CN1891865A - Electrolytic phosphating process - Google Patents
Electrolytic phosphating process Download PDFInfo
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- CN1891865A CN1891865A CNA2006100886380A CN200610088638A CN1891865A CN 1891865 A CN1891865 A CN 1891865A CN A2006100886380 A CNA2006100886380 A CN A2006100886380A CN 200610088638 A CN200610088638 A CN 200610088638A CN 1891865 A CN1891865 A CN 1891865A
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- phosphoric acid
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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Abstract
This invention provides a phosphating process that can form a film suitable for a cold forging foundation within 60 seconds and preferably 30 seconds or less. The process uses a treatment bath that is formed of a phosphate ion solution (H<SUB>2</SUB>PO<SUB>4</SUB><SUP>-</SUP>+Zn<SUP>2+</SUP>), made by dissolving zinc in phosphoric acid, contains phosphoric acid (H<SUB>3</SUB>PO<SUB>4</SUB>), phosphate ions, zinc ions and nitrate ions, may contain at least one kind of metal ion selected from the group consisting of nickel ions, cobalt ions, copper ions, manganese ions and iron ions, and further contains 0.5 g/l or below of metal ions other than the film forming components. The process involves electrolytic treatment by applying a voltage between a metal as a positive electrode and a treated article as a negative electrode and forms a phosphate film on the surface of the treated article. The phosphate ion solution prepared by dissolving zinc in phosphoric acid (H<SUB>2</SUB>PO<SUB>4</SUB><SUP>-</SUP>+Zn<SUP>2+</SUP>) is a solution obtained by dissolving 8 parts by mass to a maximum dissolution concentration of zinc in 100 parts by mass of phosphoric acid.
Description
Technical field
The present invention relates to a kind of electrolytic phosphating process (electrolytic phosphating process) that is used on the product surface of handling forming mainly the phosphate layer that constitutes by zinc phosphate.More specifically, the present invention relates to a kind of on the surface of metallic substance with electric conductivity the film forming method of shape.
Background technology
Phosphating process is the treatment technology of a kind of based process that is used to apply steel, cold forging swabbing etc.Main phosphatization is a kind of non-electrolysis treatment at present, but in order to obtain more effective bonderizing, has checked multiple electrolytic phosphating process.
For example, Japanese unexamined patent publication No. open (Kokai) No.2000-234200 has described the prior art of electrolytic phosphating, and has described the basic skills of using electrode and power supply when implementing electrolytic phosphating.The disassociation state of bathing relevant acid is mentioned and handled to this reference, and described this bath and do not contain to dissociate and be higher than the acid (for example, nitric acid) of phosphoric acid.
In addition, Japanese unexamined patent publication No. open (Kokai) No.2002-322593 has described required measure concerning continuous enforcement electrolytic phosphating process, and has described intermediate product such as N that necessary removal forms in the intermediate reaction process
2O
4Gas.Yet these prior aries required 2 minutes or longer treatment time and not have obtains the method for electrolytic phosphating process that further shortening is used for the goods of complex-shaped processing.
On the other hand, electrolysis process is used for steel wire in the past, and has also studied the shortening treatment time.Open (Kokai) No.2000-80497 of Japanese unexamined patent publication No. discloses a kind of new method and a kind of new device, they be used on the steel wire of soft steel, high carbon steel and low alloy steel forming have better performance, as the phosphate layer of lubricated base, faster and do not produce any residue than prior art.In this reference, as shown in Figure 1, this wire rod of subsequent treatment in each step.This tupe is limited to wire rod.This material has the constant staff-like shape, and its shape is favourable for surperficial electrolysisization.The purpose of swabbing (phosphate layer) is drawn steel wire material (being processed into little filament diameter from big filament diameter) and is the plastic working that limits.This purpose and purpose fundamental difference of the present invention, that is, the goods of handling are handled as the cold forging of element with the complicated shape that comprises the convex-concave shape and demanding working accuracy and are not suitable for this goods.
On the other hand, be understandable that, Japanese Patent No.3,479,609 are intended to prevent residue and accelerate handle, and estimate not to be wire rod applicable to the element machining because embodiment has used test panel.Yet, because in this reference, in handling bath, added nitric acid (HNO
3), so bathing, this processing has been to use processing to bathe with the acid that is higher than the phosphoric acid dissociation degree.The fraction of coverage that this reference has also been described film is 50%, and when implementing the catholyte processing in the time of 10 seconds in the treatment soln of only being made up of phosphoric acid, nitric acid and zinc carbonate, this is also insufficient.In bathing, this processing adds Sodium Nitrite etc. to realize 100% fraction of coverage.In other words, in order to improve the film moulding, this reference needs a kind of not additive of the same soluble ion of separating out with phosphate layer that contains.
Summary of the invention
Because directly being connected with external direct current power supply by the goods that will handle, electrolytic phosphating process provides electrolytic energy (current/voltage), so the non-electrolysis treatment of the efficiency ratio prior art of electrolytic reaction is more satisfactory.Therefore, this method is compared with the non-electrolytic system of prior art and can be shortened the treatment time (electrolysis time).
In non-electrolytic system according to prior art, the time that phosphating process is required, being generally 120 seconds for processing coated base (coating foundation), is 5-10 minute for the processing cold forging with base (foundation for coldforging).
The cold forging base need be thicker than coated base film thickness, the treatment time also becomes longer.Therefore, the cold forging base need shorten the treatment time.An object of the present invention is to provide a kind of can be at 60 seconds or shorter, form the phosphating process of the film that is applicable to cold forging in preferred 30 seconds or shorter short period of time.In the time can shortening the treatment time, just can reduce the size of treatment facility, and can make up special machine.This minimizing and saving manpower and the energy etc. that reduce littler erection space, transmission line structure, intermediate raw material are effectively, and these are the targets that will reach in the practical application of element processing.
In open (Kokai) NO.2000-234200 of above-mentioned Japanese unexamined patent publication No., described a kind of by form the system of phosphatic film by the electrolysis of handling bath (solution).The present invention uses the system of this reference as the basis, and by further this system that develops, and form the film that mainly constitutes by zinc phosphate (crystal).
In order to achieve the above object, the invention provides following invention:
(1) a kind of electrolytic phosphating process, it uses a kind of like this processing to bathe, it is by forming by zinc being dissolved in the phosphate ion solution for preparing in the phosphoric acid that this processing is bathed, phosphoric acid, phosphate anion, zine ion and nitrate ion, can contain and be selected from nickel ion, cobalt ion, cupric ion, at least a metal ion in mn ion and the iron ion, also contain 0.5g/l or the metal ion except that described film-forming components still less, this technology comprise by apply that voltage carries out electrolysis treatment between as anodal metal and goods as the processing of negative pole and the surface of the goods handled on form the step of phosphate layer.
(2), wherein bathe and carry out electrolysis treatment by using its pH value to be adjusted into processing that 1.5-2.5 and its ORP (Eo+) remain on 90-450mV (silver/silver chloride electrode current potential) as (1) described electrolytic phosphating process.
(3) as (1) or (2) described electrolytic phosphating process, wherein said processing bathe the phosphoric acid that contains 15g/l at least and phosphate anion, at least 15g/l zine ion, the nitrate ion of 12.5g/l and 0-3g/l's is selected from least a metal ion in nickel ion, cobalt ion, cupric ion, mn ion and the iron ion at least.
(4) as each described electrolytic phosphating process in (1) to (3), wherein positive pole is selected from zinc or iron.
(5) as each described electrolytic phosphating process in (1) to (4), wherein after the goods by using described processing are implemented anode electrolysis as positive pole and zinc or iron as negative pole, the goods by using described processing are implemented catholyte as negative pole and zinc or iron as positive pole.
(6), wherein apply the voltage that is not higher than 6V by connecting direct supply as each described electrolytic phosphating process in (1) to (5).
(7) as each described electrolytic phosphating process in (1) to (6), wherein by zinc being dissolved in the described phosphate ion solution (H for preparing in the phosphoric acid
2PO
4 -+ Zn
2+) be by 8 mass parts to the zinc of maxima solubility is dissolved in the solution for preparing in the phosphoric acid of 100 mass parts.
(8) as each described electrolytic phosphating process in (1) to (7), wherein by zinc being dissolved in the described phosphate ion solution (H for preparing in the phosphoric acid
2PO
4 -+ Zn
2+) be to be dissolved in the solution for preparing in the phosphoric acid of 100 mass parts by zinc with the 15-25 mass parts.
(9) as each described electrolytic phosphating process in (1) to (8), wherein by zinc being dissolved in the phosphate ion solution (H for preparing in the phosphoric acid
2PO
4 -+ Zn
2+) be solution by dissolved oxygen zinc in phosphate ion solution, zinc hydroxide or metallic zinc preparation.
(10) as each described electrolytic phosphating process in (1) to (9), the phosphate ion solution (H during wherein said electrolysis treatment is bathed
2PO
4 -+ Zn
2+) and phosphoric acid (H
3PO
4) ratio [zinc is dissolved in phosphate ion solution (H wherein by relational expression
2PO
4 -+ Zn
2+)]/[zinc dissolving phosphate ion solution (H wherein
2PO
4 -+ Zn
2+)+phosphoric acid (H
3PO
4)] expression, be 0.4-1.
(11) as each described electrolytic phosphating process in (1) to (10), wherein said electrolysis treatment is bathed and is contained zinc and be dissolved in phosphate ion solution (H in the phosphoric acid
2PO
4 -+ Zn
2+), phosphoric acid (H
3PO
4) and zinc nitrate, and can contain the metal nitrate that constitutes by at least a nitrate that is selected from nickelous nitrate, Xiao Suangu, cupric nitrate and the manganous nitrate.
(12) as each described electrolytic phosphating process in (1) to (11), wherein at 1-18A/dm
2The catholyte current density under carry out electrolysis treatment on the surface of the goods of handling, to form phosphate layer.
(13), wherein do not exist any electric current that hinders in carrying out forming phosphate layer on the surface of electrolysis treatment with the goods handled under the condition of mobile obstacle between positive pole and negative pole as each described electrolytic phosphating process in (1) to (12).
(14) as each described electrolytic phosphating process in (1) to (13), wherein by with the electrolysis treatment time set being 60 seconds or the shorter lithoform that forms.
(15) as each defined electrolytic phosphating process in (1) to (14), it applies two or more voltage and currents wherein to utilize two or more power supplys and electrode pair according to the position of the goods of handling.
The present invention can shorten the phosphorization treatment time as the element of the goods of handling.Shorten phosphorization treatment time and allow little erection space and series connection (transmission line) structure.In other words, because be independent of front and back operation installation, so element is stored in the front and back of treatment unit according to the big bonderizing device of prior art.Yet, because can reduce size, so can the bonderizing device be installed near the front and back installation steps.Therefore, storage element before and after the bonderizing device can be eliminated, and the manpower of conveying and reservoir need can be omitted.
The invention enables installation dimension to reduce and temperature reduces, thereby reduced the usage quantity of the energy that is used to heat etc.Because the present invention does not cause unnecessary reaction, so the present invention can prevent the generation of by product (residue) and the amount of minimizing chemical reagent.
Effect of the present invention helps the improvement of gained film.This relatively can obviously find out with the film of the comparative example 4 that occurs subsequently from the embodiment 7 of appearance subsequently and 8 film.In embodiment 7 and 8, be formed uniformly tiny zinc phosphate crystal from the teeth outwards, but formed the film of macrocrystal in the comparative example 4 cursorily.The difference of this surface appearance has reflected the difference of lubricated active principle deposition.In other words, the zinc phosphate crystal is favourable to the formation of lubricated active principle uniformly, thereby effective to cold ductility.
Description of drawings
Fig. 1 is the synoptic diagram of the present invention basis phosphating process system;
Fig. 2 shows the formation state of the film in embodiment and the comparative example;
Fig. 3 shows the formation state of the film in embodiment and the comparative example;
Fig. 4 shows mobile electric current when applying 3V voltage between zinc electrode and test block in catholyte;
Fig. 5 shows employed component shape in embodiment 7,8 and comparative example 4, and wherein forming processing is structure shown in Figure 6 with its shape from alteration of form shown in Figure 5;
Fig. 6 shows element shown in Figure 5 gear-like structure after cold forging rolls;
Fig. 7 is the surface topography map of the phosphate layer of formation among the embodiment 7;
Fig. 8 is the surface topography map of the phosphate layer of formation among the embodiment 8;
Fig. 9 is the surface topography map of the phosphate layer of formation in the comparative example 4; With
Figure 10 shows the element B (tube element with cylinder hollow part) that is used for phosphating process in embodiment 12.
Embodiment
In electrolytic phosphating process according to the present invention, handling bath is by using zinc to be dissolved in phosphoric acid (H
3PO
4) the middle phosphate ion solution (H for preparing
2PO
4 -+ Zn
2+) preparation.This solution phosphoric acid (H
3PO
4) and phosphate anion, zine ion and nitrate ion, can also contain at least a metal ion that is selected from nickel ion, cobalt ion, cupric ion, mn ion and the iron ion.The content of the metal ion except that film-forming components is not more than 0.5g/l.By using metal as positive pole and use the goods handled as negative pole and apply voltage enforcement electrolysis treatment and on the surface of the goods of handling, form phosphate layer.
For example, electrolysis treatment according to the present invention is bathed the phosphate ion solution (H of solving zinc in the phosphoric acid suitably
2PO
4 -+ Zn
2+), phosphoric acid (H
3PO
4) and zinc nitrate and the metal nitrate that constitutes by at least a metal that is selected from nickel, cobalt, copper and the manganese.For iron, iron is the same with zinc preferably to be provided by the solution that dissolved ferric iron is prepared in phosphoric acid.Iron nitrate is unwanted, because it is with trivalent iron salt (Fe
3+), (Fe (NO
3)
3Form exist, thereby form residue.
Sodium and potassium are the examples of the metal ion except film-forming components, and the present invention handles bath and do not contain these metal ions (not being higher than 0.5g/l) substantially.
The main element that constitutes the electrolytic phosphating process system is " handle and bathe " and " electrolysis process ".In order to shorten the film formation time in electrolytic phosphating process, realize electrolytic phosphating process of the present invention by check at length " processing is bathed " and " electrolysis process ".
I) check-1 of " handling and bathing ":
The control of phosphoric acid disassociation condition
It is a kind of like this phenomenon (reaction) that zinc phosphate is separated out, wherein phosphoric acid enter with
The disassociation state of expression is with zine ion (Zn
2+) coupling and formation zinc phosphate (Zn
3(PO
4)
2 Reaction process in, solid), or the solution becomes alkalize solubilised state acidity becomes high to the left, but forms phosphate compounds (crystal: to the right.The zinc phosphate of the form membrane that electrolysis treatment forms be make the electrolysis of solutions that contains solubilised state phosphoric acid, phosphate anion and zine ion with the disassociation that promotes phosphoric acid (that is, with
Represent), and make grey sour zinc crystal (Zn
3(PO
4)
2) separate out with the form of film on the surface of the goods of handling.Therefore, bonderizing is bathed and is necessary for solubilised state, and the disassociation of phosphoric acid must be limited to H
3PO
4→ H
2PO
4 -Scope.
Electrolysis treatment is bathed preferably transparent.In order to promote phosphoric acid salt to separate out, must promote to handle the disassociation state of phosphoric acid in bathing.Can pass through zinc oxide (ZnO), zinc hydroxide (Zn (OH)
2) or metallic zinc (Zn) be dissolved in H
3PO
4Promote the disassociation state of phosphoric acid in the solution.In other words, can promote and control the disassociation of phosphoric acid by following reaction formula.
Above-mentioned reaction formula (1)-(3) can passed through by weight in the H of 100 mass parts
3PO
4Middle dissolving 8 mass parts are to the Zn of maximum concentration of ordinary dissolution
2+Solution in carry out basicly stablely.The phosphate ion solution of preferred dissolution zinc contains the zinc of 15-25 mass parts in the phosphoric acid of 100 mass parts.In the present invention, for simplicity, can be with H in 100 mass parts
3PO
4Middle dissolving 8 mass parts are to the Zn of maximum concentration of ordinary dissolution
2+Solution be called " by H
2PO
4 -: 100 weight parts+Zn
2+: the key element component that 25 weight parts are formed ".Can use only by " H like this, in the present invention
3PO
4" the key element component formed and by " H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts " the key element component formed." H
3PO
4" component is a formation component of the prior art, and " H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts " be the formation component that the present invention proposes.In other words, be clear that pure " H
3PO
4" and " H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts " between the disassociation state of phosphate ion be different.
As mentioned above, the present invention uses two kinds of components, i.e. [H
3PO
4] and [H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts] as constituting the phosphoric acid components that bonderizing is bathed.The present invention proposes ratio [H
2PO
4-: 100 weight parts+Zn
2+: 25 weight parts]/[H
3PO
4]+[H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts] (weight ratio), and it is defined as [zinc dissolving phosphoric acid salt ion solution is than (zincdissolvingphosphateionratio)] (be also referred to as [Zn25% dissolving phosphoric acid salt ion solution than]).
Therefore, the solution of [zinc dissolving phosphoric acid salt ion solution ratio]=1 represents to constitute the phosphoric acid of processing bath fully by [H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts] form.The solution of [zinc dissolving phosphoric acid salt ion solution than]=0.5 represents to constitute that to handle 50% of the phosphoric acid of bathing be [H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts], remaining by pure [H
3PO
4] form.The solution of [zinc dissolving phosphoric acid salt ion solution ratio]=0 represents to constitute the phosphoric acid of processing bath only by pure [H
3PO
4] form.
Zinc dissolving phosphoric acid salt ion solution ratio during electrolysis treatment of the present invention is bathed, the i.e. [phosphate ion solution (H of solving zinc in phosphate ion solution
2PO
4 -+ Zn
2+)]/[phosphate ion solution (H of solving zinc in phosphate ion solution
2PO
4 -+ Zn
2+)+phosphoric acid (H
3PO
4)] be suitably 0.4-1.
The processing bath that [zinc dissolving phosphoric acid salt ion solution ratio] is little is pure [H
3PO
4] bathe than big processing, in this solution, need big (disassociation) energy to promote H
3PO
4Dehydrogenation.On the contrary, the processing bath that [zinc dissolving phosphoric acid salt ion solution ratio] is big is [H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts] to bathe than big processing, it is than the former easier promotion H
3PO
4Dehydrogenation.Therefore, back one solution is than the former the easier zinc phosphate crystal of separating out, and with still less electrolytic energy.
By the way, the disassociation condition of phosphoric acid is also relevant with the hydrogen ion concentration (pH) of handle bathing, and therefore most suitably being to use pH is that the processing of 1.5-2.5 is bathed and carried out electrolysis treatment.
Ii) " check that processing is bathed "-2:
Observe the outer soluble metal ion (iron ion) that dezincifies in the phosphoric acid
Iron be a kind of in phosphate ion solution soluble metal and in phosphoric acid, show the performance similar to zinc.Iron is the possibility from the material dissolves of handling is bathed to processing as material of handling and existence normally.Therefore, must understand the performance of iron ion.
Iron can only be dissolved in the phosphoric acid by metallic state.Situation is as follows.
In formula (4), Fe can fully be dissolved as Fe
2+: by quality ratio, Fe is at 100 mass parts H
3PO
4In can be dissolved to up to 20 mass parts.
Different with zinc, iron can not be dissolved in the phosphoric acid by the state of oxide compound and oxyhydroxide basically.Therefore, the dissolving of the oxide compound of iron and oxyhydroxide is influenced by following formula:
Formula (5) is also pointed out Fe
2+Be oxidized to Fe
2+Oxygen in the standard air promotes this reaction usually.Under this standard conditions, iron protoxide (FeO) and ferrous hydroxide (Fe (OH)
2) influenced and oxidized by oxygen, respectively with Fe
2O
3And Fe (OH)
3Form exist.The oxide compound of this iron can not be dissolved in the phosphoric acid.
Relation in the formula (5) also influences the stability that bonderizing is bathed.In other words, the Fe ion has Fe in bonderizing is bathed
2+→ Fe
3+Variation tendency.Yet, because Fe
3+Solubleness be far smaller than Fe
3+Solubleness, in handle bathing along with this transformation (Fe
2+→ Fe
3+) formed a large amount of residues.This phenomenon is never desirable in bonderizing is bathed.
Therefore, be to form in purpose and contain with zinc phosphate the present invention as the film of main component, bonderizing is bathed the Fe ion that can contain and is provided by the solution that is dissolved in the phosphoric acid, and preferably limits meltage (concentration).Meltage is about 3g/l.When this concentration was higher, method of the present invention had formed a large amount of undesirable residues in handling bath.
For the metal beyond the Fe, Mn for example, with regard to maximum weight than with regard to, with H
3PO
4: 100 weight part meters, Mn
2+: 0.5 weight part.Under this concentration, be difficult to form the manganous phosphate film.Among the present invention, can contain the metal ion that 0-2g/l is insoluble to other metal of phosphate ion solution, as nickel, cobalt or copper.
The iii) check of [electrolysis process]-1
The qualification and the control of the reaction except that the phosphoric acid disassociation
Forming film by the phosphoric acid disassociation is to be restricted to [H by the situation that will handle phosphoric acid in the bath
3PO
4→ H
2PO
4 -] scope, and promote [H
3PO
4→ H
2PO
4 -] → PO
4 3-Film carries out thereby with forming on product surface by electrolytic dissociation.In other words, PO
4 3-With Zn ion (Zn
2+) at the coupling of the surface of negative pole (goods of handling), zinc phosphate (Zn
3(PO
4)
2) form of crystal formation film.
The most important thing is to suppress other reaction (such as the such reaction of water electrolysis).When taking place, form the reaction product (condition is to react as long as need just to allow control) except that phosphoric acid salt except that other reaction of phosphoric acid disassociation.
Can under the voltage that is lower than water electrolysis voltage, carry out the disassociation of phosphoric acid.More particularly, can promote the disassociation of phosphoric acid, but electrolysis is restricted to 6V or lower impressed voltage (detailed content is with reference to open (Kokai) NO.2004-52058 of Japanese unexamined patent publication No.).The processing that the phosphate ion solution that the special use of the present invention obtains by solving zinc in phosphoric acid prepares is bathed and is promoted phosphoric acid to dissociate in advance.Therefore, the present invention can easily make the phosphoric acid disassociation be separated out up to coating under 6V or lower voltage.
The iv) check of [electrolysis process]-2
Reduce measure---the electrode materials of electrode surface direct current resistance
In order to obtain film at short notice by electrolytic treatment system, must be by big as far as possible electric current under 6V or lower voltage.For bigger electric current is passed through, a) must be [surface-area that when material is identical, increases electrode], and b) [reducing the direct current resistance of electrode surface].Measure is clearly to everyone a).Measure b) needs to select to be applicable to electrode materials of the present invention.In other words, selecting zinc or iron is suitable as the anode electrode material.Especially, zinc is a kind of big dissolving power that has in phosphoric acid, easy dissolved metal under low voltage, thereby make it can pass through big electric current.
The iv) check of [electrolysis process]-3
Reduce the measure of the goods direct current resistance of handling---adjust and handle the Eo+ (ORP) of bathing
Because under the voltage (electrolysis voltage) of the hydrolysis that water electrolysis does not take place, carry out electrolysis treatment of the present invention, so the flowing of electric current on the product surface that must consider to handle.Eo+ (ORP) and metallic substance dissolved are observed and can be obtained by Pourbaix figure.Though Pourbaix figure is not based on kinetics, can infer Eo+ to be arranged on corrosion area (current potential) more favourable than being arranged on passive area.The metallic substance of the present invention imagination is iron and steel (comprising steel alloy), aluminium, copper etc.These metals are corroded under the Eo+ of 300-660mV (hydrogen electrode current potential).Adjust scope so far when handling the oxidation-reduction voltage of bathing, can reduce the direct current resistance on workpiece (goods of handling) surface and can flow through big electric current.Therefore it is effective that the Eo+ that will handle bath transfers to 90-450mV (silver/silver chloride electrode current potential) (300-660mV (hydrogen electrode current potential)).
The preferred embodiments of the present invention will be set forth hereinafter.Fig. 1 is the synoptic diagram of the present invention basis phosphatization treatment system.
Use following A or B to bathe as handling.
A: this is handled to bathe to use and constitutes two kinds of phosphate compositions that bonderizing is bathed, that is, and and [H
3PO
4] and [H
2PO
4 --: 100 weight parts+Zn
2+: 25 weight parts].The present invention has pointed out to handle the disassociation state of phosphoric acid in the bath and use dissolving phosphoric acid salt ion solution to bathe than the processing in the scope of 0.4-1, and wherein dissolving phosphoric acid salt ion solution ratio is by [H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts]/[H
3PO
4]+[H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts] (weight ratio) expression.This handles to bathe and does not comprise the composition of following dissolved ferric iron in phosphoric acid.
This processing is bathed and is comprised the phosphate anion of 15g/l at least, at least the zine ion of 15g/l, at least the metal ion that is selected from nickel, cobalt, copper, chromium and manganese of the nitrate ion of 12.5g/l, 0-2g/l is no more than the dissolved iron ion from the goods handled and electrode of 3g/l and is no more than the dissolved ions except that above-mentioned ion of 0.5g/l.
B: by will [zinc-dissolving phosphoric acid salt ion solution than] being no more than the processing bath that prepare in the solution of 3g/l for the solution of 0.4-1 joins iron is dissolved in the phosphoric acid in advance to concentration.
This processing bathe the phosphate anion that contains 15g/l at least, at least 15g/l zine ion, at least 12.5g/l nitrate ion, 0-2g/l be selected from metal ion in nickel, cobalt, copper, chromium and the manganese, dissolved iron ion and be no more than the dissolved ions except that above-mentioned ion of 0.5g/l from the goods handled and electrode.
By implement anode electrolysis then catholyte carry out electrolysis treatment substantially.In other words, by use the goods handled as positive pole and zinc or iron as negative pole enforcement anode electrolysis after, preferably the goods of handling by use carry out catholyte as negative pole and zinc or iron as positive pole.According to circumstances can omit anode electrolysis.
By using a supporting electrode as negative pole, the goods of handling carry out anode electrolysis as positive pole.Supporting electrode generally uses iron.General by using main electrode (zinc) as anodal, the goods of handling carry out catholyte as negative pole.Impressed voltage is preferably 6V or lower in these two kinds of electrolysis.Preferably by the catholyte current density is arranged on 1-18A/dm
2Scope in, and on the surface of the goods of handling, form phosphate layer and carry out electrolysis treatment.In this article, electrolysis treatment is not exist under the state that hinders electric current mobile obstacle between positive pole and the negative pole carries out, and forms phosphate layer on the surface of the goods of handling.
Among the present invention, the time of electrolysis treatment can be 60 seconds or shorter, but can be not limited to the aforementioned time according to the condition and the purpose prolongation of electrolysis treatment.
In order to form phosphate layer by the present invention, two or more power supplys and electrode can be used for goods of handling, the position of the goods of crossing according to same treatment applies two or more different voltage and currents and form phosphate layer on the surface as the goods of the embodiment 12 described processing that occur later.
Preferably, be set in the scope of 1.5-2.5 handling the pH value of bathing, ORP is set in 90-450mV (silver/silver chloride electrode current potential) (300-660mV (hydrogen electrode current potential)).
To describe the present invention but the present invention is not limited thereto by embodiment and comparative example.
Embodiment 1-6 and comparative example 1-3:
Handle and do not comprise Fe ionic embodiment in the bath:
The test block that uses among embodiment 1-6 and the comparative example 1-3 is mild steel material (the SPCC material: cold-rolled steel sheet) that is of a size of 50mm * 25mm * 1mm (t).After the oil removing, all immerse each test block in the titanium type colloidal solution and carry out phosphating process to form film.Carry out electrolytic phosphating process by anodizing (7 seconds) → cathode treatment (23 seconds).The electrolysis treatment time is 30 seconds, and is shorter than the time of the prior art.
Table 1 has been listed the condition and the result thereof of embodiment and comparative example enforcement.In other words, table 1 listed pH value (hydrogen ion concentration) that composition, electrolytic condition, processing that bonderizing bathes bathe, ORP (Eo+), temperature, total acidity (by bathe with this processings of 0.1N caustic soda neutralization titration 10ml to the color of the phenolphthalein that is used as indicator be the index that milliliter numerical table of the required 0.1N caustic soda of redness shows) and coating formation condition.Processing in the table 1 is bathed and is not allowed to have a mind to comprise the Fe ion solution.
By the way, electrolysis treatment is a kind of system, wherein makes voltage be increased to predetermined voltage and electric current is flowed between electrode and the goods handled.The electrode materials that is used for electrolysis treatment is listed in table 2, is zinc and iron.
Electrolysis voltage of the present invention is 6V or lower, and the peak voltage among embodiment 1-6 and the comparative example 1-3 is 3V.The 3V voltage that adds is for suppressing the voltage of water decomposition.
Table 1
| Comparative example 1 | Embodiment 1 | Embodiment 2 | Comparative example 2 | Embodiment 3 | Embodiment 4 | Comparative example 3 | Embodiment 5 | Embodiment 6 | |||
| 13 | 23 | 15 | 14 | 6 | 16 | 19 | 7 | 17 | |||
| Handle to bathe and form | The disassociation index of phosphoric acid | [H 3PO 4(100)+phosphoric acid among the Zn (25)]/[H 3PO 4(100)+phosphoric acid among the Zn (25)]+H 3PO 4In phosphoric acid] | 0 | 0.5 | 1 | 0 | 0.67 | 1 | 0 | 0.67 | 1 |
| Phosphoric acid concentration | Total phosphoric acid concentration: g/l | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| H 3PO 4(100)+phosphoric acid concentration among the Zn (25): g/l | 0 | 15 | 30 | 0 | 20 | 30 | 0 | 20 | 30 | ||
| H 3PO 4In phosphoric acid concentration: g/l | 30 | 15 | 0 | 30 | 10 | 0 | 30 | 10 | 0 | ||
| Zinc concentration | Total zinc concentration: g/l | 15 | 15 | 15 | 20 | 20 | 20 | 30 | 30 | 30 | |
| H 3PO 4(100)+Zn (25) in the concentration of Zn: g/l | 0 | 3.75 | 7.7 | 0 | 5 | 7.7 | 0 | 5 | 7.7 | ||
| The concentration of Zn: g/l among the nitric acid Zn | 15 | 11.25 | 7.3 | 20 | 15 | 12.3 | 30 | 25 | 22.3 | ||
| Nitrate ion concentration | Total NO 3Concentration: g/l | 31 | 23.5 | 16 | 41 | 31 | 26 | 61 | 51 | 46 | |
| NO among the phosphoric acid Zn 3 -Concentration: g/l | 30 | 22.5 | 15 | 40 | 30 | 25 | 60 | 50 | 45 | ||
| NO in the phosphoric acid 3 -Concentration: g/l | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | ||
| Nickel concentration | The concentration of Ni: g/l among the nitric acid Ni | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| Electrolytic condition | Anode electrolysis | Voltage | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Electric current: A/ work | -0.2 | -0.2 | 0.6 | -0.2 | -0.2 | 0.6 | -0.2 | -0.2 | -0.2 | ||
| Time | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | ||
| Zn: catholyte | Voltage | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| Electric current :/A work | l.3 | 1.7 | 1.1 | 1.4 | 1.8 | 1.3 | 32 | 1.7 | 2 | ||
| Time | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | ||
| Electric current: A/dm 2 | 5.2 | 6.8 | 4.4 | 5.6 | 72 | 52 | 12.8 | 6.8 | 8 | ||
| Iron, catholyte | Voltage | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | |
| Electric current: A/ work | -0.2 | -0.2 | -0.2 | -0.2 | -0.2 | -0.2 | -0.2 | -0.2 | -0.2 | ||
| Time | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | ||
| Handle the bath condition | PH | 1.48 | 1.59 | 1.97 | 1.51 | 1.67 | 1.97 | 1.39 | 1.66 | 2.02 | |
| ORP:mV (silver/silver chloride electrode current potential) | 425 | 265 | 262 | 376 | 450 | 233 | 317 | 42.5 | 211 | ||
| Temperature: ℃ | 30-35 | 30-35 | 30-35 | 30-35 | 30-35 | 30-35 | 30-35 | 30-35 | 30-35 | ||
| Total acidity: pt | 70 | 78 | 84 | 72 | 76 | 80 | 95 | 84 | 80 | ||
| Form film | Fraction of coverage: % | 70 | 100 | 100 | 100 | 100 | 100 | 80 | 100 | 100 | |
| Thickness: μ m | 12 | 5 | 8.8 | 1.8 | 4.5 | 11.8 | 5 | 5.4 | 12 |
Fig. 2 shows the formation situation of film.Though this figure explanation is not always to form phosphate layer reliably in comparative example, has formed film in an embodiment in 30 seconds short period of time reliably.
The film that Fig. 3 shows with regard to thickness forms situation.Measure thickness by electromagnetism film thickness gauge LE-300J by K.K.Ketto Kagaku Kenkyusho preparation.Film forms excellence in an embodiment, although very poor in comparative example.Thickness in the comparative example 3 is 5 μ m, and this thickness is the thickness that film forms part.In comparative example 3, only on 80% surface, formed film.
Fig. 4 shows mobile electric current when applying 3V voltage in the catholyte process between zinc electrode and test block contrastively.This figure shows that electric current rises with the zinc and the increase of the ratio of phosphoric acid.The formation of the current density maximum in the comparative example 3 but film is also unreliable.In order to implement the formation of film reliably, the more important thing is the disassociation state of phosphoric acid in the control solution than current density.
The above results shows the inventive method and handles bath is effective for form film in 30 seconds short period of time.
Comparative example 4 representatives are according to the treatment process of prior art, and it is a kind of non-electrolytic system.Embodiment 7 and 8 is the processing under electrolysis treatment the same terms the time.Table 2 shows the main points of implementing this processing.
Table 2
| Embodiment 7 | Embodiment 8 | Compare 4 non-electrolysis treatment | |||
| Handle bath composition | The height of phosphoric acid is separated index | [H 3PO 4(100)+phosphoric acid among the Zn (25)]/[H 3PO 4(100)+phosphoric acid among the Zn (25)]+[H 3PO 4In phosphoric acid] | 0.43 | 0.43 | Palbond 3684X (the shaping chemical reagent that Nippon Parkerizing Co., Ltd produces) |
| Phosphoric acid concentration | Total phosphoric acid concentration: g/l | 42 | 42 | ||
| H 3PO 4(100)+phosphoric acid concentration among the Zn (25): g/l | 18 | 18 | |||
| H 3PO 4In phosphoric acid concentration: g/l | 24 | 24 | |||
| Zinc concentration | Total zinc concentration: g/l | 22.5 | 22.5 | ||
| H 3PO 4(100)+Zn (25) in the concentration of Zn: g/l | 4.5 | 4.5 | |||
| The concentration of Zn: g/l among the nitric acid Zn | 18 | 18 | |||
| The high sub-concentration of nitrate radical | Total NO 3 -Concentration: g/l | 38 | 38 | ||
| NO among the nitric acid Zn 3 -Concentration: g/l | 36 | 36 | |||
| NO among the nitric acid Ni 3 -Concentration: g/l | 2 | 2 | |||
| Nickel concentration | The concentration of Ni: g/l among the nitric acid Ni | 1 | 1 | ||
| Electrolytic condition | Anode electrolysis | Voltage | 1.5 | 1.5 | No electrolysis, the treatment time: 600 seconds |
| Electric current: A/ work | 0.2 | 0.2 | |||
| Time | Raise and kept 2 seconds in 3 seconds | Raise and kept 6 seconds in 4 seconds | |||
| Zn: catholyte | Voltage | 3 | 3 | ||
| Electric current: A/ work | 1.4 | 1.4 | |||
| Time | Raise and kept 7 seconds in 3 seconds | Raise and kept 16 seconds in 4 seconds | |||
| Electric current: A/dm 2 | 5.2 | 52 | |||
| Iron: catholyte | Voltage | 2 | 2 | ||
| Electric current: A/ work | -0.2 | -0.2 | |||
| Time | Raise and kept 7 seconds in 3 seconds | Raise and kept 16 seconds in 4 seconds | |||
| Handle the bath condition | pH | 1.99 | 2 | - | |
| ORP:mV (silver/silver oxide electrode current potential) | 400 | 355 | - | ||
| Temperature: ℃ | 32 | 32 | 80 | ||
| Total acidity: pt | 82 | 82 | 43 | ||
| Cocatalyst concentration | - | - | 3 | ||
| The film that forms | Fraction of coverage: % | 100 | 100 | 100 | |
| Lubricated active principle: deposition weight: g/m 2 | 4.5 | 4.4 | 1.5 | ||
| Phosphate layer: deposition weight: g/m 2 | 6.7 | 10 | 4 | ||
| The pressing machinery processibility | Cold forging rolls: processing load average value: ton | 67 | 67 | 68 |
Table 7-9 shows the pattern of the phosphate layer of formation.Among Fig. 7 is embodiment 7, and Fig. 8 is embodiment 8, and Fig. 9 is a comparative example 4.
The goods of handling are handled by following steps: oil removing → surface modulation → bonderizing → swabbing (be immersed in 80 ℃ the sodium stearate 3 minutes) (omitting surface modulation in the comparative example 4).
Difference in actual treatment between embodiment and the comparative example is tangible.Treatment time in the comparative example is 10 minutes, and is 15 seconds and 30 seconds among the embodiment.The pattern of the film that forms is also obviously different between embodiment and comparative example.Film close among the embodiment and zinc phosphate crystal are formed uniformly on the product surface of handling.Therefore, the base material steel does not directly expose.On the contrary, the phosphate layer in the comparative example (prior art) is made of thick zinc phosphate crystal.Therefore, can observe by SEM, use method of the present invention, film has covered iron surface reliably, but uses art methods, and film but makes the base material steel expose.
Lubricated (processing) membrane interaction also is shaped on zinc phosphate.Therefore, importantly whether the steel surface is covered reliably by having zinc phosphate crystalline film.When the surface was covered reliably by the zinc phosphate crystal, swabbing was bathed (stearic acid Na) and can directly do not contacted with the generation of steel surface.Yet when film was imperfect, swabbing was bathed (stearic acid Na) and can directly be contacted with the generation of steel surface.This has hindered the effect of emollient component and has formed incomplete lubricant film.In other words, when steel constituent (as iron ion etc.) be dissolved in swabbing bathe in the time, iron ion condenses lubricant film (homodisperse soap), and hinders its even formation.In other words, formed the film that comprises the component of condensing.Lubricant film (soap) should homodisperse, exists with the form of film, therefore works effectively.Therefore, it is important to form sufficient lithoform, the present invention has realized this target.
Pattern by the film that forms can confirm to reflect the embodiment of above-mentioned condition and the difference between the comparative example.As shown in table 2 be evenly to form in the lubricated active principle of lubricant film component, the mass ratio of embodiment/comparative example is 3/1, embodiment greater than and be better than comparative example.Embodiment 7 is different with the zinc phosphate deposition of embodiment 8, and lubricated active principle remains on identical level substantially.This is surmisable, because in embodiment 7 and 8, as confirming that the surface covered reliably by lithoform by SEM.
By the way, the lubricated active principle of listing in the meter 2 by the following method: form in the technology film dip lubrication handled at lubricant film and bathe in (sodium stearate bath), remove by hand the solids component of separating out from the teeth outwards (solids component as with the sodium stearate of membrane sepn), and measure and form evenly and the component of successive film.By film being dipped in 70 ℃ of ebullient Virahols 15-20 minute, measuring the weight of soaking the goods that pre-process and post-process crosses and also convert them to unit surface (m
2) value carry out the measurement of film.Being applied to by the film forming method of non-electrolysis process shape of this measuring method of lubricant film (reaction soap) and prior art is different.The difference of lubricant film formation method has reflected such fact, and non-electrolytic processing method promptly of the prior art can not form complete lithoform, but method of the present invention can form complete lithoform.
Zinc phosphate crystalline deposition is important, but has confirmed that the difference on the film formation condition also is important.Roll load for cold forging, embodiment and comparative example do not have difference, but can confirm, from the difference of film properties aspect, embodiment is more favourable.
X-ray diffraction is the result show, embodiment 7 and 8 and the film of comparative example 4 comprise the zinc phosphate crystal, though this does not illustrate in the drawings.
Embodiment 9 and comparative example 5 and 6:
In embodiment 9 and comparative example 5 and 6 be by with dissolved ferric iron in phosphoric acid, rather than zinc is dissolved in the phosphoric acid situation of the dissociation degree of regulating phosphoric acid.
Table 3 has provided the summary of embodiment.In embodiment 9 and comparative example 5 and 6, by [H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts]/[H
3PO
4]+[H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts] [the Zn 25% dissolving phosphoric acid salt ion solution than] of (mass ratio) expression all is zero.Identical among [Zn 25% dissolving phosphoric acid salt ion solution than]=0 and the comparative example 1-3.Yet, by being novel in the dissociation degree of dissolved ferric iron being regulated phosphoric acid in phosphoric acid.
Table 3
| Embodiment 10 | Embodiment 11 | Comparative example 5 | Comparative example 6 | Embodiment 9 | |||
| 24 | 25 | 26 | 27 | 28 | |||
| Handle to bathe and form | The disassociation index of phosphoric acid | [H 3PO 4(100) the phosphoric acid/[H among the Zn (25) 3PO 4(100)+phosphoric acid of Zn (25)]+[H 3PO 4In phosphoric acid] | 0.67 | 0.67 | 0.67 | 0 | 0 |
| Phosphoric acid concentration | Total phosphoric acid concentration: g/l | 30 | 30 | 30 | 30 | 30 | |
| H 3PO 4(100)+phosphoric acid concentration among the Zn (25): g/l | 20 | 20 | 0 | 0 | 0 | ||
| Phosphate anion in phosphoric acid+iron | 10 | 10 | 30 | 15 | 15 | ||
| H 3PO 4In phosphoric acid concentration: g/l | 0 | 0 | 0 | 15 | 15 | ||
| Zinc concentration | Total zinc concentration: g/l | 18 | 18 | 20 | 10 | 20 | |
| H 3PO 4(100)+Zn (25) in the concentration of Zn: g/l | 5 | 5 | 0 | 0 | 0 | ||
| The concentration of Zn: g/l among the nitric acid Zn | 13 | 13 | 20 | 10 | 20 | ||
| Nitrate ion concentration | Total NO 3 -Concentration: g/l | 27 | 27 | 41 | 21 | 41 | |
| NO among the nitric acid Zn 3 -Concentration: g/l | 26 | 26 | 40 | 20 | 40 | ||
| NO among the nitric acid Ni 3 -Concentration: g/l | 1 | 1 | 1 | 1 | 1 | ||
| Nickel concentration | The concentration of Ni: g/l among the nitric acid Ni | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| Concentration of iron | Iron concentration in nitric acid+iron | 1 | 2 | 6 | 3 | 3 | |
| Electrolytic condition | Anode electrolysis | Voltage | 2 | 2 | 2 | 2 | 2 |
| Electric current: A/ work | -0.2 | -0.2 | 0.6 | 0.8 | 1 | ||
| Time | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | Rise and kept 3 seconds in 4 seconds | ||
| Zn: catholyte | Voltage | 3 | 3 | 3 | 3 | 3 | |
| Electric current: A/ work | 1.5 | 13 | 0.9 | 0.9 | 1.4 | ||
| Time | Rise and protected in 5 seconds special 18 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | ||
| Electric current: Adm 2 | 6 | 52 | 3.6 | 3.6 | 5.6 | ||
| Iron: catholyte | Voltage | 2 | 2 | 2 | 2 | 2 | |
| Electric current: A/ work | -0.2 | -0.2 | 0.2 | -0.2 | -0.2 | ||
| Time | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | Rise and kept 18 seconds in 5 seconds | ||
| Handle the bath condition | PH | 1.93 | 1.9 | 2.22 | 1.5 | 1.49 | |
| ORP:mV (silver/silver chloride electrode current potential) | 130 | 114 | 85 | 179 | 184 | ||
| Temperature: ℃ | 30-35 | 30-35 | 30 | 30 | 30 | ||
| Total acidity: pt | 74 | 75 | 58 | 58 | 64 | ||
| Form film | Fraction of coverage: % | 100 | 100 | 100 | 70 | 100 | |
| Thickness: μ m | 62 | 5.4 | 5 | 2 | 3.6 |
Embodiment 9 and comparative example 5 and 6 use steel (the SPCC material: cold-rolled steel sheet) as test block that is of a size of 50mm * 25mm * 1mm (t).After the oil removing, each test block is immersed in titanium type colloidal solution to carry out surface adjustment, carry out phosphating process then with the formation film.Implement phosphating process by anodizing (7 seconds) → cathode treatment (23 seconds) circulation.The electrolysis treatment time is 30 seconds, and is shorter than prior art.
Comparative example 5 and 6 adopts and does not use phosphate ion solution (H
2PO
4 -+ Zn
2+) processing bathe, therefore can not obtain film of the present invention and form effect.
Embodiment 9 is film forming examples of shape under the situation that has iron ion to exist, but this processing has produced residue because of the existence of Fe ionic in bathing.
In embodiment 10 and 11, adjust the dissociation degree of phosphoric acid by two kinds of methods, that is, dissolved ferric iron is adjusted the dissociative method and use in phosphoric acid by H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts]/[H
3PO
4]+[H
2PO
4 -: 100 weight parts+Zn
2+: 25 weight parts] method of [Zn25% dissolving phosphoric acid salt ion solution than] of (mass ratio) expression.Embodiment 10 and 11 can both form film.
Do not use the Fe ion to adjust the embodiment 1-8 of phosphoric acid dissociation degree and use the Fe ion to regulate the Eo+ (ORP) that significant difference between the embodiment 9-11 of dissociation degree is to handle bath.All the former ORP of (not using the processing of Fe to bathe) are higher than 200mV (silver-silver chloride electrode current potential), and latter's's (using the processing of Fe to bathe) ORP is lower than 200mV.This shows the ORP (having reduced ORP) of dissolved Fe ion remarkably influenced solution.Therefore, handle the ORP that bathes, can use [by small amounts of iron being dissolved in the solution of adjusting the phosphoric acid dissociation degree in the phosphoric acid] in order to adjust.
Embodiment 12:
Element B shown in Figure 10 is a kind of tube element with cylinder hollow part.When this element was carried out electrolysis treatment, the electric current that flow to the bore part descended, thereby the formation of the film of this part is restricted.In embodiment 12, the supporting electrode that will be different from main electrode inserts hollow space, and implements electrolysis treatment by using the accessory power supply different with primary source to form the electrolytic treatment system that separates with main electrolysis treatment circuit.The electrode materials that the solid matter (metallic substance) of claim 1 and 7 described metal ions can be used for supporting electrode.
By using this supporting electrode on the bore part, to form film reliably.
The present invention can shorten the phosphorization treatment time as the element of the goods of handling, and can improve the performance of the film that obtains.The minimizing in treatment time makes it possible to produce a kind of special handling machine and reduces its size, thereby reduces the erection space of equipment and be converted into a kind of polyphone (transmission line) equipment.The even zinc phosphate crystal of gained is especially effective to Cold Forging.
Claims (15)
1, a kind of electrolytic phosphating process, it uses a kind of like this processing to bathe, and this processings bath is by by zinc being dissolved in the phosphate ion solution (H for preparing in the phosphoric acid
2PO
4 -+ Zn
2+) form, phosphoric acid (H
3PO
4), phosphate anion, zine ion and nitrate ion, can contain at least a metal ion that is selected from nickel ion, cobalt ion, cupric ion, mn ion and the iron ion, also contain 0.5g/l or the metal ion except that described film-forming components still less, this technology comprise by apply that voltage carries out electrolysis treatment between as anodal metal and goods as the processing of negative pole and the surface of the goods handled on form the step of phosphate layer.
2, electrolytic phosphating process as claimed in claim 1 is wherein bathed and is carried out electrolysis treatment by using its pH value to be adjusted into processing that 1.5-2.5 and its ORP (Eo+) remain on 90-450mV (silver/silver chloride electrode current potential).
3, electrolytic phosphating process as claimed in claim 1 or 2, wherein said processing bathe the phosphoric acid that contains 15g/l at least and phosphate anion, at least 15g/l zine ion, the nitrate ion of 12.5g/l and 0-3g/l's is selected from least a metal ion in nickel ion, cobalt ion, cupric ion, mn ion and the iron ion at least.
4, as each described electrolytic phosphating process in the claim 1 to 3, wherein said positive pole is selected from zinc or iron.
5, as each described electrolytic phosphating process in the claim 1 to 4, wherein after the goods by using described processing are implemented anode electrolysis as positive pole and zinc or iron as negative pole, the goods by using described processing are implemented catholyte as negative pole and zinc or iron as positive pole.
6,, wherein apply the voltage that is not higher than 6V by connecting direct supply as each described electrolytic phosphating process in the claim 1 to 5.
7, as each described electrolytic phosphating process in the claim 1 to 6, wherein by zinc being dissolved in the described phosphate ion solution (H for preparing in the phosphoric acid
2PO
4 -+ Zn
2+) be by 8 mass parts to the zinc of maxima solubility is dissolved in the solution for preparing in the phosphoric acid of 100 mass parts.
8, as each described electrolytic phosphating process in the claim 1 to 7, wherein by zinc being dissolved in the described phosphate ion solution (H for preparing in the phosphoric acid
2PO
4 -+ Zn
2+) be to be dissolved in the solution for preparing in the phosphoric acid of 100 mass parts by zinc with the 15-25 mass parts.
9, as each described electrolytic phosphating process in the claim 1 to 8, wherein by zinc being dissolved in the described phosphate ion solution (H for preparing in the phosphoric acid
2PO
4 -+ Zn
2+) be solution by dissolved oxygen zinc in phosphate ion solution, zinc hydroxide or metallic zinc preparation.
10, as each described electrolytic phosphating process in the claim 1 to 6, the phosphate ion solution (H during wherein said electrolysis treatment is bathed
2PO
4 -+ Zn
2+) and phosphoric acid (H
3PO
4) ratio [zinc is dissolved in phosphate ion solution (H wherein by relational expression
2PO
4 -+ Zn
2+)]/[zinc dissolving phosphate ion solution (H wherein
2PO
4 -+ Zn
2+)+phosphoric acid (H
3PO
4)] expression, be 0.4-1.
11, as each described electrolytic phosphating process in the claim 1 to 6, wherein said electrolysis treatment is bathed and is contained zinc and be dissolved in phosphate ion solution (H in the phosphoric acid
2PO
4 -+ Zn
2+), phosphoric acid (H
3PO
4) and zinc nitrate, and can contain the metal nitrate that constitutes by at least a nitrate that is selected from nickelous nitrate, Xiao Suangu, cupric nitrate and the manganous nitrate.
12, as each described electrolytic phosphating process in the claim 1 to 11, wherein at 1-18A/dm
2The catholyte current density under carry out electrolysis treatment on the surface of the goods of handling, to form phosphate layer.
13,, wherein do not exist any electric current that hinders in carrying out forming phosphate layer on the surface of electrolysis treatment with the goods handled under the condition of mobile obstacle between positive pole and negative pole as each described electrolytic phosphating process in the claim 1 to 12.
14, as each described electrolytic phosphating process in the claim 1 to 13, wherein by with the electrolysis treatment time set being 60 seconds or the shorter lithoform that forms.
15, as each described electrolytic phosphating process in the claim 1 to 14, it applies two or more voltage and currents wherein to utilize two or more power supplys and electrode pair according to the position of the goods of handling.
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| JP2005131600A JP4419905B2 (en) | 2005-04-28 | 2005-04-28 | Electrolytic phosphate chemical treatment method |
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| US4165242A (en) * | 1977-11-21 | 1979-08-21 | R. O. Hull & Company, Inc. | Treatment of metal parts to provide rust-inhibiting coatings by phosphating and electrophoretically depositing a siccative organic coating |
| US4486241A (en) * | 1981-09-17 | 1984-12-04 | Amchem Products, Inc. | Composition and process for treating steel |
| DE4111186A1 (en) * | 1991-04-06 | 1992-10-08 | Henkel Kgaa | METHOD FOR PHOSPHATING METAL SURFACES |
| US5645706A (en) * | 1992-04-30 | 1997-07-08 | Nippondenso Co., Ltd. | Phosphate chemical treatment method |
| US5385655A (en) * | 1992-10-30 | 1995-01-31 | Man-Gill Chemical Company | Treatment of metal parts to provide rust-inhibiting coatings |
| US6231688B1 (en) * | 1995-12-06 | 2001-05-15 | Henkel Corporation | Composition and process for zinc phosphate conversion coating |
| EP0972862A3 (en) * | 1998-07-01 | 2004-01-02 | Nihon Parkerizing Co., Ltd. | Method for forming a phosphate film on steel wires and apparatus used therefor |
| JP4019723B2 (en) * | 2001-02-23 | 2007-12-12 | 株式会社デンソー | Electrolytic phosphate chemical treatment method |
| JP3937957B2 (en) * | 2002-07-22 | 2007-06-27 | 株式会社デンソー | Method for recovering active ingredients from electrolytic phosphate chemical treatment bath |
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- 2005-04-28 JP JP2005131600A patent/JP4419905B2/en not_active Expired - Fee Related
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2006
- 2006-04-26 US US11/412,186 patent/US20060243600A1/en not_active Abandoned
- 2006-04-26 DE DE102006019496A patent/DE102006019496A1/en not_active Ceased
- 2006-04-28 CN CNA2006100886380A patent/CN1891865A/en active Pending
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| CN103952745A (en) * | 2014-05-08 | 2014-07-30 | 山东大学苏州研究院 | Method for preparing zinc phosphate conversion coating on surface of titanium |
| CN105603413A (en) * | 2016-01-04 | 2016-05-25 | 广东工业大学 | Preparation method for low alloy steel surface phosphating film |
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| CN107630243A (en) * | 2017-10-16 | 2018-01-26 | 浙江五源科技股份有限公司 | A kind of electrolytic preparation method of complex phosphate coating |
| CN107630243B (en) * | 2017-10-16 | 2019-07-02 | 浙江五源科技股份有限公司 | A kind of electrolytic preparation method of complex phosphate coating |
| CN108505099A (en) * | 2018-04-20 | 2018-09-07 | 安徽省康宇水电机械成套设备有限公司 | A kind of vehicle bridge lower thrust rod bearing anticorrosion treatment technology |
| CN109898123A (en) * | 2019-03-11 | 2019-06-18 | 山东凤阳佰乐舒家居有限公司 | A kind of steel wire drawing electrolytic phosphating liquid and preparation method thereof |
| CN113073371A (en) * | 2021-03-22 | 2021-07-06 | 领润(南京)绿色化学有限公司 | Clean anode plate friendly electrolytic phosphating solution and phosphating process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006307289A (en) | 2006-11-09 |
| DE102006019496A1 (en) | 2006-11-30 |
| US20060243600A1 (en) | 2006-11-02 |
| JP4419905B2 (en) | 2010-02-24 |
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