, PBTCA；Outward appearance：It is colourless to light yellow transparent liquid, molecular formula C₇H₁₁O₉P.Because it has the structure of phosphonic acids and carboxylic acid special Property, good scale inhibition and corrosion inhibition are made it have, better than conventional organic phospho acid, especially scale-inhibiting properties are much better than at high temperature Conventional organic phospho acid, the solubility of zinc can be improved, the oxidation susceptibility of chlorine-resistant is good, and compounding concertedness is good.

Hydroxy ethylene diphosphonic acid, also known as 1-hydroxy ethylidene-1,1-diphosphonic acid, abbreviation HEDP, molecular formula C₂H₈O₇P₂, HEDP is A kind of organic phosphine acids anti-incrustation corrosion inhibitor, energy various metals ion form stable complex compound, can dissolve the oxidation of metal surface Thing.

Phytic acid

Phytic acid is a kind of strong acid, and alias is phytic acid or inositol phosphate, has very strong sequestering power, its With 24 oxygen atoms, 12 phosphorus hydroxyls and 6 it is phosphate-based, can be formed in the range of wider pH with metal ion multiple Chelate ring, while phytic acid C-structure steric configuration is chair form type, 6 phosphates have 4 to be in same plane, thus are sent out in metal Easily one layer of fine and close unimolecule diaphragm is formed during raw complexation reaction in metal surface.Also, due in film layer contain hydroxyl and Phosphate isoreactivity group, can have an effect with organic coating, so the metal alloy treated by phytic acid, with coating Binding ability greatly improves.

Cetyl trimethylammonium bromide

Cetyl trimethylammonium bromide adds as wetting agent in the present invention, can soak alloy surface, make titanium-zirconium blunt Change film uniform and delicate, improve the compactness and corrosion resistance of passivating film.

Cetyl trimethylammonium bromide for the application is not particularly limited, and can is commercially available, can also be passed through conjunction Into obtaining.

It can be prepared in the application using any method well known by persons skilled in the art.

For example, trimethylamine aqueous solution is put into vaporizes kettle, it is heated to boiling, caused front three amine gas are after drying with third Ketone is absorbed, and trimethylamine acetone soln is generated in absorption tower, makes it into quaternized kettle.Then bromo 16 is added dropwise under agitation Alkane, the two mol ratio are 1.10 ︰ 1.30-40 DEG C is incubated during dropwise addition, insulated and stirred 1 hour again after drop finishes.Crystallisation by cooling, obtain Crude product, washed with acetone, dry, be drying to obtain.

In one embodiment, in parts by weight, the addition of the cetyl trimethylammonium bromide is 0.01- 0.05 parts by weight.

Cetyl trimethylammonium bromide is as a kind of citing of wetting agent in the present invention, and the wetting agent in the present invention is also Some other surfactants can be included, and be not limited only to cetyl trimethylammonium bromide.For example, it is also possible to including carboxylic Base betaine type amphoteric surfac-tant, alkyl polyoxyethylene ether, alkyl alcohol ethoxylates sodium sulphate, alkylsurfuric acid ammonium, alkane One or more in base phosphide ester triethanolamine and sodium alkyl sulfate.

BTA

BTA for the application is not particularly limited, and can is commercially available, can also be obtained by synthesis.

For example, BTA can be prepared as follows：Adjacent nitro phenylhydrazine is dissolved in organic solvent, there is ethanol in solvent Amine and catalyst, BTA is prepared by high-pressure hydrogenation.

BTA can also German YOUNGING oceans cherry production and sales.

In one embodiment, in parts by weight, the addition of the BTA is 0.01-0.05 parts by weight.

It is necessarily pointed out that the example above is served only for, the invention will be further described, it is impossible to is interpreted as to this The limitation of invention protection domain, professional and technical personnel in the field made according to the content of the invention described above some are nonessential Modifications and adaptations, still fall within protection scope of the present invention.

Film forming accelerating

Film forming accelerating is to shorten the Passivation Treatment time, improve a kind of material of quality of forming film, herein described film forming Accelerator is material and metal-chelator with oxidisability, can specifically include ammonium vanadate, strontium chloride, hydrofluoric acid, malonic acid, Oxalic acid, glutaric acid, malic acid, maleic acid, hydrogen peroxide, potassium permanganate, trisodium citrate, brown lead oxide, sodium hypochlorite, titanium dioxide Molybdenum, Potassiumiodate, potassium metaperiodate, permanganic acid, chloric acid, chlorous acid, perchloric acid, nitrous acid, ammonium nitrate, ammonium lactate, ammonium formate, acetic acid Ammonium, ammonium oxalate, tetrabutylammonium perchlorate, tetrabutyl ammonium nitrate, ammonium iodide, ammonium bromide, ATS (Ammonium thiosulphate), potassium peroxydisulfate, over cure Sour sodium, ammonium persulfate, ammonium dithionate, ammonium tartrate, ammonium citrate, fluorine nickel acid ammonium, ammonium metavanadate, ammonium hypophosphite, seven molybdic acids Ammonium, ammonium fluozirconate, ammonium acid fluoride, acid disodium calcium, diethylene triamine pentacetic acid (DTPA), chelating carboxylic acids, the second of hydroxyethyl vinyl diamines three Acid, 2,2- double [two（Carboxymethyl）Amine] diethyl ether, 1,2- diaminourea cyclohexanes tetraacethyl, hydroxyethyl diamine triacetic acid trisodium salt, Hydroxyethyl diamine tetraacethyl trisodium salt, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, oxalic acid, citric acid, 1,3,6- oneself Alkane tricarboxylic acids, tartaric acid, D-sorbite, 1,3- malonic acid, 1, 4- succinic acid, aminotriacetic acid, diethylene-triamine pentaacetic acid, Hydroxyethylethylene diamine tri-acetic acid, butene dioic acid, hydroxyl EDTA, dihydroxy glycine, the methene phosphonate of amino two, amino In three methene phosphonates, ethylene diamine tetra methylene phosphonic acid salt, diethylene triamine pentamethylene phosphonic salt, the methene phosphoric acid of hydroxyethyl diamine three One or more, it is preferable that the film forming accelerating be ammonium vanadate, strontium chloride, hydrofluoric acid, malonic acid, oxalic acid, glutaric acid, One or more in malic acid, maleic acid.The addition of the film forming accelerating is 0.1-2 parts by weight.

Inorganic acid

Herein described inorganic acid can include sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid, lactic acid, hydrofluoric acid, acetic acid, acid iodide, Telluric acid, osmic acid, rehenic acid, chromic acid, silicic acid, cobalt acid, vanadic acid, chloric acid, mangaic acid, molybdic acid, nickel acid, boric acid, plumbic acid, arsenic acid, metatitanic acid, carbon Acid, ferrous acid, wolframic acid, selenic acid, stannic acid, zincic acid, bromic acid, xenic acid, orthosilicic acid, former phosphoric acid, ortho-sulfuric acid, orthocarbonic acid, metasilicic acid, inclined boron Acid, metatitanic acid, inclined ferrous acid, metaphosphoric acid, metaphosphorous acid, metaarsenous acid, meta-aluminic acid, metavanadic acid, metaperiodic acid, tellurous acid, sulfurous Acid, phosphorous acid, chlorous acid, chromous acid, plumbous acid, arsenious acid, nitrous acid, stannous acid, Fluorine monohydroxide, hypoiodous acid, hypochlorous acid, secondary bromine Acid, hypophosphorous acid, sulphoxylic acid, perrhenic acid, permanganic acid, ferric acid, periodic acid, hyperbromic acid, pyrophosphoric acid, triphosphoric acid, pyrophosphorous acid, phosphorus Molybdic acid, phosphotungstic acid, thiosulfuric acid, chlorosulfonic acid, fluosulfonic acid, hydroiodic acid, hydrosulphuric acid, hydrobromic acid, fluoboric acid, fluosilicic acid, fluotitanic acid, One or more in fluorophosphoric acid, fluoplatinic acid, gold chloride, chloroplatinic acid, chloroplatinous acid, it is preferable that the inorganic acid is sulfuric acid, salt One or more in acid, phosphoric acid, perchloric acid, lactic acid, hydrofluoric acid, acetic acid.The nickel strap lug piece surface treatment inorganic acid is also Further comprise hydrofluoric acid.The effect of fluorine ion in passivating solution generally has two：First, under the conditions of film process, make place The element for managing complex fluorides in liquid keeps stable.Second, nickel alloy surfaces are etched, and make the nickel ion in solution to treatment fluid Keep stable.The addition of the inorganic acid is 0.003-0.007 parts by weight.

Other

Various additives can be contained within the scope without prejudice to the object of the present invention., can as the specific example of additive Enumerate Ce, La, Y or Nd rare-earth salts；Permanganate, chlorate, molybdate or (NH₄)₂S₂O₈Oxidant；Halide, sulfuric acid Salt, oxalates film forming agent；Acetate, glycol acid, citric acid, tartaric acid, malonic acid, formic acid, glutaric acid, propionic acid, butanedioic acid, Malic acid complexing agent, silica etc..

Embodiment

The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.

In addition, if without other explanations, raw materials used is all commercially available, and number used in following material is weight Part.

Table 1

B：Chromium trioxide

C：Inorganic acid

D：Film forming accelerating

E：Phytic acid

H：Water

I：Other：Cetyl trimethylammonium bromide, BTA, organic phospho acid

Table 2 is the composition of raw materials and dosage for preparing lug nickel strap passivation liquid composition（Parts by weight）

Method of testing

Hundred lattice are tested：According to《The scratch experiment of GBT9286-1998 paint and varnish paint films》Tested.Utilize hundred Lattice knife marks the square of 10 × 10 100 lattice, draws compartment away from for 1 mm, with 3M600 or 610 adhesive tape sticking in hundred lattice, Quick pull-up 3M adhesive tapes, test the quantity sticked by adhesive tape.

Result evaluation：Evaluated with ISO classification standards

0 grade：The edge of otch is completely smooth, and grid edge does not have any peeling；

1 grade：There is small pieces peeling in the intersection of otch, actual spoilage≤5% in Hua Ge areas；

2 grades：The edge and/or intersection of otch, which have, to be peeled off, and its area is more than 5%~15%；

3 grades：There are part peeling or whole large stretch of peeling along notching edge, or partial grid is peeled off by full wafer.The area of peeling More than 15%~35%；

4 grades：The large stretch of peeling/of notching edge or some grid parts are partly or entirely peeled off, and its area is more than Hua Ge areas 35%~65%；

5 grades：There is sheet of peeling paint at the edge of line and intersection, and the gross area that comes off is more than 65%.

Salt spray resistance is tested：According to national standard《GB/T10125-1997 metal cladding salt air corrosion experimental methods》Carry out Test.Salt spray test solution is configured to sodium chloride and distilled water, solution concentration is 5 at%, and pH value is between 6.5-7.5.Choosing It it is 35 ± 2 DEG C with the temperature in the salt spray test chamber of DCTC 1200P models, adjusting tank, salt fog settling amount is 1.0-2.0 ml / 80 cm²H, the base material after the passivation is placed in salt fog cabinet with level in 30-45 ° of direction, a base is checked per 24h Material.After 72h, experiment terminates, and the base material is spontaneously dried at ambient temperature, then cleaned with room temperature water, and dries up immediately, With the mm grids of 3 mm × 3 measurement sample rate of corrosion.

Droplet test：According to industrial standard HB 5056-77 are tested.By 3 g K₂Cr₂O₇It is dissolved in 25 ml HCl Testing liquid is configured in 75 ml distilled water.Testing liquid is dripped in nickel alloy specimen surface, solution penetrate into substrate surface with It interacts, and solution colour is changed into green from orange-yellow, and required time is the anti-corrosion time.

Boiling water test：Tested according to GB2530-2000, it is small to boil 5 in the deionized water more than or equal to 95 degree When.Criterion of acceptability：Coating surface should not have wrinkle, crackle, bubble, come off and change colour.

Penetration testing：

Nickel strap is made into nickel strap lug piece, the caking property tested between nickel strap lug piece and tab

Testing procedure：Lug piece is put into and fills electrolyte（Add moisture 1000ppm）Packaging film sack interior sealing it is good；Put Enter 85 DEG C of high temperature roasters, carry out aging in 24 hours；After aging, taking-up lug piece must be rinsed well and blown with clear water out of sack It is dry；The lug piece rinsed well is immersed in corrosion-free red penetrating fluid 1 hour；Rinsed well again with water, nickel strap lug piece Redfree penetrating fluid enters to be qualified between tab

Heat seal strength is tested：

Testing procedure：Nickel strap lug piece is put into and fills electrolyte（Add moisture 1000ppm water）Packaging film sack in it is close Seal；85 DEG C of high temperature roasters are put into, carry out aging in 24 hours；After aging, taking-up nickel strap lug piece must be rushed with water out of sack Wash clean simultaneously dries up；Nickel strap lug piece glue shoulder is eliminated；Clamp and do tensile test at the metal of nickel strap lug piece both ends, nickel strap can be obtained Lug piece and tab heat-sealing combined strength bination.

Table 3

Data above can be seen that compared with the product of the more ether compound/modified graphenes of ring-type, prepared by the present invention Lug nickel strap passivation liquid composition has higher salt spray resistance, stronger corrosion resisting property, thus provides the beneficial skill of the present invention Art effect.

Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention Feature example selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case Claim covers.

Claims

A kind of 1. lug nickel strap Surface treatment passivation solution, it is characterised in that by weight, including：

Water 100；

Chromium trioxide 0.01-0.3；

Inorganic acid 0.01-0.5；

Film forming accelerating 0.01-0.1；

The compound 0.01-1 of the more ether compounds of ring-type and modified graphene；

The structural formula of the more ether compounds of ring-type is：

Wherein, R is methylol, alkoxy, amino, carboxyl or ester group；

X is the one or more in O and N；

N=1-4；

The modified graphene is hydroxylating graphene, carboxylated graphene, sulfonic group graphite alkene or amination graphene；

The mol ratio of the more ether compounds of the ring-type and modified graphene is 35-15：1；

The inorganic acid is the one or more in sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid, hydrofluoric acid；

The film forming accelerating is in ammonium vanadate, strontium chloride, hydrofluoric acid, malonic acid, oxalic acid, glutaric acid, malic acid, maleic acid It is one or more of.
A kind of 2. lug nickel strap Surface treatment passivation solution according to claim 1, it is characterised in that the modified graphene For sulfonic group graphite alkene or hydroxylating graphene.
A kind of 3. lug nickel strap Surface treatment passivation solution according to claim 2, it is characterised in that the sulfonic group fossil The ratio of S elements is 5-10at% in black alkene；The ratio of O elements is 5- in the hydroxylating graphene and carboxylated graphene 15at%；The ratio of N element is 10-20at% in the amination graphene.
A kind of a kind of 4. metal surface of lug nickel strap Surface treatment passivation solution using as described in claim 1-3 any one Handling process, its step include：

(1) alkalescent liquid is used, removes the grease on lug nickel strap；

(2) alkalescent liquid in step (1) is cleaned up with distilled water；

(3) product in distilled water cleaning step (2) is used again, and is dried, and is immersed in the lug nickel strap Surface treatment passivation solution In；

(4) product in distilled water cleaning step (3), drying, cropping of products are used.