WO2000036191A1 - Procede de phosphatation electrolytique et revetement composite forme sur une surface d'acier - Google Patents

Procede de phosphatation electrolytique et revetement composite forme sur une surface d'acier Download PDF

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Publication number
WO2000036191A1
WO2000036191A1 PCT/JP1999/007124 JP9907124W WO0036191A1 WO 2000036191 A1 WO2000036191 A1 WO 2000036191A1 JP 9907124 W JP9907124 W JP 9907124W WO 0036191 A1 WO0036191 A1 WO 0036191A1
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Prior art keywords
bath
phosphate
electrolytic
metal
phosphoric acid
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PCT/JP1999/007124
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English (en)
Japanese (ja)
Inventor
Shigeki Matsuda
Shin Nishiya
Original Assignee
Denso Corporation
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Publication date
Application filed by Denso Corporation filed Critical Denso Corporation
Priority to CA2320865A priority Critical patent/CA2320865C/fr
Priority to EP99959898A priority patent/EP1074640A4/fr
Priority to BRPI9907916-0A priority patent/BR9907916B1/pt
Publication of WO2000036191A1 publication Critical patent/WO2000036191A1/fr

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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
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36—Phosphatising

Definitions

  • the present invention relates to a method for performing a phosphate chemical conversion method by electrolysis and to a composite film formed on a steel surface.
  • Japanese Patent Publication No. 5-82 22 481 discloses that phosphoric acid is basically composed of phosphate ions, oxo acid ions containing nitrogen, and metal ions containing film components, which do not contain sludge. It describes that the bath is electrolytically treated. This treatment bath is characterized by maintaining sludge at pH 2 to 4 and at a temperature of 40 ° C or less.
  • the phosphoric acid chemical conversion treatment bath disclosed in Japanese Patent Publication No. 5-8222481 adjusts the pH and as a promoter, it is possible to use a hydroxide that has no relation to the film forming components. It uses sodium sodium nitrite. Therefore, it cannot be said that the film was formed efficiently as an electrolytic phosphoric acid chemical conversion method.
  • the present invention has been made in view of the above problems, and provides a phosphoric acid conversion treatment method capable of efficiently forming a skin film and a composite film obtained by the method. .
  • the components in the solution do not react. It is an electrochemical reaction using an external power source as the energy source for the reaction. No chemicals (reducing agents) are used to chemically promote the electrolytic reaction during the “Electrical plating” process.
  • the electrochemical reaction is based on the reduction reaction of metal ions in the solution (force force reaction) and the reducing agent added to the solution (dissociation degree of aqueous solution). It uses the electrochemical energy (energy that forms a potential difference in a chemical reaction) that is formed between the oxidation reaction (an anodic reaction) and the oxidation reaction (an anodic reaction).
  • Metal plating forms a metal film by the reduction reaction of metal ions (cations).
  • Phosphoric acid conversion treatment involves the oxidation (dehydrogenation) of phosphate ions (anions).
  • An acid salt film is formed. Disclosure of the invention
  • the present inventor has proposed that if the electrolytic treatment and the electroless treatment can be performed in the plating, even if the same wet surface treatment is used for the phosphatization treatment, the conventional electroless phosphatization treatment can be performed.
  • the present inventors have thought that it is possible to commercialize the electrolytic treatment, and have reached the present invention.
  • the conventional surface treatment technology will be described, and the present surface treatment technology will be associated with the electrolytic phosphate chemical conversion treatment technology to be obtained.
  • the technology of the electrolytic phosphoric acid conversion treatment method of the invention was investigated.
  • surface treatment technologies are first classified into “dry surface treatment” and “wet surface treatment.”
  • the surface treatment technology of “wet surface treatment” is further divided into “electroless treatment” and “electrolytic treatment”. Processing ”.
  • specific examples of the surface treatment by “electroless treatment” include “electroless plating” and “electroless phosphoric acid conversion treatment”.
  • Examples of the surface treatment by the “electrolytic treatment” include “electroplating”, “anodic oxidation”, and “electrodeposition coating”. "Belongs to the category of" Electrical plating ".
  • wet surface treatment includes “electroless treatment” and “electrolytic treatment”.
  • Electroless treatment depends on the chemical energy of chemicals added to the treatment bath, such as a reducing agent (plated) and an oxidizing agent (phosphoric acid treatment). In contrast, “electrolysis” relies on the electric energy of an external power source. For this reason, the baths for “electroless plating” and “electrolytic plating” are basically different in “plate”, and the “electroless plating” bath is not electrolytically treated.
  • the phosphating method is basically different from that of the “electroless bath” and “electrolytic bath”. Should.
  • FIG. 1 shows a schematic diagram of the electrolytic treatment.
  • the electrolytic treatment uses an external power source, and is composed of three components, which are roughly divided into an electrode, a solution, and an object to be treated in an electrolytic cell.
  • Electrode plating means that the anode (counter electrode) and the plating film component (for example, in the case of zinc plating, the zinc electrode) are dissolved by applying a voltage and current, and pass through the solution in a complex state. , Deposited at the cathode. Therefore, only the counter electrode component dissolves.
  • the object to be treated is the cathode, There is no reaction such as dissolution in the tank.
  • “Anodic oxidation” is a process in which the aluminum material used as the anode dissolves in the treatment bath, and at that time, the solvent (water) and the solute ion (anion) decompose with an increase in the voltage, and are formed as a result. Oxygen ions (O 2 —) and dissolved aluminum are combined to form a film of aluminum oxide (A 10,) on the surface of the aluminum material.
  • the counter electrode cathode
  • Electrodeposition coating a voltage is applied to colloidal organic substances and inorganic substances dispersed in water, and the colloidal substances are subjected to electrolysis such as electrophoresis and deposition to deposit on the surface of the electrode (object to be treated). It solidifies (paint film).
  • electrolysis such as electrophoresis and deposition to deposit on the surface of the electrode (object to be treated). It solidifies (paint film).
  • electrodeposition coating is a process in which components in a solution are subjected to an electrolytic reaction, and only the solvent water and colloidal components dispersed in water react when a voltage is applied. There is no reaction such as dissolution of the electrodes (counter electrode and object).
  • the electrodeposition coating bath is always maintained at a predetermined temperature, and is subjected to microfiltration (performation).
  • the object to be treated before being electrolyzed is washed with pure water and then put into the electrolytic cell. Is being processed.
  • the “electrolytic phosphoric acid conversion treatment” of the present invention is completely different from the above three, and all three components of —counter electrode ”,“ solution ”and“ object to be treated ”dissolve and react.
  • Electrode plating is a technique in which the metal to be plated is dissolved at the anode and deposited at the cathode, but prevents the molten metal ions from binding in the electrolytic cell. A complex is used as a means to prevent the binding.
  • the treatment bath for “Electrical Metal” is a complex bath of metal salts. The reason for this is to prevent metal ions from binding and precipitating (reacting solute components in the solution) in the process of dissolving the plating metal from the electrode (anode) and depositing it on the cathode.
  • a cyanide (CN) complex is famous.
  • Electroplating baths are usually not transparent and may contain ions that do not participate in film formation, such as Na ions, but the complex does not decompose in the treatment bath Is being treated as follows. By this treatment, it becomes possible to deposit only the metal ions on the cathode surface to form a plating film. (Because Na ion, etc., has a different deposition potential from the plating metal ion, it does not deposit on the cathode. This is electrochemically consistent with the principle.)
  • Anodic oxidation refers to electrolytic treatment using the object to be treated as the anode and the insoluble electrode as the cathode. At that time, if unnecessary ions are involved in the film formation reaction, it will be affected by the dissolution reaction of the material (for example, aluminum) and the oxidation (film formation) reaction. This is because the dissolved aluminum ions are very active in the treatment bath.
  • the anodized film is formed by reacting the dissolved aluminum ion with oxygen ions (O 2 —) generated by the decomposition of water as a solvent. In order to prevent dissolved aluminum ions from reacting with other ions, the contamination of the treatment bath with impurity ions is severely restricted.
  • Electrodeposition coating is a process in which components in a solution are subjected to an electrolytic reaction on the electrode surface to form a coating film.
  • the reaction by application of voltage is the solvent water and colloidal organic substances dispersed in the water. Only. Then, the electrodes (the counter electrode and (Object to be treated) Force No reaction such as dissolution.
  • the electrodeposition coating bath It is important for the electrodeposition coating bath to maintain the solution state in a predetermined state (range) that can form a good coating film. If the components in the solution change (react) due to aggregation, decomposition, etc., and it becomes impossible to control the solution state, it is impossible to form an effective electrodeposition coating film. Therefore, in order to prevent the self-aggregation of the colloid components dispersed in the bath and maintain the dispersed state, the electrodeposition coating bath is constantly maintained at a constant temperature, and is subjected to microfiltration (Ultra-Finoreletre). One shot).
  • the contamination with interfering ions (for example, Na ions) is strictly limited, and is kept close to pure water. This is because the presence of an interfering ion interferes with the deposition reaction on the electrode surface.
  • ii Prevents self-aggregation of components in solution by constant filtration, circulation and maintenance of temperature (electrodeposition coating)
  • the electrolytic phosphoric acid conversion treatment of the present invention can be realized by embodying that components in a solution involved in film formation are not substantially reacted except at the electrode surface even when electrolysis is performed. Becomes
  • Phosphate ion and phosphoric acid, nitrate ion, and metal ions that form a complex with phosphate ion in the phosphate conversion bath are dissolved in the phosphate conversion bath
  • the potential at which the ions are reduced and precipitated as metal is higher than the anodic electrolysis reaction potential of water, which is a solvent, or less than 0.83 V (expressed as hydrogen standard electrode potential).
  • An object to be treated having conductivity is brought into contact with a phosphatization treatment bath containing at least one of the above, and electrolytic treatment is performed to form the phosphate and the phosphate on the surface of the object to be treated.
  • the object to be treated is a metal material that forms a complex with phosphate ions in the phosphating bath in the phosphating bath, and is dissolved in the phosphating bath.
  • a metal material whose potential is reduced and the potential that precipitates as a metal is higher than the anode electrolysis reaction potential of water as a solvent or higher than 0.83 V (expressed as hydrogen standard electrode potential).
  • the phosphate conversion treatment bath reduces the metal ions other than the components of the coating to 0 to 400 ppm and forms the coating. By substantially eliminating solids that affect the reaction, reactions other than the formation of a film in the bath are suppressed as much as possible. This makes it possible to smoothly and efficiently perform a film formation reaction on the surface of a physical material.
  • the phosphatization treatment bath contains 0 to 40 ppm of metal ions other than the components of the film and substantially removes solid substances that affect the film formation reaction. Since it is not so contained, the deposition reaction can be performed without mainly depositing the phosphate from the bath. It is possible to obtain, for the first time, a film containing at least an acid salt and the metal that does not form phosphate.
  • the phosphatization treatment bath contains metal ions other than the components of the film containing at least the above-mentioned phosphinate in an amount of 0 to 10 O ppm, so that the film can be efficiently formed. I like it.
  • the ion nitrate concentration is 6 g / l to 140 g / I
  • the concentrations of the phosphate ion and the phosphoric acid are as follows. 0.5 to 0.68 / 1
  • the concentration of metal ions forming a complex with phosphate ions in the phosphate conversion bath was 0.5 g Z 1 to 70 g Z 1
  • the potential at which the ions dissolved in the phosphatization bath are reduced and precipitated as a metal is greater than or equal to 0.83 V ( It is preferable that the concentration of the metal ion that is equal to or higher than 0 g Z1 to 40 g Z1 be represented.
  • the phosphate chemical conversion treatment bath does not contain an acid having a degree of dissociation of an acid larger than the degree of dissociation of the acid of the phosphate ions.
  • the acid having a degree of dissociation of canine acid that is lower than the degree of dissociation of the acid of phosphoric acid is, for example, nitric acid.
  • the film-forming reaction of the phosphate on the surface of the object to be treated is performed in the treatment bath. It hinders, and cannot perform an efficient reaction.
  • the metal ion which forms a complex with the phosphate ion in the phosphate conversion bath is preferably made of at least one of zinc, iron, manganese and calcium.
  • the potential at which the ions dissolved in the phosphatization bath are reduced and precipitated as a metal is higher than or equal to the anode electrolysis reaction potential of water, which is the solvent, or 0.83 V (hydrogen It is preferable that the metal ion having the above-mentioned value is at least one of nickel and copper.
  • the present invention provides a phosphoric acid salt containing at least phosphate ions, phosphoric acid, nitrate ions, and a metal ion that forms a complex with a phosphate ionization treatment bath with a phosphate ion.
  • a method for forming a film containing at least phosphoric acid on the surface of the object to be treated by bringing an object having conductivity into contact with a pretreatment bath and performing an electrolytic treatment,
  • the phosphoric acid conversion treatment bath has a metal ion other than the components of the film in a range of 0 to 400 ppm and substantially does not contain a solid substance that affects a film forming reaction.
  • the object to be treated is an electrolytic phosphoric acid salt which is electrolyzed in the phosphoric acid conversion treatment bath between a phosphate ion and a metal material which forms a complex in the phosphate treatment bath.
  • the present invention provides a processing method.
  • the obtained film is a chemical conversion film mainly composed of phosphate, and the metal phosphate other than the components of the skin is contained in the phosphate chemical conversion bath.
  • the film formation reaction in the phosphatization can be performed efficiently.
  • the phosphate chemical conversion bath contains metal ions other than the components of the film containing at least the above-mentioned phosphate in a range of about 0 to 10 Oppm.
  • the ion nitrate concentration is 6 gZ 1 to 140 g / the phosphate ion and the phosphoric acid concentration is 0.5 g / l to 60 g / l.
  • the concentration of the metal ion which forms a complex with the phosphate ion in the phosphate conversion treatment bath is 0.5 g / l to 70 g / l.
  • the phosphoric acid conversion treatment bath does not contain an acid having a degree of dissociation of a dog acid rather than the degree of dissociation of the acid of the phosphoric acid ion.
  • an acid having a larger acid dissociation degree than the acid dissociation degree of the phosphoric acid ion is, for example, nitric acid.
  • the metal ion forming a complex with the phosphate ion in the phosphate conversion bath is preferably made of at least one of zinc, iron, manganese and calcium.
  • an electrolytic treatment may be performed using the object to be treated as an anode.
  • electrolytic treatment may be performed using the object to be treated as a cathode.
  • the phosphoric acid conversion treatment method comprises the steps of: After the treatment, it is preferable to perform the electrolytic treatment using the object to be treated as the cathode.
  • a film forming reaction on the surface of the object to be processed can be performed after exposing a new surface by etching the surface of the object to be processed. Therefore, a film having improved adhesion to the surface of the workpiece can be obtained.
  • the cathodic electrolytic treatment of performing the electrolytic treatment using the object to be treated as a cathode in the phosphatization method is the same as the metal in which ions dissolved in the phosphatization bath are reduced and deposited.
  • Electrolytic treatment using a conductive material insoluble in a phosphate chemical conversion bath as an anode, and a metal material forming a complex in the phosphate phosphate bath as an anode An electrolytic phosphoric acid conversion treatment method composed of at least one of the electrolytic treatments is preferred.
  • a film having the following can be formed on the surface of the object to be processed.
  • the cathodic electrolytic treatment of performing the electrolytic treatment using the object to be treated as a cathode in the phosphatization method is the same as the metal in which ions dissolved in the phosphatization bath are reduced and deposited.
  • a metal material forming a complex in the phosphating bath After conducting an electrolytic treatment using a conductive material insoluble in Z or a phosphating bath as an anode, a metal material forming a complex in the phosphating bath.
  • the electrolytic phosphoric acid conversion method in which the electrolytic treatment using the anode is performed in one cycle and this cycle is performed at least once is preferable.
  • the cathodic electrolytic treatment of performing the electrolytic treatment using the object to be treated as a cathode in the phosphatization method is the same as the metal in which ions dissolved in the phosphatization bath are reduced and deposited.
  • An electrolytic tank for performing an electrolytic treatment using a conductive material insoluble in a phosphating chemical bath as an anode, and a metal forming a complex in the phosphating bath An electrolytic phosphoric acid conversion treatment method in which the electrolytic treatment is performed by separating the electrolytic treatment using the material as the anode and performing the electrolytic treatment is preferable.
  • At least one of nickel and copper is the same metal material as the metal that is reduced and precipitated out of the metal dissolved in the phosphatization bath.
  • the metal material forming a complex in the phosphatization bath is preferably at least one of zinc, iron, manganese and calcium.
  • the metal material used as the anode is used as the cathode during the electrolytic treatment using the object as the cathode, and the phosphor is used as the anode. It is preferable to use a material that is insoluble in the acidification treatment bath as an anode and apply a voltage of 5 V or less between the anode and the cathode.
  • the metal material used as the anode is used as the cathode during the electrolytic treatment using the object as the cathode; It is preferable that a material insoluble in the acidification chemical treatment bath is used as an anode, and a voltage is applied between the anode and the cathode to such an extent that the cathode is not substantially dissolved. In this way, by performing the treatment when the object is not in contact with the phosphatization bath, the dissolution of the metal material when the object is not being treated is suppressed. can do.
  • a part of the phosphating bath is taken out of the bath having the phosphating bath, and the energy state of the phosphating bath as a liquid is thermodynamically determined. It is preferable to stabilize the condition and then return it to the bathtub again.
  • a part of the phosphatization bath is taken out of the bath having the phosphatization bath, and solids precipitated during the phosphatization during the film formation reaction are removed. After the treatment, it is preferable to return to the bathtub again.
  • a reaction product sludge
  • a nitrogen oxide NO, etc.
  • a part of the phosphatization bath is taken out, and the phosphatization bath is constituted with respect to the removed bath. It is preferable to supply a replenisher containing a treatment bath component having a concentration higher than at least one of the components.
  • the present invention relates to an electrolytic phosphoric acid conversion coating method in which an object to be treated is subjected to electrolytic treatment using a cathode, and the method comprises: The potential at which ions dissolved in the bath are reduced and precipitated as metal is higher than the anode electrolysis reaction potential of water as a solvent or -0.83 V (at the hydrogen standard electrode potential). display) The above-mentioned metals are dissolved in the phosphatization bath and are converted from cations by electrolysis to be reduced by electrolysis and deposited on the surface of the object to be treated. In the phosphate bath, metal ions that complex with phosphate ions in the phosphate conversion bath precipitate as phosphate crystals in response to the dehydrogenation of phosphate ions.
  • An electrolytic phosphoric acid conversion treatment method comprising:
  • the metal ion to be complexed with the phosphate ion is at least one of Fe, Zn, Mn, Ca and Mg.
  • the potential at which the ions dissolved in the phosphatization bath are reduced and precipitated as metal is equal to or higher than the anodic electrolysis reaction potential of the solvent water, or 0.83 V (hydrogen standard). It is preferable that the metal having electrode potential or higher is at least one of Ni, Cu, Fe, and Zn.
  • the composition of the treatment bath is determined by the concentration of the metal ion complexed with the phosphate ion (gZl) / (the concentration of the phosphate ion and the phosphoric acid (gZ1 It is preferable that the ratio of)) is 0.1 or more.
  • the ratio of the concentration of the metal ion complexing with the phosphate ion (gZl) / is preferably 0.1 or more, more preferably. More specifically, by setting it to 0.25 or more, phosphoric acid (H 2 P 0,) can be present as phosphoric acid ion (HP 0,) in the treatment bath. Thus, the oxidation reaction of phosphoric acid ion on the cathode surface can be controlled. It also controls the phosphoric acid present in the treatment bath.
  • the metal forming an anode and a cathode is used at the start of the electrolytic treatment. It is preferable to vary the voltage applied between the materials.
  • the fluctuation of the applied voltage at the start of the electrolysis treatment is pulse-like.
  • the present invention provides a film comprising a metal that does not form phosphate and a phosphate compound on a steel surface, wherein the metal and the phosphate compound constituting the film are dispersed throughout the film.
  • Providing a composite coating The present invention relates to a film composed of a metal that does not form phosphate and a phosphate compound on the surface of steel, wherein at least no phosphate is formed on the outermost surface of the film.
  • the present invention relates to a film composed of a metal that does not form phosphate and a phosphate compound on a steel surface, wherein the film is inevitable for phosphate by X-ray diffraction analysis. Provide a composite film that shows no peak other than the peak.
  • the present invention relates to a film comprising a metal that does not form a phosphate and a phosphate compound on a steel surface, wherein the number of atoms of the metal that does not form a phosphate is a phosphate crystal.
  • the present invention provides a composite film having 0.25 or more of the number of atoms of the phosphorus constituting the same.
  • the non-phosphate-forming metal is preferably at least one of Ni, Cu, Fe and Zn.
  • the metal forming the phosphate compound is preferably at least one of Fe, Zn, Mn, Ca and Mg.
  • the iron or steel preferably contains iron (Fe) in an amount of 95% by weight or more when the entire steel is 100% by weight.
  • the X-ray diffraction analysis is preferably performed by ESCA or EDX.
  • Figure 1 is a schematic diagram showing the outline of the electrolytic treatment.
  • Figure 2 is a schematic diagram of the electrolytic reaction system.
  • FIG. 3 is a configuration diagram showing the configuration of the electrolytic phosphoric acid conversion treatment apparatus.
  • FIG. 4 is a perspective view of the object to be processed in Example 1 and Comparative Example 1.
  • FIG. 5 is an EDX analysis chart of the plane portion of the object to be processed in the first embodiment.
  • FIG. 6 is an EDX analysis chart of the outer peripheral portion of the workpiece in the first embodiment.
  • FIG. 7 is an EDX analysis chart of a plane portion of the object to be processed in Comparative Example 1.
  • FIG. 8 is an EDX analysis chart of the outer peripheral portion of the workpiece in Comparative Example 1.
  • FIG. 9 is a GDS analysis chart of the plane portion of the object to be processed in the first embodiment.
  • FIG. 10 is a GDS analysis chart of the outer peripheral portion of the workpiece in the first embodiment.
  • FIG. 11 is a GDS analysis chart of the flat part of the object in Comparative Example 1.
  • FIG. 12 is a GDS analysis chart of the outer peripheral portion of the workpiece in Comparative Example I.
  • FIG. 13 is a perspective view of an object to be processed in Example 2 and Comparative Example 2.
  • FIG. 14 is an EDX analysis chart of a plane portion of the object to be processed in Example 2.
  • Figure 15 shows an EDX analysis chart of the planar part of the workpiece in Comparative Example 2. It is a block diagram.
  • FIG. 16 is an EDX analysis chart of a plane portion of the object to be processed in the third embodiment.
  • FIG. 17 is an EDX analysis chart of the outer peripheral portion of the workpiece in the third embodiment.
  • FIG. 18 is an EDX analysis chart of the plane portion of the workpiece in Comparative Example 1.
  • FIG. 19 is an EDX analysis chart of the outer peripheral portion of the workpiece in Comparative Example 1.
  • FIG. 20 is an SEM photograph of a plane portion of the object to be processed in Example 3.
  • FIG. 21 is an analysis photograph of the phosphorus in the flat portion of the object to be processed in Example 3.
  • FIG. 22 is an analysis photograph of zinc in the plane portion of the article to be treated in Example 3.
  • FIG. 23 is an analysis photograph of nickel in the flat portion of the object to be processed in Example 3.
  • FIG. 24 is an analysis photograph of iron in a plane portion of the object to be processed in Example 3.
  • FIG. 25 is an SEM photograph of the outer peripheral portion of the workpiece in Example 3.
  • FIG. 26 is an analysis photograph of the phosphorus at the outer peripheral portion of the object to be processed in Example 3.
  • FIG. 27 is an analysis photograph of zinc in the outer peripheral portion of the article to be treated in Example 3.
  • FIG. 28 is an analysis photograph of nickel in the outer peripheral portion of the object to be processed in Example 3.
  • FIG. 29 is an analysis photograph of iron in the outer peripheral portion of the object to be processed in Example 3.
  • the treatment bath has an extremely active and easily decomposable bath composition. This is because the reaction in the solution cannot be performed unless the treatment bath is activated.
  • the conventional electroless phosphoric acid conversion treatment bath uses sodium hydroxide. In some cases, PH (concentration of hydrogen ion) was added to a predetermined range, or nitrite ion was added as an oxidation promoter to promote the reaction.
  • the phosphating treatment contains a large amount of Na ion, and as a result, the electroless phosphating bath does not become a phosphate film.
  • the bath contains many impurities (unnecessary substances).
  • the conventional electrolytic phosphoric acid conversion treatment method used a phosphoric acid conversion treatment bath containing such a component other than the film component.
  • the phosphatization bath of the present invention ions that are not involved in the film formation reaction such as Na, which are metal ions other than the film components, are added to the phosphatization bath. ⁇ ! 0 ppm or less, preferably 10 ppm O ppm or less was adopted. As a result, the stability of the treatment bath as a solution is greatly improved, and no sludge is generated. Furthermore, it is possible to adopt a configuration in which the components in the solution are reacted only on the electrode surface by the electrolytic treatment. The treatment bath reacts only on the electrode surface during the electrolytic treatment, and at other times and places, I was able to make it virtually non-reactive.
  • the following means as a means for reacting only at the electrode surface during the electrolytic treatment and at substantially other times and places so as not to substantially react.
  • a part of the phosphatization bath is taken out of the bath having the phosphatization bath, and the energy state of the phosphatization bath as a liquid is thermodynamically determined. And then return it to the bath again, and take out a part of the phosphatization bath from the bath having the phosphatization bath, In the membrane reaction process, it is preferable to return the film to the bath again through a filter for removing solids precipitated during the phosphoric acid conversion treatment.
  • the metal material used as the anode is used as the cathode during the electrolytic treatment using the object as the cathode
  • a material that is insoluble in the phosphating bath is used as an anode
  • a voltage of 5 V or less is applied between the anode and the cathode.
  • the metal material used as the anode is used as the cathode during the electrolytic treatment using the object to be treated as the cathode, and the material is insoluble in the phosphate chemical conversion bath.
  • a voltage is applied between the anode and the cathode so that the cathode does not substantially dissolve.
  • a part of the phosphatization bath is taken out and the phosphatization bath is taken out of the bath. It is preferable that a replenishing solution containing a processing bath component having a concentration higher than at least one of the components constituting the processing bath is added to a portion other than the electrolytic cell.
  • composition of the treatment bath during the electrolytic treatment is determined by the following formula: the concentration of the metal ion complexed with the phosphate ion (gZl) / (the concentration of the phosphate ion and the phosphate (gZl) It is preferable that the ratio of 1))) is 0.1 or more.
  • the phosphoric acid chemical conversion treatment bath does not substantially contain solids that affect the film formation reaction, and reacts only on the electrode surface during the electrolytic treatment. At other times and places, it can be made virtually unresponsive.
  • the “electrolytic phosphoric acid conversion treatment method” of the present invention the “electrodeposition coating” of forming a coating film by reacting components in a solution is careful to prevent aggregation and decomposition of components in the solution.
  • the solution is an organic substance, it is possible to prevent contamination of impurities and maintain the processing bath at a predetermined temperature and always filter the solution.
  • the “electrolytic phosphoric acid conversion treatment method” of the present invention is an electrolysis in an inorganic acid solution, it is preferable to perform the above-mentioned correspondence in addition to the treatment of electrodeposition coating.
  • metal ions other than the metal ions serving as components for film formation such as Na as a conventional reaction accelerator, are not substantially contained, so that the metal ions are not substantially contained.
  • phosphate ions and metal ions that form a complex in the phosphate chemical treatment bath can be present as a complex. Therefore, even though metal ions are dissolved in the solution in the treatment bath, they are stably present. As a result, it was possible to suppress phenomena such as the generation of sludge in the treatment bath, and to cause a film deposition reaction only on the surface of the object to be treated.
  • cyanide complexes are often used in conventional electroplating, and these cyanine complexes do not decompose in solution, but only on the cathode surface where charges are concentrated, forming a metal film. It corresponds to precipitation.
  • Complexes have also been used in conventional electroless phosphatization baths.
  • metal ions Fe 3 , Zn 2 ⁇ Mn, etc.
  • the phosphate ion complex used in the conventional electroless phosphate conversion treatment bath contains Na ions, etc. and is in an active (unstable) state, so it is used for electroplating.
  • the stability as a complex is smaller than that of a cyanide complex or the like. Therefore, even if it is electroless, it is easily decomposed into a film and a sludge, and the present invention is not used at all.
  • the cyanine complex has high stability, and the complex cannot be dissociated (decomposed) by electroless treatment (electroless plating). Therefore, if the stability of a phosphoric acid ion complex that is used only for electrolysis is increased, the cyanide complex will not be easily decomposed.
  • the low stability of the phosphoric acid ion complex used in the conventional electroless phosphoric acid conversion treatment bath is due to the pH adjustment of the bath.
  • phosphate ions are easily dissociated (oxidatively decomposed) (by adding Na ions, etc.).
  • the pH of the bath to which Na is added is not adjusted. Therefore, the stability of the phosphate ion complex can be increased.
  • such a treatment bath having a high stability of the phosphate ion complex does not decompose without electrolysis, and the film is not formed. Do not form. Also, even during the electrolytic treatment, it does not decompose in a solution as in the case of electroplating, but only decomposes on the cathode surface where charges are concentrated, forming a film. Therefore, basically no sludge is formed.
  • the treatment bath remains transparent.
  • the phosphoric acid ion complex is too stable, it is not suitable for film formation in cathodic electrolysis. Therefore, it is necessary to maintain the stability of the phosphate complex in an appropriate range.
  • the composition of the treatment bath during the electrolytic treatment is such that the concentration of the metal ion that forms a complex with the phosphate ion (gZl) I (phosphate ion and phosphate ion) It is preferable that the ratio of the acid concentration (gZl)) is 0.1 or more. Thereby, the stability of the complex can be ensured.
  • the electrolytic treatment of the present invention in the phosphoric acid conversion treatment method, after performing the electrolytic treatment using the object to be treated as an anode, the electrolytic treatment is performed using the object to be treated as a cathode Things are preferred.
  • a film-forming metal or the like Fe, Ni, Zn, etc.
  • anode it is preferable to use an object to be treated as the cathode.
  • the electrode material installed in the electrolytic cell as the anode may be the following two cases.
  • the anode material is electrochemically dissolved by the action of the external power supply, and exists in the solution in a dissolved ion state. Deposits (solidifies) to form a film.
  • the insoluble material that does not dissolve or hardly dissolves in (2) is used as the anode
  • the cation dissolved in the solution is deposited on the cathode by applying an external power supply.
  • the phosphoric acid conversion coating film to be formed it can be used properly.
  • metals that form phosphate compounds for example, Fe, Zn
  • the metal that “the metal ion dissolved in the phosphatization bath is reduced and precipitated as a metal element to form a solid” is a conventional metal.
  • some metals eg, can be easily dissolved and precipitated, but large voltages and currents are required to dissolve and precipitate them.
  • Some metals eg, N i do.
  • a metal that requires a large voltage and current for melting and deposition eg, Ni
  • a large voltage is applied.
  • current is required.
  • electrolysis applies relatively large voltages and currents to the entire treatment bath.
  • electrolysis (which requires a large voltage and current) requires electrolysis of a phosphate compound-forming metal (Fe, Zn) that can be electrolyzed by applying a small voltage. Is not appropriate.
  • the present inventor recognizes that there are basically two types of “cathode electrolysis” as a feature of the electrolytic phosphatization. Then, it is necessary to recognize the difference between the two cathodic electrolysis methods according to the required properties of the film, and use them appropriately. That is, the composition of the processing bath and the metal material used for the anode are determined according to the required film, and the electrolytic treatment (voltage and current) corresponding to the processing bath and electrode material is used properly.
  • the second response is when using “materials that hardly dissolve or are insoluble”.
  • the metal component required for the film component is required. It is impossible to obtain all on by dissolution from the electrode.
  • the cathodic electrolysis only covers the cathodic electrolysis (reduction and precipitation). In this way, for example, the electrolytic voltage for incorporating Ni into the film component can be made smaller than when assuming that the film is formed by dissolving Ni from the anode.
  • Such a device is preferable for practical use of electrolytic phosphoric acid conversion treatment.
  • the present invention forms a new electrochemical phosphatization reaction by providing an environment for performing an electrolytic phosphatization reaction.
  • the outline below The point is explained.
  • the electrolytic phosphoric acid conversion treatment reaction of the present invention basically does not include sludge.
  • the electrochemical reaction system consists of an anode reaction and a cathode reaction.
  • the anode reaction is an anodic reaction and an oxidation reaction.
  • the power source reaction is a cathodic reaction and a reduction reaction.
  • its electrode potential is defined as being higher in force force reaction than in anode reaction.
  • Figure 2 does not outline the formation of the electrochemical reaction system formed in the electrolytic treatment.
  • reaction system between electrodes separated in solution an anode-cathode reaction system is formed during separation.
  • the breakdown is as follows
  • Electrochemical reaction system involving positive ion between electrodes (anode at anode)
  • Electrochemical reaction system involving anion and solvent between electrodes cathode reaction at anode and anode reaction at cathode
  • reaction system on the same electrode surface that has not been separated in the solution is the reaction between cations, anions, and solvents on the same electrode surface.
  • a reaction system is formed. The breakdown is as follows.
  • electrochemical reaction system consisting of a cathodic reaction and an anode reaction is formed when an electrochemical reaction system is formed irrespective of “electroless treatment” or “electrolytic treatment”.
  • electrochemical reaction system of the “electroless treatment” consists only of a cathode reaction and an anode reaction on the same surface.
  • the reaction system of 2-1 and 2-2 is composed of a metal (solid) and a solution (liquid).
  • An electrochemical reaction system may be composed of only a pair of cathodic and anodic reactions, or may be composed of a plurality of pairs of force and anodic reactions.
  • the electrochemical reaction system of the phosphatization treatment is a complex one composed of a plurality of pairs of cathode reactions and anode reactions. And the complexity makes control of the reaction system difficult.
  • Oxidation reaction of acid ion system 1. Oxidation reaction of gold JS ion accompanied by oxidation of the load
  • the part is skin a «component
  • the ions are deposited on the cathode surface as phosphate.
  • Electrochemical reaction of phosphoric acid conversion-1 (Electroless treatment reaction)
  • the electroless phosphoric acid conversion reaction is based on the anode and cathode reactions shown in the above table. It is a situation that is performed on the same surface without being polarized.
  • electroless phosphating is mainly applied only to steel materials is that the electrochemical reaction system spontaneously forms between the phosphating bath and the electroless system even if it is electroless.
  • the material to be treated is copper (Cu)
  • chlorine ions (C1) are added.
  • the object to be processed is an aluminum material (A 1)
  • fluorine ions (F—) are added.
  • F- fluoride ion
  • an electrochemical reaction system is formed on the same surface, and the formation of a film limits the dissolution of the material (object to be treated). Therefore, the film cannot be thickened without destroying it. If the reaction is continued forcibly to obtain a thick film, the reaction will involve the dissolution of the material (object to be processed), resulting in a rough film. Formed from electroless treatment (heating bath) and used for cold forging press lubrication That is why the thick coatings are rough.
  • the electroless phosphoric acid conversion treatment reaction is an electrochemical reaction system on the same surface without using an external power supply
  • the reductive precipitation reaction of metal ions accompanied by a change in charge is extremely limited.
  • reductive precipitation of Ni can be performed very little.
  • N i can be deposited only at the initial stage of film formation in which Fe dissolves.
  • the film to be formed is mainly composed of phosphate. This is the basis for calling the conventional electroless treatment a phosphoric acid conversion treatment.
  • composition of the treatment bath differs between the case where the film is formed only by anodic electrolysis and the case where the film is formed by anodic electrolysis + cathodic electrolysis o
  • Electrochemical reaction of phosphoric acid conversion treatment-3 (Cathode treatment)
  • the method of “anodic treatment cathodic treatment” is adopted.
  • the function of the anodic treatment is to dissolve the surface of the object to be treated and to secure the adhesion of the film.
  • the cathodic treatment forms a film.
  • the anodic treatment can be omitted in some cases. This is because if the adhesion of the skin is not required, and if the electrolytic phosphoric acid conversion treatment bath has a lower pH than the conventional electroless treatment bath and tends to dissolve the material even without electrolysis, It is when the reaction is carried out without electrolysis.
  • This interelectrode reaction is formed by a cathodic surface force side reaction (reduction and precipitation of metal ions) and an anode reaction (dissolution of metal) on the anode surface. .
  • This is an electrolytic reaction using an external power supply.
  • the cathode surface receives a large amount of electrochemical energy in a force-side reaction, so that a precipitation reaction involving a change (reduction) in charge can be performed.
  • the force source precipitation reaction is a precipitation reaction involving a change in charge (reduction) of metal ions such as nickel, copper, iron, and zinc, and has the same effect on the underlying metal as an electric plating. Combine with.
  • Metals that form a phosphate film such as iron and zinc are deposited preferentially as phosphates with no change in electric charge. It is higher than the anode reaction potential (0.83 V), and it is possible to change the charge and precipitate as a metal.
  • the reaction between the electrodes consists of an anode reaction on the cathode surface (dissociation of phosphoric acid ion, oxidation and formation of phosphate, and oxidation of solvent (water)), and a force source reaction on the anode surface (nitric acid). (Ion reduction and solvent (water) reduction).
  • anode reaction on the cathode surface dissociation of phosphoric acid ion, oxidation and formation of phosphate, and oxidation of solvent (water)
  • nitric acid nitric acid
  • Ion reduction and solvent (water) reduction When this electrochemical reaction system is formed, the phosphate crystals that are formed are firmly electrochemically bonded to the cathode surface as a film. Iii Anion / solvent (water) on the cathode surface
  • This reaction system consists of the oxidation reaction of water on the cathode surface (Equation (19), anode reaction), and the force ion precipitation reaction ((13), It is formed between (14), (15) and (16).
  • the formation of this reaction system reduces the ions dissolved in the phosphatization bath, and the potential (dissolution-precipitation equilibrium potential) to precipitate as metal ⁇ water anode About 0.83 V (hydrogen standard electrode potential) which is the reaction potential Direct deposition of a metal of a degree or more is possible.
  • V hydrogen standard electrode potential
  • metal ions having a dissolution-precipitation equilibrium potential equal to or higher than zinc can be deposited. Ensure that it is possible. That is, the metal that can be deposited at is determined.
  • Metals with low dissolution-precipitation equilibrium potential are those that cannot be electrolytically deposited and do not become film components. Therefore, those metal ions hinder the formation of the electrolytically treated film.
  • Zn, Fe, etc. can theoretically be changed as a metal and be deposited by changing the charge.
  • Zn, Fe, and the like generally exist in the form of a complex with phosphate ions in the treatment bath. Further, it is easier in terms of energy to precipitate as phosphate. Therefore, Zn, Fe, etc. are preferentially present as phosphate in the film.
  • the metal ions other than the components of the film are set to about 0 to 400 ppm, preferably 0 to 100 ppm or less, and solid substances that affect the film formation reaction
  • metal that does not form phosphate can be incorporated into the composite coating because it does not substantially contain, so that the composite coating itself can approach the characteristics of the conventional plating.
  • the phosphoric acid conversion coating film that was formed received high electrochemical energy and was able to adhere and fix to the cathode (object).
  • an oxidation-reduction (dissolution-precipitation) reaction system of metal ions between electrodes is continuously formed by connecting an external power supply. . Therefore, metals such as Ni can be reduced, deposited, and distributed in the entire film formation process. In addition, it is possible to include only a specific metal, and not to include a certain metal. In other words, it was possible to control the cathodic treatment film formation reaction.
  • the electrolytic phosphate film can be said to be a “phosphoric acid-containing composite electroplating film”.
  • the atomic number concentration ratio of the non-phosphate-forming metal (eg, Ni) of phosphorus (P), which is the element that forms phosphate is determined.
  • a film containing more than 1Z4 could be formed.
  • electrolytic phosphoric acid conversion treatment film of the present invention is that when the film is subjected to X-ray diffraction, a film having no peak of phosphate crystals is formed.
  • metal eg, Ni
  • the film formation is an electrolytic treatment, the deposition of metal (eg, Ni) with a change in electric charge occurs during the entire period of film formation. It is possible through.
  • the precipitation of phosphate crystals is caused by a change in the charge of a metal (eg, N This is considered to be the result of making the phosphate crystals finely dispersed in the metal component, depending on the precipitation of i).
  • the film of Example 3 is a film containing phosphorus (P) and Zn and containing phosphinate, but the phosphite crystals are dispersed with Ni metal to form a film. This is shown in the EPMA element analysis photographs of the film cross-sectional direction (Table 17, Fig. 20-29). This film can be referred to as a “phosphoric acid-containing composite electroplated film”.
  • the present invention has developed an electrolytic phosphoric acid conversion treatment suitable for the principle of the electrochemical reaction.
  • the phosphatized chemical conversion film can be used to form a film composed of phosphate and metal from a conventional film mainly composed of phosphite crystals. It was possible to provide a processing method. Furthermore, the composite film obtained by the present invention could be a material containing a metal material that was not phosphate.
  • this new phosphoric acid conversion treatment can provide a composite coating that can be applied to many metal materials, just as electroplating is applied regardless of the type of metal.
  • the electrolytic phosphoric acid conversion treatment consists of (1) equipment, (2) treatment bath composition, (3) treatment bath electrochemical conditions, and (4) electrolysis method.
  • Figure 3 shows the configuration during cathodic electrolysis.
  • 1 is a phosphating chemical treatment bath of the present invention
  • 2 is an object to be treated
  • 3 and 4 are working electrodes
  • 3 is a phosphating chemical treatment bath.
  • the working electrode 4 is composed of a phosphating chemical treatment bath, the ion dissolved in the phosphating bath is reduced, and the potential to precipitate as a metal is higher than the potential of the anodic electrolytic decomposition reaction of water as a solvent.
  • a working electrode made of a metal material having a voltage of not less than 0.83 V represented by hydrogen standard electrode potential).
  • 5 is a power supply for applying a voltage between the object 2 and the working electrodes 3 and 4, and 6 is a phosphoric acid conversion bath from the bath having the phosphatization bath 1.
  • 1 is a filtration / circulation pump that removes part of 1 and thermodynamically stabilizes the energy state of the phosphatization bath 1 as a liquid. This is a filter that removes solids precipitated in the phosphatization bath 1.
  • Reference numeral 8 denotes a non-electrolytic positive electrode made of a material that is insoluble in the phosphating bath 1 when the object is not in contact with the phosphating bath.
  • a replenishing chemical 10 having a concentration higher than the concentration of the components of the phosphatizing bath 1 is a chemical replenishing pump for introducing the replenishing chemical into the processing bath.
  • Reference numeral 11 denotes a control computer for controlling the supply amount of the replenishment chemicals, the applied voltage, and the like based on information from the sensor 12 for measuring the pH and the RP of the treatment bath.
  • the object to be processed (object to be processed) is connected to the cathode via a DC power supply, and is formed of an electrode made of a metal forming a phosphate film or a conductive material insoluble in a bath. (Hereinafter referred to as the working electrode) is connected to the positive electrode.
  • the working electrode is connected to the positive electrode.
  • the object to be treated is connected to the anode, and a conductive material insoluble in the bath is connected to the cathode.
  • An electrode for resting electrolysis is installed in the treatment tank.
  • the electrolysis electrode (cathode) for the rest electrolysis uses a conductive material that is insoluble in the bath. The role of this electrode is to prevent the working electrode from dissolving when the object to be processed (object to be processed) is not processed (during electrolysis suspension).
  • the insoluble conductive material is used as an anode and the working electrode is used as a cathode, and connected to a DC power supply.
  • microelectrolysis is performed to such an extent that the working electrode is not dissolved.
  • This electrolysis is called rest electrolysis. This resting electrolysis prevents the working electrode from dissolving in the bath when electrolysis is stopped, and prevents decomposition of the treatment bath.
  • a circulation pump is used to filter and circulate the treatment bath.
  • a filter is used to remove sludge that has been generated.
  • the electrolysis is terminated and the current to the object is stopped, the charge accumulated in the object is released to the processing bath. At that time, a part of the film is released into the bath. As they accumulate, they produce sludge. If these phenomena continue, sludge will continue to be generated. Filtration and circulation of the treatment bath suppresses those phenomena.
  • the sensor one electrode tank is provided with a PH electrode, an ORT electrode, an EC (electrical conductivity) electrode, a thermometer electrode, and the like. These electrodes cannot be installed in the treatment tank because the electrolytic current flows. Therefore, install separately o
  • Supplementary chemical tanks and pumps will be installed to supply chemicals. It is desirable that chemicals be supplied to the part (tank) after separation from the electrolytic cell in the filtration and circulation route of the treatment bath. This is because the electrolyzer is always microelectrolyzed even when it is not in operation, and is very electrochemically active. This is because, when the active tank is replenished with a higher concentration than the treatment bath in a simple tank, the chemical component ions react before dissolving in the bath, and a sludge is easily formed.
  • the control computer is installed to perform the electrolysis (reaction) properly.
  • the electrolytic phosphating bath of the present invention is a phosphating bath having a pH of 0.5 to 5.
  • the main factor that changes the phosphatization bath is the dissociation of phosphoric acid (H 3 P 0), which is a component of the phosphating bath. That is, the phosphoric acid (HP 0,) decomposes and increases the acid dissociation index (p Ka) of the phosphoric acid.
  • the acid dissociation index (pK a) is the logarithm of the reciprocal of the dissociation constant, and a larger value indicates a lower acid dissociation degree. That is, the strength as an acid is low.
  • the treatment bath contains phosphate ions, but the state is determined by electrolysis as HP 0, ⁇ HP 0, ⁇ HP 0, 2 ⁇ P 0, 3
  • H : i P 0, in the treatment bath is under the influence of always dissociating to H ”P ⁇ .
  • the acid activity of the treatment bath becomes relatively large, and HP 0 consumes acid (H +) in the treatment bath. Stabilizes in the direction (the direction in which phosphoric acid dissociates). That is, the solution containing mainly H 3 P 0, consumes the acid (H—), but the object is to dissolve the Fe electrode immersed in the treatment bath and consume the acid (H). You. One such effect is that the treatment bath decomposes and produces sludge.
  • the treatment bath mainly composed of H 3 P 0 contains a large amount of acid (H—), and as the ratio of the acid (H—) is large, the amount of metal ions dissolved in the treatment bath becomes large. The ratio becomes smaller. As a result, the ratio of “metal (Zn, Fe, Mn, etc.) component ion / (phosphate ion and phosphate)” in the treatment bath to the phosphate film is relatively high. Get smaller
  • the treatment bath is mainly composed of H 2 P 0,-, it will contain metal ions instead of a large amount of acid (H—), and the proportion of metal ions dissolved in the treatment bath becomes larger.
  • the ratio of the metal (Zn, Fe, Mn, etc.) component ion / (phosphoric acid ion and phosphoric acid) in the treatment bath, which becomes phosphoric acid and enters the film, is relatively high. It becomes larger.
  • the degree of dissociation of phosphoric acid in the treatment bath is as follows: “The metal (Zn, Fe, ⁇ , etc.) that forms phosphoric acid and enters the film is ion Z (phosphoric acid and phosphoric acid).
  • the stability of the treatment bath in the electrolytic treatment is determined by controlling the ratio of the metal (Zn, Fe , Mn, etc.) by controlling the ratio of component ion / (phosphoric acid ion and phosphoric acid).
  • Metal entering the film becomes re emissions salt (Z n, F e, M n , etc.) to focus on the component ions are those metal ions are Li phosphate ions in solution (H 2 P 0, -) and This is because a complex is formed, thereby stabilizing the phosphate ion (H 2 P 0). Therefore, even if metal (N i, Cu, etc.) ions that do not become phosphoric acid are dissolved, complexation of phosphate ions P 0, Does not contribute to the stabilization of the treatment bath.
  • the ratio of ““ metals (Zn, Fe, Mn, etc.) that form phosphate and enter into the film) component ions Z (phosphate ions and phosphate) ” is determined by the ion concentration (g / ) The ratio can be displayed.
  • the nitrate ion-metal entering the film becomes re emissions salt (Z n, F e, M n , etc.) component ions, metal that do not re-emission salt (N i, C U, etc.)
  • Z n, F e, M n , etc. concentration of metals that become phosphates and enter the film
  • Z (phosphoric acid) concentration of ion and phosphoric acid (g / 1)
  • the treatment bath is orthophosphoric acid (H 3 P
  • the upper limit of the above ratio is determined from “solubility of a metal (Zn, Mn, etc.) component ion in a treatment bath that becomes phosphate and enters the film” and “a practical viewpoint”.
  • the metal ions that become phosphate and enter the film are dissolved in nitrate to form a solution (treatment bath).
  • Zn nitrate and Mn nitrate are highly soluble compounds.
  • Nitric acid Zn solution or nitric acid Zn + nitric acid Ni It is possible to add 1 to 10 g / l of phosphoric acid to the solution for electrolytic treatment. In such a case, a major factor that hinders the film formation by turbidity of the treatment bath is the solubility of the solution.
  • the electrolytic phosphoric acid conversion treatment it is assumed that Zn, Ni, etc. are dissolved, but if dissolved as zinc nitrate, it is possible to dissolve zinc in lOOg / 1. is there.
  • the concentration of metal (Zn, Fe, Mn, etc.) component ions (g / 1) / (phosphate ion and phosphate concentration)
  • the upper limit of degree (g / 1)) is about 10 to 100.
  • Electrolytic phosphoric acid conversion treatment baths are basically classified into the following components.
  • the anions are as follows: 1) Nitrate ion (oxo acid (oxygen acid) ion containing nitrogen, where ion nitrate is obtained by dissolving nitrate Ni, nitrate Zn, etc. And must not be supplied from nitric acid (HNCh). 2) Contains phosphate ions.
  • the cations are as follows: (1) Metal ions that crystallize as a phosphate in films of zinc, manganese, calcium, iron, etc., and are used as phosphate ions and phosphate conversion baths. Metal ions that form a complex in the metal; (2) Nickel, copper, etc.
  • this treatment bath composition classification is that the treatment bath components are classified into four according to the role (function) in the film formation reaction. This view (recognition) does not exist in the conventional phosphoric acid conversion treatment.
  • examples include fluoride ions when targeting aluminum materials and chlorine ions when targeting copper materials.
  • the only metal ions that change (reduce) the charge of metal ions and deposit (form a film) are nickel when treating steel.
  • nickel only precipitates at the interface of iron and cannot be present on the outermost surface of the film. This indicates that the reaction is performed only in response to the precipitation of iron with a change in nickel charge and the dissolution of iron.
  • Nickel does not precipitate except at the steel interface because there is no dissolution of iron.
  • the metal ions that change (reduce) the charge of metal ions such as nickel and deposit (form a film) in an electrolyte solution in an environment that can be reduced using an external power supply The range can be expanded.
  • electrolytic treatment it is a dissolution-precipitation equilibrium potential (force source deposition reaction potential) that is higher than the anode electrolysis reaction potential (10.83 V) of water on the cathode surface.
  • Metal ions can be deposited.
  • Corresponding metals are copper, nickel, iron, zinc, tin, lead, chromium, etc.
  • the treatment bath contains a small amount (0.1 lg Zl or less) or no metal ion that changes (reduces) the charge of the metal ion and deposits (forms a film).
  • a small amount 0.1 lg Zl or less
  • no metal ion that changes (reduces) the charge of the metal ion and deposits (forms a film).
  • the film used for lubrication treatment of steel for cold forging be formed of a uniform zinc phosphate crystal with reduced adhesion to the material. This is because good adhesion reduces lubrication.
  • Such a film formation requires a bath that does not contain metal ions that change (reduce) the Ni and other charges.
  • the concentration of ion nitrate is 6 gZl to 140 g / l, and the concentration of ion phosphate and phosphoric acid is 0.5 gZ1 to 60 gZ1, for example, zinc,
  • the concentration of metal ions that form a complex with at least one phosphate ion of manganese, iron and calcium in a phosphate conversion bath is 1 g / 1 to 70 g Z1 and For example, ions dissolved in at least one of the phosphoric acid conversion baths of nickel, copper, iron, zinc and chromium are reduced, and the potential to precipitate as metal is reduced.
  • the concentration of the metal ion described above is preferably 0 gZ1 to 40 gZ1.
  • Items specified for the treatment bath electrochemical conditions include P H, ORP (redox potential), EC (electric conductivity), and temperature.
  • the driving energy for the electrochemical reaction was dependent on the chemical energy of the chemical treatment bath. Therefore, it is necessary to strictly define the electrochemical conditions that define the situation of the electrochemical reaction.
  • the electrolysis process depends on an external power source for the driving energy of the electrochemical reaction. In other words, the degree to which the electrochemical conditions contribute to the promotion of the reaction is small compared to the electroless treatment. Therefore, it is not necessary to strictly specify the electrochemical conditions of the treatment bath.
  • a preferable range of PH is 0.5 to 5.
  • the reason why the pH width is large is that it corresponds to the composition of the treatment bath.
  • the treatment bath of this embodiment is an electrolyte treatment bath that does not contain substances that do not participate in film formation. Therefore, even in the region of pH 4 or more, the treatment bath can exist without generating sludge.
  • the ORP (oxidation-reduction potential) of the treatment bath reflects the composition of the treatment bath.
  • Table 3 shows the reaction formulas involved in the electrolytic phosphoric acid conversion treatment. Among them, the one with the highest reaction potential is the power-soil decomposition reaction of water (1.23 V). Also, the one that shows the lowest reaction potential is the anode electrolysis reaction of water (-0.83 V). Therefore, the ORP of the treatment bath of the present invention is in principle preferably between -0.83 V force and 1.23 V. Further, a range of 0 to 1 V (hydrogen standard electrode potential) is preferable.
  • E C electrical conductivity
  • the method of measuring conductivity is not strictly standardized. For general measurements, a range of 4 to 60 ms is preferred.
  • the treatment bath temperature is preferably in the range of 10 to 90 ° C. This is because the treatment bath does not contain ions that do not participate in film formation, is stable against heat, and uses an external power supply to promote the reaction, so it can capture energy even in a low-temperature region.
  • the practical temperature depends on the composition of the treatment bath.
  • a metal material is selected as the anode electrode material that forms a film.
  • iron, zinc, nickel and copper are common.
  • manganese-containing alloys, calcium-containing alloys, and magnesium alloys that form phosphate compounds it is also possible to use a metal material having a standard electrode potential of 0.83 V or more, such as tin or lead. These metals can be used alone or as a combination of multiple materials as anodes.
  • the composition of the treatment bath (anion, cation) is described above.
  • the treatment bath does not contain anions other than nitrate ions and phosphate ions in principle, but contains other ions depending on the type of the material to be treated.
  • fluorine ion In the case of coating the aluminum material, a small amount of fluorine ion can be included for the purpose of accelerating the dissolution reaction of the aluminum material. In this case, fluorine ion does not become a film component, but is effective in accelerating the dissolution reaction of the aluminum material. Therefore, it is permissible to add a small amount of fluorine ion to replenish the amount removed from the treatment bath.
  • Electrolysis method and conditions are what voltage and current should be applied between the selected working electrode (anode) and the workpiece (cathode). Electrolysis method • Conditions vary depending on the type of working electrode selected and the type of film to be formed. In general, the working electrode is composed of two types of metals, which crystallize as phosphate (zinc, iron,) and metals that reduce and precipitate metal ions (nickel, copper,). Used.
  • the electrolysis voltage is 1 to 50 V, and the electrolysis current is 0.01 to 1 O A / dm-'.
  • the electrolysis time is not specified.
  • Various films can be formed by devising the cathodic electrolytic treatment. For example By using a zinc-rich bath and using a zinc electrode, it is possible to form a zinc-rich coating. Such coatings are applied to cold forged substrates.
  • electrolysis is first performed using the Mi electrode, and then each electrolysis is performed using the Ni electrode and the iron electrode.
  • a film containing a large amount of can be formed. Films containing a large amount of nickel have excellent adhesion to iron substrates (substrates) and are suitable for painting substrates.
  • Table 5 shows the differences from the conventional electrolytic phosphoric acid conversion treatment method.
  • the fundamental difference is the composition of the treatment bath.
  • the treatment bath of the present embodiment is a “bath that does not contain impurities suitable for reacting components in a solution in an electrolytic reaction”, whereas a conventional electrolytic treatment bath is a “bath of an electroless treatment bath”. Is a bath that contains impurities.
  • Treatment bath composition (1) Phosphorus ion, nitrate ion (1) Phosphate ion, nitrate ion
  • the content of the electrochemical reaction of the film forming reaction of the present embodiment is different from that of the conventional method.
  • the content of the electrochemical reaction of the present embodiment is mainly “electrode-electrode reaction” as shown in the classification of cathodic electrolysis reaction (Table 4).
  • Japanese Patent Publication No. 5-8222481 does not assume such an "electrolytic reaction between electrodes".
  • Japanese Patent Publication No. 5-82222480 intends electrolytic treatment to reinforce the electrochemical reaction in conventional electroless phosphatization.
  • the electrolysis reaction mainly consists of “electrolysis reaction between the object to be treated (solid) and the treatment bath (liquid) on the same metal surface”.
  • Table 6 summarizes the differences (contents) between the present invention and the electroless treatment.
  • Table 6 Differences in electrolysis reaction Electroless treatment Electrolysis treatment (invention) t * Electric repulsion between electrodes in treatment bath f
  • the feature of the film of the present invention is that the film mainly consists of an electrochemical reaction between the electrodes. In other words, it is a film formed by obtaining greater electrochemical energy than a film obtained by electroless treatment.
  • Table 7 shows the steps of Examples and Comparative Examples.
  • Table 8 shows the compositions and electrochemical conditions of the phosphating baths of the examples and comparative examples.
  • Table 8 Composition and electrochemical conditions of phosphate chemical conversion treatment
  • Comparative Example 2 is a thick film type film used for cold forging lubrication. In order to form a thick film by electroless treatment, it is necessary to heat the bath, and the bath is maintained at 80 ° C
  • the air-conditioner parts for automobiles (clutches, steatanos, wings) shown in the figure were used as the objects to be treated.
  • the plate (blow-cut part) that becomes the flat part 20 in the coating evaluation test and the housing (the pressed part) that becomes the outer peripheral part 21 are welded. And joined .
  • the housing, which is the outer periphery, is obtained by pressing a flat plate into a structure with irregularities. Therefore, the outer periphery of the housing is a surface that has been greatly deformed by press working. A large deformed surface is deformed significantly during pressing, and at the same time, the lubricating oil adheres strongly.
  • the object to be treated was subjected to the phosphorylation treatment under the conditions shown in Table 7 and Tables 8 and 9.
  • the 0RP display value in Table 8 is the potential (mV) displayed with reference to the AgZAgC1 electrode.
  • +21 OmV is applied to the value displayed with reference to the Ag / AgC1 electrode, it is converted to the hydrogen standard electrode potential.
  • the workpiece was subjected to electrodeposition coating in the steps after the chemical conversion treatment in Table 7.
  • the workpieces subjected to the electrodeposition coating were subjected to a coating corrosion resistance evaluation test.
  • the coating corrosion resistance evaluation test the coating film was scratched until it reached the base with a knife on the flat part and the outer peripheral part of the object to be treated. Soaked for hours.
  • the object to be treated after immersion for 240 hours was washed with water, allowed to stand for about 2 hours or more and dried, and then an adhesive tape was applied to the coating surface damaged by knife to strongly peel. Measure the width of the peeled coating film by tape peeling and evaluate the coating corrosion resistance. (4) Smaller separation force ⁇ , good corrosion resistance.
  • the results of the coating corrosion resistance evaluation are shown in Table 10 in comparison with Comparative Example 1. Comparative Example 1
  • the object to be treated is the same as that in Example 1.
  • the process is surface adjustment Except that the process was added and that the phosphatization was performed electrolessly.
  • the phosphoric acid conversion treatment was performed by electroless treatment according to the methods shown in Tables 8 and 9.
  • the coating corrosion resistance was evaluated in the same manner as in Example 1.
  • the results of the coating corrosion resistance evaluation are shown in Table 10 in comparison with Example 1.
  • Table 10 shows the results of the coating corrosion resistance evaluation.
  • the comparison between Example 1 and Comparative Example 1 clearly shows that Example has better corrosion resistance.
  • the flat part and the outer peripheral part the flat part is better.
  • Comparative Example 1 a large difference in the corrosion resistance occurred between the flat portion and the outer peripheral portion. This is because, as mentioned earlier, in the electroless treatment, the effect of the reduction of the chemical conversion treatment reaction on the metal surface due to the press working has come out.
  • Example 1 is an electrolytic treatment, large electrochemical energy can be used for the electrolytic reaction. Therefore, it has good corrosion resistance because it forms a phosphoric acid conversion coating without being affected by press working.
  • Paint corrosion resistance evaluation results maximum peel width
  • Example 1 The phosphoric acid conversion coatings of Example 1 and Comparative Example 1 are analyzed with an energy dispersive X-ray analyzer (EDX) and a glow discharge analyzer (GDS). c The analysis was performed separately for the flat part and the outer part. Table 11 shows the results. Table 11 List of analysis results (chit) of coatings
  • EDX provides information on the constituent elements of the coating.
  • the film analysis was performed under the same conditions from Fig. 5 to Fig. 8.
  • the chart of EDX is compared between Example 1 (FIGS. 5 and 6) and Comparative Example 1 (FIGS. 7 and 8) at the same portion of the object to be processed. Compare the flat parts. In Figure 5 (electrolytic treatment), the nickel peak is higher than the zinc peak, while in Figure 7 (electroless treatment), the zinc peak is higher than nickel. This tendency is also seen in the comparison of the outer periphery (Figs. 6 and 8).
  • Table 12 shows the atomic number concentration analysis results of the film obtained from the EDX analysis results performed under the same conditions from FIG. 5 to FIG.
  • the atomic number concentration obtained from the EDX analysis results includes carbon (C) and gold (Au). However, since carbon and gold are not film components, they are excluded from consideration.
  • the ratio of the constituent elements of the coating is determined by the phosphate coating. Calculate the atomic number concentration ratio of each element to the phosphorus (P) that must be included.
  • Example 1 has many Nis at 2.1 and 1.9 at both the flat part and the outer peripheral part, but Comparative Example 1 has a flat part at 0.0. 1, the outer circumference 0.12 and P are extremely large. This indicates that the film formed by the electrolytic treatment contains a large amount of metal ( ⁇ 'i) that does not become phosphate. On the other hand, in the electroless treatment, a phosphate-based film was formed strongly, and the result of Comparative Example-1 proves this fact. These results indicate that a film containing a large amount of metal i) which does not become phosphate is suitable for the undercoat treatment and improves the corrosion resistance. Note that in Comparative Example 1, the plane portion had more lins than the outer peripheral portion. The reason for this is that it is difficult to form a film on the outer periphery, and the phosphoric acid conversion film is not formed reliably, so that the number of phosphorus, the main component of the film, is reduced.
  • F e is an element that is a base and also forms a film with phosphate crystals.
  • the ratio of Ni / Fe indicates the ratio of Ni to Fe in the skin if the film is formed reliably, and the ratio of Ni to the substrate surface if the film is not formed reliably. Indicates the ratio of i.
  • Ni / Fe is 1 or more in both the flat portion and the outer peripheral portion, whereas in Comparative Example 1, Ni / Fe is 1 or less in both the flat portion and the outer peripheral portion.
  • GDS performs a glow discharge on the film, thereby analyzing the elements coming out of the film
  • GDS informs of (1) the distribution of the elements in the film and (2) the strength of the bond between the films.
  • Distribution of elements in the coating can be read directly from the GDS chart.
  • the “strength of the film” can be compared by the time it takes to reach the iron substrate when the analysis is performed under the same conditions. In other words, the longer the time to reach the iron substrate, the stronger the film.
  • the applied voltage was changed depending on the type of element. Therefore, the analysis results of each film do not give information on the “abundance ratio between elements in the film”.
  • the analyzes in Figures 9 to 12 are performed under the same conditions. Therefore, it is possible to compare the presence of elements in the film between each sample (film).
  • the GDS is also the same part of the object to be processed, and is compared between the embodiment (FIGS. 9 and 10) and the comparative example (FIGS. 11 and 12).
  • the flat part can be analyzed for how nickel is included in the film by looking at the charts in Fig. 9 (electrolytic treatment) and Fig. 11 (electroless treatment).
  • Figure 9 electrolysis treatment
  • Fig. 11 electroless treatment
  • Fig. 9 electrolytic treatment
  • iron atoms increase slowly in the film, indicating that the iron electrode (anode) used in the electrolytic treatment was dissolved to form a film. Suggests. Since iron behaves differently from phosphorus (P), it is presumed that iron can be incorporated into the film as an iron atom (metal) in the same way as nickel.
  • the bond strength of the film is considered.
  • the bond strength of the film can be obtained by comparing the time (A) required for the film to pass through the GDS and reach the iron substrate (A).
  • Table 13 shows the results.
  • Table 13 3 Depth of film by GDS analysis (strength of film) This evaluation shows that the chemical conversion treatment time of the article to be treated is almost the same as the force ⁇ , and that Example 1 has three times the strength of Comparative Example 1.
  • Example 2 the treatment bath of Example 1 had a nitrate ion concentration that was about 1/2 that of the treatment bath of Comparative Example 1. This is only possible if the electrolysis is carried out in a sodium-free bath. Since the nitric acid concentration is reduced, the present invention is an environment-friendly technology.
  • Example 2
  • This part (pipe shape with a diameter of 23 mm and a length of 8 O mm) has a spiral (spline shape) groove formed by cold forging to engage gears inside the pipe shape. Formed.
  • the material is an alloy containing about 1% chromium.
  • the phosphoric acid conversion treatment is performed as a cold forging press lubrication base. Therefore, the purpose of the phosphate conversion coating is to reduce the load during cold forging. Therefore, the evaluation of the film is also based on the load during cold working.
  • the subject was subjected to electrolytic phosphate conversion treatment under the conditions shown in Table 7 and the conditions shown in Tables 8 and 9.
  • the object to be treated reacts sodium stearate with the phosphate conversion film to form a metal stone film (zinc stearate). After that, cold forging press work is performed.
  • Example 2 An object to be treated is the same as that in Example 2.
  • the process is the same as Example 2 except that the pickling was performed and the surface conditioning process was omitted, and that the phosphoric acid conversion treatment was different.
  • the phosphoric acid conversion treatment was carried out by electroless treatment (80 ° C) by the methods shown in Tables 8 and 9. Comparative Example 2 This is a processing method for mass production equipment that is currently flowing.
  • Table 14 summarizes the evaluation of the cold forging press working load and the analysis of the film.
  • the “cold forging press, working load” in Table 14 is the load received by the press machine during cold forging press working. Lubricating performance is better when the cold stamping load is lower.
  • the weight of the coating was analyzed by the following method.
  • the “melt content” is obtained by immersing the object in water at 100 ° C. for 10 minutes, measuring the weight before and after the immersion, and dividing the obtained weight by the surface area of the object.
  • metal stone component the object to be treated is immersed in isopropyl alcohol (IPA) at 75 ° C for 20 minutes, the weight before and after the immersion is measured, and the obtained weight is calculated as the surface area of the object. It is divided.
  • IPA isopropyl alcohol
  • Li emissions salt coating fraction is the weight of soaked 2 0 minutes to the object to be treated 5 0 70 ° 5% chromic acid C (C r ⁇ 3), was weighed before and after, the resulting Is divided by the surface area of the workpiece.
  • Table 14 shows the analysis results of the atomic number concentration (%) of EDX. Table 14 Evaluation of cold curse load and analysis of coating
  • Example 2 shows that it is superior to Comparative Example 2.
  • Table 14 “Results of layer stratification and weight analysis”.
  • Table 14 “Film layers And the results of the gravimetric analysis ”, the coating of Example 2 contains about 5 times as much metal stone as the coating of Comparative Example 2.
  • Metallic stone components greatly contribute to cold forging press working lubrication. Therefore, it is clear that the higher the content of the component, the lower the cold forging press working load.
  • the metal stone component is zinc stearate, it is necessary to contain a large amount of zinc in the film.
  • the zinc in the film can be known from the results of EDX analysis. Comparing the charts of FIGS. 14 and 15, the electrolytically treated film, Example 2 (FIG. 14), contains less iron and more zinc. You can confirm that you are out. In addition, it is confirmed quantitatively by comparing the atomic number concentration (%) of EDX in Table 12. When the chemical structure of-phosphate chloride conversion coating and Z n 3 (P 0 4) 2, atomic concentration ratio of Z n for P (Z n ZP) becomes 1.5.
  • composition of the film can be changed by the electrolytic treatment.
  • excess Zn in relation to the chemical structure of Zn 3 (P 0,) 2 is changed into a film as zinc metal with a change in charge. This is made possible for the first time by the electrolytic treatment of the present invention. And that contributes greatly to the reduction of cold forging press working load.
  • Example 3 shows that it is a film coating of Example 2 contains no lambda tau i is a Rana have metal such as Li down salt. Electrolytic phosphoric acid conversion treatment can also exclude such metals that do not turn into phosphate.
  • Example 3 and Comparative Example 3 confirm the difference in the film formed by the electrolytic treatment.
  • Example 3 and Comparative Example 3 using the automotive air conditioner parts used in Example 1 and Comparative Example 1 as the objects to be treated, phosphoric acid conversion treatment was performed in the process shown in Table 7. And electrodeposition coating. The electrolytic phosphoric acid conversion treatment was performed under the conditions shown in Tables 8 and 9. The main difference between Example 3 and Comparative Example 3 is the difference in the phosphatization treatment bath. The bath of Example 3 does not contain Na ions, while the bath of Comparative Example 3 contains Na ions. The coating corrosion resistance of Example 3 and Comparative Example 3 was evaluated in the same manner as in Example 1 and Comparative Example 1. Table 15 shows the results. Table 15 Evaluation results of coating corrosion resistance (maximum peel width)
  • Table 16 shows the results of X-ray diffraction diagrams of the phosphoric acid chloride conversion coatings of Example 3 and Comparative Example 3. Table 16 X-ray diffraction results of the coating
  • Example 3 The difference between Example 3 and Comparative Example 3 regarding the phosphate conversion coating
  • Example 3 did not contain phosphate crystals. This indicates that the phosphate crystals are very fine. As a result, this indicates that the composite of Ni metal and phosphate crystals is progressing.
  • Table 17 summarizes the fact that the coating of Example 3 shows that the composite of Ni metal and phosphate crystals is progressing.
  • EPMA Electro Probe Micro Analysis
  • Example 4 and Example 5 were examples in which Ni was reliably formed under the phosphate for the base of the coating, the amount of Fe electrolysis was reduced, and the decomposition tendency of the treatment bath was reduced as much as possible. It is. Therefore, in the cathodic electrolysis, in the first stage, electrolysis of only Ni is performed, and then electrolysis of Ni and Fe is performed simultaneously. At this time, the amount of electrolysis of Fe was as small as 1 Z 3 to 18 of Example 3.
  • Example 4 the air conditioning component for the vehicle used in Example 3 was used as the object to be treated, and the phosphoric acid conversion treatment and the electrodeposition were performed in the processes shown in Table 6. Painting is done.
  • the electrolytic phosphoric acid conversion treatment was performed under the conditions shown in Tables 8 and 9-The coating corrosion resistance of Examples 4 and 5 was evaluated in the same manner as in Example 1. The results are shown in Table 18. 00/36191 Table 18 Evaluation results of coating corrosion resistance (maximum peel width)
  • Example 4 and Example 5 are also excellent when compared with Comparative Example 3. As described in Example 1, the outer periphery is a place where it is difficult to form a film by electroless treatment. Example 4 and Example 5 show that if the electrolytic treatment of the present invention is performed, a film can be formed on such a surface, and corrosion resistance can be ensured.
  • Atomic number concentration (%) Atomic number S degree ratio to P Atomic number S degree ratio
  • Embodiments 4 and 5 show an example in which two electrodes, Fe and Ni, are used to carry out the cathodic electrolytic treatment. And it shows that the method is effective.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Cette invention se rapporte à un procédé de phosphatation convenant à un traitement électrolytique, qui utilise un bain de phosphatation contenant un ion phosphate et de l'acide phosphorique, de l'acide nitrique, un ion métallique capable de former un complexe avec le ion phosphate dans le bain de phosphatation et un ion métallique ayant un potentiel électrique auquel l'ion métallique dissous dans le bain de phosphatation est réduit et se dépose sous la forme de métal d'une valeur identique ou supérieure à celle de la réaction par électrolyse anodique de l'eau, ainsi qu'au solvant utilisé dans ce bain. Ce bain contient un ion métallique autre qu'un constituant du revêtement devant être formé selon une quantité comprise entre 0 et 400 ppm et ce bain est sensiblement exempt de particules solides pouvant affecter la réaction de formation du film de revêtement.
PCT/JP1999/007124 1998-12-17 1999-12-17 Procede de phosphatation electrolytique et revetement composite forme sur une surface d'acier WO2000036191A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CA2320865A CA2320865C (fr) 1998-12-17 1999-12-17 Procede de phosphatation electrolytique et revetement composite forme sur une surface d'acier
EP99959898A EP1074640A4 (fr) 1998-12-17 1999-12-17 Procede de phosphatation electrolytique et revetement composite forme sur une surface d'acier
BRPI9907916-0A BR9907916B1 (pt) 1998-12-17 1999-12-17 processo de tratamento quÍmico por fosfato eletrolÍtico para formar uma pelÍcula, e, pelÍcula composta sobre uma superfÍcie de aÇo.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP35925498 1998-12-17
JP10/359254 1998-12-17

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WO2000036191A1 true WO2000036191A1 (fr) 2000-06-22

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JP3479609B2 (ja) * 1999-03-02 2003-12-15 日本パーカライジング株式会社 スラッジ発生のないリン酸亜鉛処理液およびリン酸亜鉛処理方法
JP4019723B2 (ja) * 2001-02-23 2007-12-12 株式会社デンソー 電解リン酸塩化成処理方法
WO2006007730A1 (fr) * 2004-07-21 2006-01-26 The University Of British Columbia Implants osseux et procedes d'enrobage de ces implants
DE102005023023B4 (de) * 2005-05-19 2017-02-09 Chemetall Gmbh Verfahren zur Vorbereitung von metallischen Werkstücken zum Kaltumformen, mit dem Verfahren beschichtete Werkstücke und ihre Verwendung
EP2186928A1 (fr) * 2008-11-14 2010-05-19 Enthone, Inc. Procédé pour le post-traitement des couches métalliques
CN113073371A (zh) * 2021-03-22 2021-07-06 领润(南京)绿色化学有限公司 一种清洁型对阳极板友好型电解磷化液及其磷化工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993022481A1 (fr) * 1992-04-30 1993-11-11 Nippondenso Co., Ltd. Procede de phosphatation

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DE4111186A1 (de) * 1991-04-06 1992-10-08 Henkel Kgaa Verfahren zum phosphatieren von metalloberflaechen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993022481A1 (fr) * 1992-04-30 1993-11-11 Nippondenso Co., Ltd. Procede de phosphatation

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Title
See also references of EP1074640A4 *

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CN1293720A (zh) 2001-05-02
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CA2320865C (fr) 2010-03-16
BR9907916A (pt) 2002-04-30
CA2320865A1 (fr) 2000-06-22
KR20010040816A (ko) 2001-05-15
EP1074640A1 (fr) 2001-02-07
BR9907916B1 (pt) 2011-07-26
KR100400522B1 (ko) 2003-10-10

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