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WO2011013360A1 - Liquide de traitement pour former un film protecteur pour élément en acier comportant une couche de composé d'azote, et film protecteur de couche composite - Google Patents

Liquide de traitement pour former un film protecteur pour élément en acier comportant une couche de composé d'azote, et film protecteur de couche composite Download PDF

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Publication number
WO2011013360A1
WO2011013360A1 PCT/JP2010/004780 JP2010004780W WO2011013360A1 WO 2011013360 A1 WO2011013360 A1 WO 2011013360A1 JP 2010004780 W JP2010004780 W JP 2010004780W WO 2011013360 A1 WO2011013360 A1 WO 2011013360A1
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compound layer
protective film
treatment
treatment liquid
steel material
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PCT/JP2010/004780
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English (en)
Japanese (ja)
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小西知義
池田芳宏
別府正昭
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日本パーカライジング株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
    • C21D1/10—Surface hardening by direct application of electrical or wave energy; by particle radiation by electric induction
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
    • C23C8/48—Nitriding
    • C23C8/50—Nitriding of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present invention relates to a hardened steel material used as a mechanical structural component having excellent mechanical strength such as surface pressure strength, wear resistance, bending fatigue strength, a manufacturing method thereof, and a treatment liquid used therefor.
  • nitriding treatment including soft nitriding treatment
  • carburizing and quenching and induction hardening
  • induction hardening are performed on cast iron and steel mechanical structural parts.
  • a compound layer made of nitride formed on the outermost surface by nitriding treatment is known to have excellent sliding properties, wear resistance, and high seizure resistance (hereinafter referred to as nitrogen compound).
  • nitrogen compound a compound layer made of nitride formed on the outermost surface by nitriding treatment
  • nitrogen compound high seizure resistance
  • Called layer effect I
  • nitriding treatment is inferior in surface pressure strength, fatigue strength, etc. compared to carburizing quenching and induction quenching.
  • the nitrogen compound layer peels from the steel substrate. There is a case.
  • the nitrogen compound layer had rather an adverse effect in fatigue tests at high surface pressures exceeding 2 GPa.
  • the present inventors have found that this factor is not in the compound layer itself but because the hardened layer depth of the substrate supporting the compound layer is shallow. In other words, the nitriding unit alone has insufficient the depth of the hardened layer immediately below it in order to make full use of the good slidability of the outermost compound layer.
  • a steel material containing nitrogen has a finer martensite structure obtained after quenching than a steel material not containing nitrogen, so that the hardness is increased, and the hardening depth is increased by improving the hardenability.
  • the nitriding treatment can also be used as a nitrogen diffusion pretreatment for forming a nitrogen diffusion layer for improving hardenability (hereinafter referred to as effect II by forming a nitrogen compound layer). That is, the characteristics that can be obtained by using this effect II are not due to the action of the nitrogen compound layer itself, but due to the action of diffused nitrogen in the steel immediately below the nitrogen compound layer generated when the nitrogen compound layer is formed.
  • the nitrogen-containing martensite structure obtained by quenching has high surface pressure strength and high fatigue strength due to resistance to temper softening, resistance to crack initiation and growth, in addition to the above-mentioned high hardness and hardenability improvement. It has been known.
  • the quenching temperature needs to be at least the temperature Ac3 transformation point at which an austenite structure is formed, and is usually selected from a temperature range of 750 to 1050 ° C.
  • the nitrogen compound layer formed at a nitriding temperature of 570 ° C. is a combination of iron and nitrogen.
  • the nitrogen compound layer undergoes oxidation and decomposes. It is released as a gas and the nitrogen compound layer disappears. This has been reported for a long time (Non-Patent Document 1).
  • the combined heat treatment technique by nitriding and quenching usually uses only the effect II of the nitrogen diffusion layer obtained by nitriding, and does not use the effect I of the nitrogen compound layer formed by nitriding. That is, the nitrogen compound layer does not stop disappearing during quenching, which is a subsequent process of nitriding.
  • this technology for example, the composite heat treatment disclosed in Patent Documents 1 to 5.
  • Patent Document 6 discloses a composite heat treatment method in which a nitriding treatment is performed at a temperature of 600 ° C. or higher to form a nitrogen compound layer having a thickness of 5 ⁇ m or less, followed by induction hardening to obtain a quenched member having a nitrogen compound layer having a thickness of 2 ⁇ m or less. ing.
  • the reason why the nitriding condition is set to a high temperature of 600 ° C. or higher in the present technology is that a higher concentration of nitrogen diffusion can be expected at the deeper side of the steel material, but the nitrogen compound layer obtained at a nitriding temperature exceeding 600 ° C. has a hardness.
  • Patent Document 7 discloses this.
  • Patent Document 8 to be used for both effects I and II, a hard nitride layer is formed on the surface of the steel material, and further, Ti, Zr, Hf, V, Nb, Ta, Cr, W are formed thereon.
  • hardened steel member characterized by the inorganic compound layer containing at least one metal oxide selected from the group consisting of Mo and Al is formed is disclosed.
  • Patent No. 3193320 Japanese Patent No. 3327386 Japanese Patent No. 3145517 JP-A-7-90364 JP 2007-154254 A JP 2007-77411 A JP 58-96815 Heat treatment Vol.16 No.4 P206 1976 JP 2008-038220
  • the object of the present invention is to provide a method for producing a hardened steel material, a steel material, and a treatment liquid used therefor that prevent oxidation by induction hardening of a compound layer formed on the surface of the steel material by nitriding.
  • the present invention (1) is a treatment liquid for forming a protective film for protecting a nitride on a nitride layer formed after nitriding treatment on a steel material, and includes Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and at least one selected from the group consisting of Mo, phosphate ion, condensed phosphate ion, Contains 0.1 to 60 g / L of at least one anion selected from the group consisting of phosphite ions, fluoride ions, carbonate ions and silicate ions, and the treatment solution has a pH of 4 to 14 It is a compound layer protective film formation processing liquid characterized by being.
  • the treatment solution is a compound layer protective film formation treatment liquid in the invention (1), characterized in that it comprises at least one amine of 0.1 ⁇ 400g / L.
  • the treatment liquid is selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo.
  • At least one dissolved ion selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg and Mo Dispersed particles having an average particle size of 4 to 40 nm including at least one selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al,
  • the compound layer protective film of the invention (4) is formed on the nitride layer and is heated to a predetermined heating temperature. subjected to heat 0.3-5 seconds until it reaches its ultimate temperature is hardened steel material, characterized in that the induction hardening process is applied is 750 ⁇ 860 ° C..
  • Application process invention (6) preparing a steel nitride layer is formed on the surface by nitriding treatment, to be applied to the invention (1) to (3) one of the process liquid nitride layer A protective film forming step of drying the treatment liquid after the application step and forming a compound layer protective film on the nitride layer; and after the protective film forming step, 0.3 to 5 seconds until a predetermined heating temperature is reached.
  • a method for producing a hardened steel material comprising: heating and induction hardening with an ultimate temperature of 750 to 860 ° C.
  • the protective layer forming film of the present invention is formed on the compound layer obtained by nitriding treatment.
  • the compound layer protective film it is possible to effectively suppress oxidative decomposition of the compound layer due to subsequent induction hardening.
  • the steel member obtained by the present invention maintains the mechanical strength, sliding resistance, wear resistance and the like based on the characteristics of the compound layer as a result of the remaining compound layer having good sliding characteristics.
  • steel members whose hardenability is improved by the diffused nitrogen can obtain a deep hardening depth and high hardness by induction hardening, so that the surface pressure strength, wear resistance, and bending fatigue strength are high. It can be suitably used for machine structural parts that require strength.
  • the steel material to which the present invention is applied is not particularly limited, and examples thereof include carbon steel, low alloy steel, medium alloy steel, high alloy steel, cast iron and the like.
  • a preferable material in terms of cost is carbon steel, low alloy steel, or the like.
  • carbon steel for machine structural use (S20C to S58C) is suitable as carbon steel, and nickel chrome steel (SNC 236 to 836), nickel chrome molybdenum steel (SNCM 220 to 815), chrome, etc. as low alloy steel.
  • Molybdenum steel (SCM 415 to 445, 822), chromium steel (SCr 415 to 445), manganese steel for mechanical structure (SMn 420 to 443), manganese chrome steel (SMnC 420, 443) and the like are suitable.
  • a tempered steel material (H material) whose hardenability is ensured by tempering
  • a tempered steel material with a non-tempered ferrite-pearlite structure may be used.
  • Preferred materials from the viewpoint of cost are carbon steel, low alloy steel, and the like.
  • alloy steel tends to have higher surface hardness, a sufficiently deep hardening depth can be obtained even with carbon steel because of the effect of improving the hardenability of effect II by nitrogen.
  • the effect II by nitrogen in yet present invention, it is not always necessary to use the heat-treated steel, a non-heat treated steels ferritic - obtain a sufficient mechanical strength even in pearlite structure of the steel.
  • the nitrogen compound layer on the surface of the steel material is obtained by a surface hardening treatment that diffuses active nitrogen on the surface of the steel material to generate a hard and stable nitride.
  • a nitrogen compound layer it is usually composed mainly of Fe as a base material component, and a nitride containing Ti, Zr, Mo, W, Cr, Mn, Al, Ni, C, B, Si, etc. It is preferable that it is a layer.
  • a nitrogen compound layer having an effect I such as salt bath nitriding treatment such as tuftride treatment, isonite treatment, and pulsonite treatment, gas soft nitriding treatment, ion nitriding treatment, plasma nitriding treatment, and nitrogen immediately below the nitrogen compound layer
  • the nitriding heat treatment temperature for forming the nitrogen compound layer for achieving the effect I is preferably 600 ° C. or lower, more preferably 580 ° C. or lower, and further preferably 570 ° C. or lower.
  • the thickness of the nitrogen compound layer obtained at a processing temperature exceeding 600 ° C. is increased, the effect I can no longer be expected because the hardness decreases.
  • a minimum is not specifically limited, For example, it is 350 degreeC.
  • the thickness of the nitrogen compound layer obtained by nitriding before induction hardening is not particularly limited, but it is usually sufficient if it is formed with a thickness of 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 3 ⁇ 15 ⁇ m.
  • a protective film is formed using a treatment liquid for protecting the nitrogen compound layer.
  • the treatment liquid is at least one selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo.
  • the aqueous treatment liquid is contained and the pH of the treatment liquid is 4 to 14.
  • the aqueous treatment liquid in the present invention is a single phase, the content of water in the solvent is 30 mass% or more, more preferably 80% by mass or more, the even more preferably not less than 95 wt% Say.
  • the content of water in the solvent since the scatter is small environmental impact of carbon compounds to the protective film forming time in the atmosphere is reduced, the content of water from the environmental aspect is the more preferred.
  • concentration containing species the coating method, and may be a concentration which can be a predetermined deposition amount of the compound layer protective film by the coating repeat count, for example, if the content of 0.5 ⁇ 100 g / L Good.
  • the treatment liquid of the present invention is at least selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo. From 4 to 40 nm in average particle size including one dissolved ion and / or at least one selected from the group consisting of Si, Ti, Zr, Hf, Nb, Cr, W, Al, Sr and Mo And at least one selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo And a dispersed particle having an average particle size of 40 to 400 nm, the ratio of the mass occupied by the former as a dry solid state and the mass occupied by the latter as a dry solid state is 1:10 to 10: 1 Preferably there is.
  • the average particle diameter in the present specification can be measured using a particle size distribution measuring apparatus by a dynamic light scattering method.
  • Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg and Mo decompose and oxidize the nitrogen compound layer during high-frequency heating performed thereafter.
  • Si, Ti, Zr, Ce, Cr, W, Al, and Mo are more preferable because the diffusion rate of ions in these metal compounds is small.
  • the main components of the protective film Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo are film forming components and stress relaxation components. It is preferable to be composed of two. As a film-forming component, the above components are dissolved as ions, oxoacid ions, peroxoacid ions, or complex ions, or in the liquid as very fine particles of 4 to 40 nm with many active sites on the surface. It is distributed.
  • the stress relaxation component of the protective film is selected from the group consisting of Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg, and Mo.
  • the average particle diameter comprising at least one member contains dispersed particles, consisting of 40 ⁇ 400 nm.
  • dispersed particles consisting of 40 ⁇ 400 nm.
  • oxides, hydroxides, nitrides, fluorides, carbonates, and phosphate compounds can be used as the dispersed particles of the film forming component and the stress relaxation component.
  • the amorphous particles are more preferable than the crystalline particles because they have many active points on the surface and good film-forming properties.
  • the dispersed particles of the stress relaxation component the crystalline particles are preferable to the amorphous particles because the volume shrinkage during heating is small, and the effect as a protective film is high because the particles are chemically and physically stable.
  • the film formation is poor because the reactivity is low and the average particle size is large, and as a result, the continuity and adhesion as a film are weak, so that it does not work as a protective film. May be sufficient.
  • the film forming component When only the film forming component is applied, a continuous film can be formed on the nitrogen compound layer, but the stress in the protective film caused by large volume shrinkage during drying cannot be relieved, and the protective film may crack or peel. is there.
  • the film-forming component has high bonding reactivity, but it cannot be said to have sufficient chemical and physical stability and may not always exhibit the protective film effect.
  • the film forming component and the stress relaxation component are both incorporated into the film and formed, and the mass ratio of the two in the dry solid state (the dry solid state in the protective film before quenching) is 1:10 to 10
  • the effect as a protective film becomes the highest. More preferably, it is 1: 5 to 5: 1, and still more preferably 1: 3 to 3: 1.
  • the “dried solid state” in the claims and the present specification refers to an oxide equivalent value assuming that all of the metal-containing components as raw materials are oxides. In practice, there may be components that volatilize or exist in other forms or remain in the form of raw material components. However, the ⁇ dry solid state '' in the claims and the specification is only It is an assumed value (theoretical value) on a raw material basis.
  • Phosphate ions, condensed phosphate ions, phosphite ions, fluoride ions, carbonate ions, and silicate ions effectively prevent decomposition and oxidation of the nitrogen compound layer, especially when applying and drying treatment liquids. .
  • the technique described in Japanese Patent Application Laid-Open No. 2008-038220 is not necessarily sufficient for preventing the oxidation of the nitrogen compound layer.
  • a part of the surface layer of the nitrogen compound layer is oxidatively decomposed after high-frequency heating. There was a case.
  • the role required of the protective film is not only to prevent decomposition and oxidation of the nitrogen compound layer that occurs during high-frequency heating performed after the formation of the protective film, but first of all. Furthermore, it has been found that it is essential to prevent decomposition and oxidation of the nitrogen compound layer when forming the protective film itself. Although the nitrogen compound layer has higher corrosion resistance than the iron substrate itself, it decomposes and oxidizes when it is heated to 50 ° C or higher, especially during wet semi-drying, until the treatment liquid is applied and fixed and dried as a protective film. Cheap.
  • Conceivable It contains 0.1 to 60 g / L of at least one anion selected from the group consisting of phosphate ion, condensed phosphate ion, phosphite ion, fluoride ion, carbonate ion and silicate ion. Preferably, it is 0.5 to 30 g / L, and more preferably 1 to 10 g / L. If the content is less than 0.1 g / L, the effect due to the addition does not sufficiently appear, and if it exceeds 60 g / L, the effect is already saturated and disadvantageous in cost.
  • the treatment liquid of the present invention is aqueous
  • the pH is preferably 4 to 14 in the passive region of iron in order to prevent corrosion of the steel substrate. More preferably, it is 7 to 13, and still more preferably 8 to 12.
  • this processing liquid contains a solvent other than water as a liquid medium
  • the above-mentioned pH value is a pH when the liquid medium is only water.
  • the treatment liquid of the present invention preferably further contains 0.1 to 400 g / L of amines. More preferably, it is 0.5 to 200 g / L, and still more preferably 1 to 100 g / L.
  • the amines keeping the processing solution at a predetermined pH, also high adsorptivity to the surface of the nitrogen compound layer is added nitrogen compound layer to the same stable state as passivation region of iron. These amines also have an effect of suppressing oxidation / decomposition of the nitrogen compound layer during high-frequency heating. As a mechanism for this, the present inventors have released nitrogen during high-frequency heating, and the nitrogen is on the nitrogen compound layer side. I guess to spread.
  • amines to be added include ammonia, urea, methylamine, ethylamine, trimethylamine, triethylamine, triethanolamine, N, N-diisopropylethylamine, piperidine, piperazine, morpholine, pyridine, 4-dimethylaminopyridine, ethylenediamine, Tetramethylethylenediamine, hexamethylenediamine, aniline, catecholamine, phenethylamine, and the like can be used. Any of these can be decomposed or volatilized when heated.
  • a non-volatile material such as an alkali metal is used to maintain the pH here, it will remain in the protective film that has been dried and fixed, and in particular, Li ions, Na ions, and K ions will easily enter the protective film when subjected to high temperature load. Since it may be a factor that can move and reduce the effect as an antioxidant, it is preferable not to use it as much as possible.
  • an antifoaming agent or a surfactant called a wettability improver for obtaining a uniform film on the surface to be coated, a thickener, and other organic / inorganic additions are suitably supplemented. It can also be added.
  • the components in the treatment solution according to the present invention may be derived from the same raw material Good.
  • first component such as Si
  • the second component is an anion such as phosphate ion
  • a third component such as an amine
  • ammonium zirconium carbonate is one raw material in Example 1, zirconium as a first component, a carbonate ion as a second component, and supplies the ammonium as a third component in the liquid.
  • one component in the treatment liquid according to the present invention may have a function as a plurality of components.
  • silicate ions are both Si as the first component and anions as the second component.
  • the existence form of these components in the treatment liquid may be in a state separated from each other, or may exist as a complex such as a complex.
  • the numerical value of each component in this invention shall be calculated on a raw material basis (it estimates from the numerical value of a raw material about the numerical value of a reaction product).
  • the numerical value of each component is calculated independently of each other. Specifically, in the case of functions both as a first component as being components (content or amount A) is, for example, the first component, calculates a first component amount based on the content A, the content A Based on this, the second component amount is calculated. The same applies when a plurality of components are present in the liquid as a complex.
  • the coating method of the treatment liquid is not particularly limited, but a dip coating method, a spin coating method, a spray method, a brush coating, or the like can be used.
  • the coating drying / firing temperature at the time of application is preferably 60 to 550 ° C., more preferably 100 to 400 ° C., and further preferably 120 to 300 ° C.
  • the heating time may be 30 seconds to 60 minutes, for example, and it may be sufficiently solidified, dried and fixed by exposure to the atmosphere.
  • the atmosphere during drying is preferably an inert atmosphere, but may be an air atmosphere.
  • the compound layer protective film is formed by coating Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, and the like on a nitride layer formed after nitriding treatment on a steel material as a dry solid state. Containing at least one metal selected from the group consisting of Cr, W, Al, Sr, Zn, Mg, and Mo, and 0.05 to 3 g / m 2 in total in terms of the metal Formed in range. More preferably, it is 0.1 to 1 g / m 2 .
  • the protective effect of the nitride layer is insufficient, and if it exceeds 3000 mg / m 2 , the effect is already saturated, which is not preferable in terms of cost.
  • the film thickness is about 2 to 4 ⁇ m, which is overwhelmingly thinner than Patent Document 7 covering a millimeter-order film and does not impair hardenability. It is thick.
  • induction hardening performed after forming the compound layer protective film it is subjected to induction heating by heating for 0.3 to 5 seconds so as to reach a predetermined heating temperature set at 750 to 860 ° C. After reaching a predetermined temperature, it is immediately cooled by a coolant, whereby a fine martensitic structure containing nitrogen can be obtained.
  • a more preferable heating temperature is 770 to 840 ° C.
  • a further preferable heating temperature is 780 to 830 ° C.
  • the heating time is more preferably 0.8 to 3 seconds, and further preferably 1 to 2 seconds.
  • the heating exceeds 860 ° C., the effect of the compound layer protective film is no longer effective, and the decomposition of the compound layer can no longer be suppressed, and excessive residual austenite tends to be generated in the martensite structure immediately below the compound layer. It is not preferable. Even if the heating time is 0.3 seconds or less, nitrogen is diffused, but it is not sufficiently austenitized, resulting in insufficient quenching. A heating time exceeding 5 seconds is not preferable because the effect of the heating time is almost saturated and the function of the compound layer protective film is lowered.
  • the nitrogen compound layer is sufficiently suppressed from oxidation and decomposition even when the atmosphere during high-frequency heating is in the air.
  • the atmosphere during high-frequency heating may be a vacuum atmosphere, an inert atmosphere with argon gas or nitrogen gas, a low oxygen atmosphere, a hydrocarbon-based reducing atmosphere, an ammonia gas atmosphere, or the like. it can.
  • a multistage temperature raising method including preheating can be appropriately performed. After quenching by high-frequency heating, tempering treatment may be performed under appropriate conditions in the same manner as a normal quenching technique.
  • compound layer protective film may not be removed be removed can be selected as needed.
  • the removal of the protective film of the compound layer can be easily performed because the hardness is lower than that of the compound layer, and can be appropriately performed by, for example, lapping, emery paper polishing, buffing, shot blasting, shot pinning, or the like.
  • the nitrogen compound layer remains with the compound layer protective film of the present invention, but the nitrogen compound layer does not necessarily remain 100% of the state of the compound layer before the high frequency heating, and the minimum film thickness is 1 ⁇ m or more.
  • the layer thickness should just be ensured. More preferably, it is 2 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the hardness of the nitrogen compound layer is HV630 or more in terms of Vickers hardness
  • the hardness region exceeding HV550 of the hard layer containing a fine martensite structure is 200 ⁇ m or more, preferably 400 ⁇ m or more, more preferably 600 ⁇ m or more in terms of the distance from the surface.
  • a steel material having an existing hardness distribution can be obtained.
  • an upper limit is not specifically limited, For example, it is 1.5 mm.
  • the machine part subjected to the treatment of the present invention has high slidability and seizure resistance due to the nitrogen compound layer formed on the outermost surface, and high temper softening resistance due to the nitrogen-containing fine martensite structure. It has crack initiation / crack growth resistance, surface pressure resistance, high fatigue strength, and deep cure depth.
  • the quenching by induction heating by the composite heat treatment according to the present invention is 750 to 860 ° C., and the quenching temperature is sufficiently lower than the induction quenching and carburizing quenching usually performed at temperatures exceeding 900 ° C. This is extremely advantageous in terms of thermal deformation and cracking, and enables a significant reduction in the post-cutting process for adjusting the dimensional accuracy performed after general induction hardening or carburizing and quenching.
  • the steel material to which the present invention is applied is not necessarily required to use a tempered steel because of the effect of improving the hardenability of the effect II caused by nitrogen. Sufficient mechanical strength can be obtained even with steel.
  • alloy steel tends to have a slightly higher surface hardness
  • a sufficiently deep hardening depth can be obtained even with inexpensive carbon steel due to the effect II of nitrogen.
  • a carbon steel for mechanical structure such as S45C is a heat treatment material having a hardness profile with sufficient hardness and sufficient depth.
  • S45C is not necessarily a tempered material, and even if the heat treatment of the present invention is applied to a steel member having a non-tempered ferrite-pearlite structure, sufficient martensitic transformation occurs, and sufficient mechanical properties are obtained. It can be a heat-treated machine part with high strength.
  • the application of the present invention improves the mechanical strength of the parts, reduces the cutting process and switches to inexpensive materials, thereby reducing the size and weight of the entire mechanical parts by downsizing the parts, and nitriding and induction hardening. It is possible to reduce the actual cost by surplus to compensate for the cost increase due to the combined processing.
  • the compound layer protective film of the present invention is formed after nitriding treatment by, for example, laser quenching by short-time heating for several seconds at the longest or impact quenching for short heating of several milliseconds. If you make quenching the component, a nitride layer is sufficiently protected, base steel lower part of the layer can be obtained quenched structure according to the quenching method using.
  • the hardened steel member according to the present invention is suitable for those used in a high load / high surface pressure region.
  • the shape and part type of the steel member are not particularly limited, and examples thereof include shafts, gears, pistons, shafts, cams, and the like, which are suitable for transmission-related parts and powertrain parts for automobiles and construction machinery.
  • Example 1 SCM435 tempered material having a diameter of 8 mm and a length of 50 mm was used as a base material. After degreasing and cleaning this surface, salt bath soft nitriding treatment at 560 ° C. for 2 hours in a molten salt bath (Isonite treatment: Nippon Parkerizing Co., Ltd.) Ltd.) to oil cooling, to form a nitrogen compound layer consisting mainly of iron nitride having a thickness of about 10 ⁇ m on the surface of the steel material.
  • salt bath soft nitriding treatment at 560 ° C. for 2 hours in a molten salt bath (Isonite treatment: Nippon Parkerizing Co., Ltd.) Ltd.) to oil cooling, to form a nitrogen compound layer consisting mainly of iron nitride having a thickness of about 10 ⁇ m on the surface of the steel material.
  • Zirconium-dissolved zirconium carbonate solution was 22.2 g / L in terms of zirconium (11 g / L as carbonate ions), and zirconium oxide particles having an average particle size of 50 nm (tetragonal crystal structure) was 7.4 g / L in terms of zirconium.
  • a pH 9.5 treatment solution containing 1 g / L of ammonium orthophosphate as phosphate ions and 11 g / L of methylamine was prepared.
  • the treatment liquid was applied to the substrate using a dip coating method, and after removing excess liquid, the process of drying at 40 ° C. ⁇ 10 minutes was repeated three times, and finally, baking was performed at 200 ° C. for 10 minutes.
  • the adhesion amount as Zr was 520 mg / m 2 .
  • the ratio of the film-forming component / stress-relaxing component was 3 with respect to the calculated film-forming component zirconium oxide and the stress-relaxing component zirconium oxide.
  • the heating is stopped immediately after reaching 820 ° C. in 1 second after the start of heating using the induction hardening apparatus. Then, it was cooled and quenched. Later, the steel surface was shot blasted to remove only the compound layer protective film.
  • Example 2 S45C tempered material having a diameter of 8 mm and a length of 50 mm was used as a base material. After degreasing and cleaning this surface, salt bath soft nitriding treatment (Isonite treatment: Nippon Parkerizing Co., Ltd.) at 560 ° C. in a molten salt bath for 2 hours Ltd.) to oil cooling, to form a nitrogen compound layer mainly having a thickness of about 13 ⁇ m iron nitride surface of the steel material.
  • salt bath soft nitriding treatment Isonite treatment: Nippon Parkerizing Co., Ltd.
  • Polymer titanium hydroxide sol particles (crystal structure is amorphous) with an average particle size of 7 nm is 9.0 g / L in terms of titanium, and titanium oxide particles with an average particle size of 45 nm (crystal structure is anatase) is converted to titanium.
  • the treatment liquid was applied to the substrate using the dip coating method, and after removing the excess liquid, the process of drying at 150 ° C. for 20 minutes was repeated twice.
  • the adhesion amount of the Ti was 250 mg / m 2.
  • the ratio of the film-forming component / stress-relaxing component was 0.6 for the calculated film-forming component of titanium oxide and the stress-relaxing component of titanium oxide.
  • the heating is stopped immediately after reaching 820 ° C. in 1 second after the start of heating using the induction hardening apparatus. Then, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Example 3 An S45C non-heat treated material (ferrite / pearlite structure) having a diameter of 8 mm and a length of 50 mm was used as a base material. After degreasing and cleaning this surface, salt bath soft nitriding treatment (Isonite) at 560 ° C. for 1 hour in a molten salt bath Treatment: manufactured by Nihon Parkerizing Co., Ltd.) and water-cooled to form a nitrogen compound layer mainly composed of iron nitride having a thickness of about 12 ⁇ m on the steel surface.
  • salt bath soft nitriding treatment Isonite
  • a treatment solution was prepared. This treatment liquid was applied to the substrate using a spray method, and after removing excess liquid, baking was performed at 320 ° C. for 10 minutes. Measurement of the Si deposition amount on the substrate with a fluorescent X-ray analyzer, the adhesion amount of the Si was 70 mg / m 2.
  • the heating is stopped immediately after reaching 820 ° C. in 1 second after the start of heating using the induction hardening apparatus. Then, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Example 4 A SCM440 tempered material with a diameter of 8 mm and a length of 50 mm was used as a base material. After this surface was degreased and cleaned, gas nitriding was performed in an ammonia atmosphere at 570 ° C. for 24 hours, and the steel material surface was nitrided with a thickness of about 8 ⁇ m A nitrogen compound layer mainly composed of iron was formed.
  • the temperature reached 830 ° C. in 0.8 seconds after the start of heating using an induction hardening apparatus, and immediately thereafter. Heating was stopped, cooling was performed, and quenching was performed. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Example 5 A non-refined SCM440 material (ferrite / pearlite structure) with a diameter of 8 mm and a length of 50 mm was used as the base material, and after degreasing and cleaning this surface, a gas at 570 ° C. in a mixed atmosphere of RX gas and ammonia for 3 hours. treated soft nitrided to form a nitrogen compound layer consisting mainly of iron nitride having a thickness of about 12 ⁇ m on the surface of the steel material.
  • Chromium fluoride is 14.3 g / L in terms of Cr (18 g / L as fluoride ion), orthophosphoric acid is 10 g / L as phosphate ion, and ammonia is 5.4 g / L.
  • a treatment solution was prepared. This treatment liquid was applied to the substrate using a dip coating method, and after removing the excess liquid, baking was performed at 120 ° C. for 30 minutes. Measurement of the Cr deposition amount on the substrate with a fluorescent X-ray analyzer, the adhesion amount of the Cr was 180 mg / m 2.
  • the steel material in which the compound layer protective film containing chromium oxide was formed on the nitrogen compound layer in this way was further heated using an induction hardening device after reaching 820 ° C. in 1 second after the start of heating. Then, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Example 6 S45C tempered material with a diameter of 8 mm and a length of 50 mm was used as the base material, and after this surface was degreased and cleaned, it was subjected to plasma nitriding treatment at 570 ° C. for 40 hours in a mixed atmosphere of nitrogen gas and hydrogen gas. A nitrogen compound layer mainly composed of iron nitride having a thickness of about 15 ⁇ m was formed.
  • Zircon hydrofluoric acid in terms of zirconium oxide was 20 g / L (14.8 g / L as Zr, 18.5 g / L as fluoride ion), 3 g / L as ethylamine, and 5 g / L as orthophosphoric acid as phosphate ion.
  • a treatment solution having a pH of 4.5 was prepared.
  • 50% of zirconium in zircon hydrofluoric acid was converted to zirconium hydroxide particles having an average particle diameter of 50 nm, and was dispersed and clouded. The process of applying this treatment liquid to the substrate using the dip coating method, removing excess liquid, and baking at 180 ° C. for 20 minutes was repeated 10 times.
  • the adhesion amount as Zr was 1200 mg / m 2 .
  • the ratio of the film-forming component / stress-relaxing component was 1 with respect to the calculated film-forming component zirconium oxide and the stress-relaxing component zirconium oxide.
  • the steel material on which the compound layer protective film containing zirconium oxide is formed on the nitrogen compound layer is further heated immediately after reaching 800 ° C. in 1.5 seconds after the start of heating using an induction hardening apparatus. After stopping, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Example 7 SCM440 tempered material having a diameter of 8 mm and a length of 50 mm was used as the base material, and after degreasing and cleaning the surface, salt bath soft nitriding treatment at 560 ° C. in a molten salt bath (Isonite treatment: Nippon Parkerizing Co., Ltd. And a nitrogen compound layer mainly composed of iron nitride having a thickness of about 7 ⁇ m was formed on the surface of the steel material.
  • the steel material on which the compound layer protective film containing tungsten oxide is formed on the nitrogen compound layer is further heated immediately after reaching 860 ° C. in 0.8 seconds after the start of heating using an induction hardening apparatus. After stopping, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Example 8 SCM440 tempered material having a diameter of 8 mm and a length of 50 mm was used as a base material. After degreasing and cleaning the surface, salt bath soft nitriding treatment at 560 ° C. for 2 hours in a molten salt bath (Isonite treatment: Nippon Parkerizing Co., Ltd.) And a nitrogen compound layer mainly composed of iron nitride having a thickness of about 9 ⁇ m was formed on the surface of the steel material.
  • Zirconium oxide sol particles having an average particle size of 5 nm are 7.4 g / L in terms of zirconium, and zirconium oxide particles having an average particle size of 70 nm (crystal structure is tetragonal) are 22 in terms of zirconium.
  • a treatment solution of pH 9.5 containing 2 g / L, 4 g / L of pyrophosphate as pyrophosphate ions, and 9 g / L of ammonia was prepared. This treatment liquid was applied to the base material using a dip coating method, and after removing the excess liquid, it was calcined at 50 ° C. for 20 minutes, and then calcined at 200 ° C. for 30 minutes.
  • the adhesion amount as Zr was 280 mg / m 2 .
  • the ratio of the film-forming component / stress-relaxing component was 0.3 for the calculated film-forming component zirconium oxide and the stress-relaxing component zirconium oxide.
  • the heating is stopped immediately after reaching 790 ° C. in one second after the start of heating using an induction hardening apparatus. Then, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Example 9 SCM440 tempered material having a diameter of 8 mm and a length of 50 mm was used as a base material. After degreasing and cleaning this surface, salt bath soft nitriding treatment at 560 ° C. in a molten salt bath (Isonite treatment: Nippon Parkerizing Co., Ltd.) And a nitrogen compound layer mainly composed of iron nitride having a thickness of about 9 ⁇ m was formed on the surface of the steel material.
  • a pH 8.5 treatment solution containing 10.3 g / L of potassium aluminate in terms of aluminum, 12 g / L of pyrophosphate as pyrophosphate ions, and 42 g / L of morpholine was prepared.
  • the treatment liquid a polymer body of aluminum hydroxide having an average particle diameter of 25 nm was formed and became cloudy.
  • This treatment liquid was applied to the substrate using a dip coating method, and after removing the excess liquid, baking was performed at 150 ° C. for 30 minutes.
  • the adhesion amount of Al on the substrate was measured with a fluorescent X-ray analyzer, the adhesion amount as Al was 150 mg / m 2 .
  • the steel material in which the compound layer protective film containing aluminum oxide was thus formed on the nitrogen compound layer was further heated using an induction hardening device after reaching 780 ° C. in 3 seconds after heating was started. Then, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Chromium fluoride is 14.3 g / L in terms of Cr (18 g / L as fluoride ion), orthophosphoric acid is 50 g / L as phosphate ion, and ammonia is 5.4 g / L.
  • a treatment solution was prepared. This treatment liquid was applied to the substrate using a dip coating method, and after removing the excess liquid, baking was performed at 120 ° C. for 30 minutes. When the amount of Cr deposited on the substrate was measured with a fluorescent X-ray analyzer, the amount deposited as Cr was 210 mg / m 2 .
  • the steel material in which the compound layer protective film containing chromium oxide is formed on the nitrogen compound layer is further heated immediately after reaching 860 ° C. in 0.8 seconds after the start of heating using an induction hardening apparatus. After stopping, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • a treatment liquid having a pH of 8.8 was prepared by adding 60 g / L of ammonium tungstate in terms of tungsten oxide (47.6 g / L as W) and 20 g / L of ammonia together with components from ammonium tungstate.
  • This treatment liquid was applied to the substrate using a dip coating method, and after removing the excess liquid, it was baked at 180 ° C. for 30 minutes.
  • the adhesion amount of W on the substrate was measured with a fluorescent X-ray analyzer, the adhesion amount as W was 160 mg / m 2 .
  • the steel material on which the compound layer protective film containing tungsten oxide is formed on the nitrogen compound layer is further heated immediately after reaching 860 ° C. in 0.8 seconds after the start of heating using an induction hardening apparatus. After stopping, it was cooled and quenched. Later, the steel surface was shot blasted to remove the compound layer protective film.
  • Table 1 shows a list of evaluation results.
  • the effective hardening depth in the table the depth from the surface portion having a hardness of more than Hv 550 (mm).
  • Figure 1 respectively in Example 1 in FIGS. 2 and 3, a cross-sectional photograph of Example 7 and Comparative Example 1, respectively as an example.
  • the cross-sectional hardness distribution of Example 3 and 9 is shown in FIG.
  • Example 1 the nitrogen compound layer on the surface remains without significant damage even after induction hardening as shown in FIG.
  • Example 1 the nitrogen compound layer was more effectively protected.
  • Comparative Example 1 without the compound layer protective film, it was observed that the entire surface was oxidized as shown in FIG. Further, in Comparative Examples 2 and 3, which are outside the scope of the present invention, the nitrogen compound layer was significantly oxidized as in Comparative Example 1, and the action as a protective film was insufficient.

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Abstract

L'invention porte sur des moyens pour empêcher l'oxydation d'une couche composite par durcissement à haute fréquence, ladite couche composite ayant été formée sur la surface d'un matériau en acier par nitruration. Il est décrit de façon spécifique un liquide de traitement pour former un film protecteur de couche composite, lequel est un liquide de traitement pour former une couche protectrice sur une couche de nitrure dans le but de protéger le nitrure, ladite couche de nitrure ayant été formée sur un matériau en acier après nitruration. Le liquide de traitement pour former un film protecteur de couche composite est caractérisé en ce qu'il contient au moins un élément sélectionné parmi le groupe comprenant Si, Ti, Zr, Hf, V, Ta, Ca, Ce, Sc, Nb, Cr, W, Al, Sr, Zn, Mg et Mo, et en ce qu'il contient de 0,1 à 60 g/l d'au moins un type d'anions sélectionnés parmi le groupe comprenant des ions phosphate, des ions phosphate condensés, des ions phosphite, des ions fluorure, des ions carbonate et des ions silicate. Le liquide de traitement pour former un film protecteur de couche composite est également caractérisé en ce qu'il a un pH de 4 à 14.
PCT/JP2010/004780 2009-07-31 2010-07-28 Liquide de traitement pour former un film protecteur pour élément en acier comportant une couche de composé d'azote, et film protecteur de couche composite WO2011013360A1 (fr)

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US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

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JP5886537B2 (ja) * 2011-04-18 2016-03-16 日本パーカライジング株式会社 高耐久性エンジンバルブ
JP6036177B2 (ja) * 2012-10-31 2016-11-30 住友大阪セメント株式会社 親水性膜と親水性膜コーティング物品及び親水性膜形成用塗布液並びに親水性膜の製造方法
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
CN111621777A (zh) * 2020-04-30 2020-09-04 华帝股份有限公司 一种金属材料、表面处理剂及表面处理方法
CN112176277A (zh) * 2020-09-28 2021-01-05 常州市汇丰天元热处理有限公司 一种耐晶间腐蚀型结构钢的速效渗氮方法

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JP5328545B2 (ja) * 2009-07-31 2013-10-30 日本パーカライジング株式会社 窒素化合物層を有する鉄鋼部材、及びその製造方法

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JPS5183846A (fr) * 1975-01-21 1976-07-22 Hino Motors Ltd
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Cited By (4)

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Publication number Priority date Publication date Assignee Title
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

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