WO2018036465A1 - Feuille d'acier galvanisée traitée en surface inorganique, son procédé de préparation, et agent de traitement de surface inorganique aqueux associé - Google Patents

Feuille d'acier galvanisée traitée en surface inorganique, son procédé de préparation, et agent de traitement de surface inorganique aqueux associé Download PDF

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WO2018036465A1
WO2018036465A1 PCT/CN2017/098430 CN2017098430W WO2018036465A1 WO 2018036465 A1 WO2018036465 A1 WO 2018036465A1 CN 2017098430 W CN2017098430 W CN 2017098430W WO 2018036465 A1 WO2018036465 A1 WO 2018036465A1
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parts
group
inorganic film
inorganic
hydrophobic
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PCT/CN2017/098430
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English (en)
Chinese (zh)
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张剑萍
张文麒
戴毅刚
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宝山钢铁股份有限公司
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Priority to JP2019510612A priority Critical patent/JP6839755B2/ja
Priority to EP17842888.4A priority patent/EP3505655B1/fr
Publication of WO2018036465A1 publication Critical patent/WO2018036465A1/fr

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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the invention belongs to the technical field of surface treatment of galvanized steel sheets, in particular to an inorganic surface treatment galvanized steel sheet, a preparation method thereof and an aqueous inorganic surface treatment agent, the inorganic surface treatment galvanized steel sheet according to the invention and a preparation method thereof
  • the surface-treated galvanized steel sheet and the preparation method thereof can satisfy the rapid deep-drawing processing of the progressive die in the field of micro-motors, and at the same time have excellent red rust resistance and surface conductivity of the parts.
  • Galvanized steel sheets are widely used in various fields such as automobiles, home appliances, and construction, and are often used as parts for automobiles, household appliances, and micro-motors. At the same time, the degree of mechanical automation has increased, making various types of micro-motors widely used in automobiles, processing machinery or electrical equipment.
  • the anti-red rust performance corresponds to the service life of the micro-motor, and the surface conductivity corresponds to the grounding safety and electromagnetic characteristics of the micro-motor.
  • the past method mainly involves chromic acid passivation surface treatment of galvanized steel sheets, which can improve the corrosion resistance of steel sheets, but has limited improvement in processing formability and other resistance.
  • solid lubricating additives usually low surface energy polymers such as polyolefin and poly four
  • the organic resin of vinyl fluoride has both corrosion resistance and lubrication effect, but this type of organic film usually has low cohesive energy.
  • the inorganic lubricating film is mainly a film containing inorganic compounds such as silicon, manganese, phosphorus, etc., and the inorganic film has high cohesive energy, and the inorganic lubricating film is not likely to be delaminated and the film is peeled off due to friction of the mold during the pressing process. Therefore, this type of product can also obtain a good appearance after deep drawing processing, but the inorganic lubricating film can not significantly improve the corrosion resistance of the galvanized steel sheet, and does not have good surface conductivity, and cannot Used in areas where the grounding safety and electromagnetic characteristics of parts are required.
  • the organic/inorganic composite lubricating film is a composite film of a resin, a corrosion inhibitor, a silane coupling agent, a silica colloid, and a solid lubricating agent, and has excellent lubricity and corrosion resistance, and Various chemical media have good resistance such as fingerprint resistance and alkali resistance.
  • the content of organic resin in the organic/inorganic composite lubricating film is high, and the low cohesive energy of the organic resin tends to cause interlayer peeling of the organic film in the rapid deep drawing process of the micro-motor field, which leads to the surface of the part.
  • the black shavings or organic film peeling off not only affects the appearance of the stamped parts, but also the organic polymer debris that falls off adheres to the parts or molds, causing frequent cleaning of the mold and affecting the efficiency of the stamping line.
  • the organic/inorganic composite lubricating film usually does not have excellent surface electrical conductivity, and cannot be used in a field where the grounding safety and electromagnetic characteristics of parts are required to be high. Therefore, the current chromium-free environmentally friendly products (including inorganic and organic/inorganic composite types) cannot meet the requirements of high-speed deep-drawing characteristics, red rust resistance and surface conductivity of the micro-motor field.
  • Chinese Patent Publication No. CN 101376859A discloses the use of an inorganic treating agent containing manganese, nickel, phosphate ions and silane to form a thin transparent inorganic solid film on the surface of a galvanized steel sheet, which can improve the stamping forming property of the galvanized steel sheet. Eliminate or reduce the viscous zinc in galvanized steel sheets during stamping With the phenomenon of powdered shedding.
  • Chinese Patent Publication No. CN 1177020A China Authorized Patent is a lubricating steel sheet containing a protective film containing silicic acid or silicate on a steel sheet having fine irregularities on its surface, and its film coverage is about 60%, which has phosphatability and good properties. Lubricity. All of the above patents give the steel plate good lubricity, but the corrosion resistance is not as good as that of the chromium-containing passivation product, and it cannot meet the requirements of the micro-motor for the red rust resistance of the material.
  • Chinese Patent Publication No. CN 101787527A provides a galvanized steel sheet having excellent processability and alkali resistance and solvent resistance, the surface of which is covered with an organic/inorganic composite protective film containing an aqueous cationic polyurethane resin, one or one. More than one organosilane coupling agent, as well as corrosion inhibitors and oxidized polyethylene particles.
  • the protective film imparts excellent press formability, solvent resistance, and alkali resistance to the surface of the galvanized steel sheet, and at the same time, the galvanized steel sheet has excellent corrosion resistance and coating adhesion.
  • the micro-motor has high requirements on the surface conductivity.
  • the organic/inorganic composite protective film does not have excellent surface electrical conductivity, and cannot be used in a field where the grounding safety and electromagnetic characteristics of parts are required to be high.
  • the Chinese Patent Publication No. CN 101394998A patent provides a coated steel sheet excellent in bending workability, press formability, solvent resistance, chemical resistance, corrosion resistance, and having a good surface appearance and sufficient coating film hardness.
  • the steel plate is a single-layer thick coating product with a film thickness of 2-10 micrometers, and the manufacturing process is a two-step process, first forming a chemical conversion film containing no chromium, and then coating a polyester resin, that is, a post-treatment film needs to pass Two coatings, two baking, usually the second baking is required to be heated at a steel plate temperature of 170-250 ° C.
  • the patent requires relatively high production equipment, and does not have surface conductivity, not suitable for micro The field of motors.
  • the present invention aims to provide an inorganic surface-treated galvanized steel sheet, a preparation method thereof and an aqueous inorganic surface treatment agent thereof, wherein the inorganic surface-treated galvanized steel sheet and an aqueous inorganic surface treatment agent thereof are environmentally friendly and chrome-free It can meet the rapid deep-drawing processing of micro-motor field progressive die, and at the same time, it has excellent red rust resistance and surface conductivity to meet the environmental protection, surface conductivity and red rust resistance of galvanized steel sheets for users in the field of micro-motors. And fast stamping processability requirements.
  • the present invention also provides an environmentally-friendly aqueous inorganic surface treatment agent for producing the above surface-treated galvanized steel sheet.
  • An inorganic surface-treated galvanized steel sheet is coated on the surface of a galvanized steel sheet with a single-layer inorganic film having a thickness of 0.3-1.0 ⁇ m, wherein
  • the inorganic film contains:
  • the hydrophobic monoorganosilane coupling agent contains X hydrophobic groups (X is 1 or 2) and 4-X reactive groups;
  • the system crosslinking agent is one or more of orthosilicate, titanate or a diorganosilane coupling agent having a bridging structure;
  • the water-soluble nano sol has a mass fraction of 20-30%
  • the orthosilicate-modified graphene oxide is a dark brown n-propanol suspension, wherein the orthosilicate-modified graphene oxide has a mass fraction of 1-5%.
  • An inorganic surface-treated galvanized steel sheet according to the present invention characterized in that
  • the inorganic film further contains:
  • F a water-soluble fluorine-containing compound, wherein the fluorine element is in an amount of 1 to 4 parts by weight in the inorganic film;
  • G a water-soluble phosphorus-containing compound, wherein the phosphorus element is 0.5-4 parts by weight in the inorganic film;
  • the hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) is selected from the group consisting of -CH 3 (methyl), -C 2 H 5 (ethyl), -C 3 H 7 (propyl) ), -C 6 H 5 (phenyl), -CF 3 (perfluoromethyl), -C 2 F 5 (perfluoroethyl), -C 3 F 7 (perfluoropropyl), -C 5 F One or two of 11 (perfluoropentyl), -C 7 F 15 (perfluoroheptyl) or -C 9 F 19 (perfluorodecyl);
  • the reactive group in the hydrophobic monoorganosilane coupling agent is selected from the group consisting of -OCH 3 (methoxy), -OC 2 H 5 (ethoxy), vinyl, propenyl, epoxy One to three of an amino group, a hydroxyl group, a carboxyl group, an amide group or a 2,3-epoxypropoxy group;
  • the sum of the number of hydrophobic groups and the number of reactive groups in the hydrophobic monoorganosilane coupling agent is equal to four;
  • the hydrophobic monoorganic silane coupling agent is contained in the inorganic film in an amount of 40 to 60 parts by weight, preferably 45 to 55 parts by weight.
  • the system cross-linking agent (B) may be a tetrasilicate having 4 reactive groups, a titanate having 4 reactive groups, or a double-bridged structure having 6 reactive groups.
  • organosilane coupling agents One or more of organosilane coupling agents;
  • the reactive group in the orthosilicate is selected from any one of a methoxy group, an ethoxy group, a propoxy group or a butoxy group;
  • the reactive group in the titanate is selected from one or more of an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl ester group;
  • the bridging structure of the bis-organosilane coupling agent is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups;
  • the reactive group of the bis-organosilane coupling agent is selected from any one of a methoxy group, an ethoxy group or a propoxy group.
  • the aqueous nanosol (C) is an aqueous inorganic oxide or a metal oxide sol
  • the aqueous nanosol is selected from one or more of an aqueous silica sol, an aqueous titanium dioxide sol, an aqueous zirconia sol or an aqueous alumina sol.
  • the surface-modified high-density polyethylene particles (D) have a particle diameter of between 0.1 and 0.5 ⁇ m; the surface-modifying group is reactive, and is specifically selected from an amino group, a hydroxyl group, a carboxyl group, an epoxy group or a urethane.
  • the bases One or more of the bases;
  • the number of layers of the orthosilicate-modified graphene oxide (E) layer is between 1-5 layers (thickness is between 0.35 nm and 1.75 nm); the size of the orthosilicate-modified graphene oxide is Between 2-5 microns, the aspect ratio of graphene is between 1100-14000.
  • the orthosilicate in the orthosilicate-modified graphene oxide is one or more selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or butyl orthosilicate.
  • the orthosilicate-modified graphene oxide has a carbon oxide atom number ratio of ⁇ 3 and a silicon element content of 5-12%.
  • the water-soluble fluorine-containing compound (F) is a fluorine-containing metal salt or a fluorine-containing acid, and is selected from the group consisting of sodium fluoride, ammonium fluorotitanate, sodium fluorosilicate, hexafluorotitanate, and fluorosilicic acid. Kind or more.
  • the water-soluble phosphorus-containing compound (G) is a phosphate or a phosphoric acid-containing compound selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, and tripolyphosphoric acid.
  • a phosphate or a phosphoric acid-containing compound selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, and tripolyphosphoric acid.
  • One or more of aluminum and ammonium polyphosphate is a phosphate or a phosphoric acid-containing compound selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, and tripolyphosphoric acid.
  • One or more of aluminum and ammonium polyphosphate is a phosphate or a phosphoric acid-containing compound selected from the group
  • the water-soluble metal salt compound (H) is one or more of a titanium salt, a phosphonium salt, a phosphonium salt, a molybdenum salt, a tungsten salt, a cobalt salt, and a zirconium salt.
  • the titanium salt is selected from one or more of ammonium fluorotitanate, hexafluorotitanate, titanium orthosulfate, titanium oxysulfate or titanium chloride.
  • the onium salt is selected from one or more of cerium nitrate, barium sulfate, a fluorine-containing phosphonium salt, and a cerium ammonium complex salt.
  • the onium salt may be one or more of barium chloride, barium sulfate, and barium nitrate.
  • the molybdenum salt is selected from one or more of ammonium molybdate, magnesium molybdate or sodium molybdate.
  • the tungsten salt is selected from one or more of ammonium tungstate, magnesium tungstate, ammonium paratungstate or ammonium metatungstate.
  • the cobalt salt may be an inorganic cobalt salt such as cobalt nitrate, cobalt sulfate or cobalt chloride, or may be one or more of cobalt naphthenate, cobalt oxalate or cobalt stearate.
  • the zirconium salt may be one or more of potassium zirconium fluorophosphate, zirconium nitrate, and zirconium sulfate.
  • the above inorganic surface-treated galvanized steel prepared according to the invention has environmentally friendly chromium-free steel, can meet the rapid deep-drawing processing of the progressive die in the field of micro-motors, and has excellent red rust resistance and surface electrical conductivity at the same time.
  • the object of the present invention is also to provide a method for preparing an inorganic surface-treated galvanized steel sheet, which can satisfy the rapid deep-drawing processing of the progressive die in the field of micro-motors, and at the same time has excellent red rust resistance and surface conductivity of the parts, and the technology thereof
  • the plan is as follows:
  • the inorganic film contains:
  • the hydrophobic monoorganosilane coupling agent contains X hydrophobic groups (X is 1 or 2) and 4-X reactive groups;
  • the system crosslinking agent is selected from one or more of a orthosilicate, a titanate or a diorganosilane coupling agent having a bridging structure;
  • the water-soluble nano sol has a mass fraction of 20-30%
  • the orthosilicate-modified graphene oxide is a dark brown n-propanol suspension, wherein the orthosilicate-modified graphene oxide has a mass fraction of 1-5%.
  • a method for preparing an inorganic surface-treated galvanized steel sheet according to the present invention characterized in that
  • the inorganic film further contains:
  • F a water-soluble fluorine-containing compound, wherein the fluorine element is in an amount of 1 to 4 parts by weight in the inorganic film;
  • G a water-soluble phosphorus-containing compound, wherein the phosphorus element is 0.5-4 parts by weight in the inorganic film;
  • the hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) may be -CH 3 (methyl), -C 2 H 5 (ethyl), -C 3 H 7 (propyl), -C 6 H 5 (phenyl), -CF 3 (perfluoromethyl), -C 2 F 5 (perfluoroethyl), -C 3 F 7 (perfluoropropyl), -C 5 F 11 (perfluoro One or two of pentyl), -C 7 F 15 (perfluoroheptyl) or -C 9 F 19 (perfluorodecyl); a reactive group in the hydrophobic monoorganosilane coupling agent It may be -OCH 3 (methoxy), -OC 2 H 5 (ethoxy), vinyl, propenyl, epoxy, amino, hydroxy, carboxyl, amide or 2,3-epoxypropoxy Up to three of them; the sum of the number of hydrophobic groups and the number of reactive groups in the
  • the system cross-linking agent (B) may be an orthosilicate having 4 reactive groups, and has 4 reactivity.
  • the reactive group in the orthosilicate may be methoxy Any one of a group, an ethoxy group, a propoxy group or a butoxy group;
  • the reactive group in the titanate may be an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl group
  • the bridging structure of the bis-organosilane coupling agent is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups;
  • the reactive group may be any one of a methoxy group, an ethoxy group or a propoxy group.
  • the aqueous nanosol (C) is an aqueous inorganic oxide or metal oxide sol; the aqueous nanosol is selected from one of an aqueous silica sol, an aqueous titanium oxide sol, an aqueous zirconia sol or an aqueous alumina sol or A variety.
  • the surface-modified high-density polyethylene particles (D) have a particle diameter of between 0.1 and 0.5 ⁇ m; the surface-modifying group has reactivity, specifically selected from amino, hydroxyl, carboxyl, epoxy or carbamic acid. One or more of the ester groups.
  • the number of layers of the orthosilicate-modified graphene oxide (E) layer is between 1-5 layers (thickness is between 0.35 nm and 1.75 nm); the size of the orthosilicate-modified graphene oxide is Between 2-5 microns, the aspect ratio of graphene is between 1100-14000.
  • the orthosilicate in the orthosilicate-modified graphene oxide is one or more selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate or butyl orthosilicate.
  • methyl orthosilicate ethyl orthosilicate
  • propyl orthosilicate propyl orthosilicate or butyl orthosilicate.
  • the orthosilicate-modified graphene oxide has a carbon oxide atom number ratio of ⁇ 3 and a silicon element content of 5-12%.
  • the water-soluble fluorine-containing compound (F) is a fluorine-containing metal salt or a fluorine-containing acid, and is selected from the group consisting of sodium fluoride, ammonium fluorotitanate, sodium fluorosilicate, hexafluorotitanate, and fluorosilicic acid. Kind or more.
  • the water-soluble phosphorus-containing compound (G) is a phosphate or a phosphoric acid-containing compound selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, and tripolyphosphoric acid.
  • a phosphate or a phosphoric acid-containing compound selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, and tripolyphosphoric acid.
  • One or more of aluminum and ammonium polyphosphate is a phosphate or a phosphoric acid-containing compound selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, and tripolyphosphoric acid.
  • One or more of aluminum and ammonium polyphosphate is a phosphate or a phosphoric acid-containing compound selected from the group
  • the water-soluble metal salt compound (H) is one or more of a titanium salt, a phosphonium salt, a phosphonium salt, a molybdenum salt, a tungsten salt, a cobalt salt, and a zirconium salt.
  • the titanium salt is selected from one or more of ammonium fluorotitanate, hexafluorotitanate, titanium orthosulfate, titanium oxysulfate or titanium chloride.
  • the onium salt is selected from one or more of cerium nitrate, barium sulfate, a fluorine-containing phosphonium salt, and a cerium ammonium complex salt.
  • the onium salt may be one or more of barium chloride, barium sulfate, and barium nitrate.
  • the molybdenum salt is selected from one or more of ammonium molybdate, magnesium molybdate or sodium molybdate.
  • the tungsten salt is selected from one or more of ammonium tungstate, magnesium tungstate, ammonium paratungstate or ammonium metatungstate.
  • the cobalt salt may be an inorganic cobalt salt such as cobalt nitrate, cobalt sulfate or cobalt chloride, or may be one or more of cobalt naphthenate, cobalt oxalate or cobalt stearate.
  • the zirconium salt may be one or more of potassium zirconium fluorophosphate, zirconium nitrate, and zirconium sulfate.
  • the above inorganic surface-treated galvanized steel prepared by the method of the invention has the advantages of environmentally friendly and chrome-free, can meet the rapid deep drawing processing of the progressive die of the micro-motor field, and has excellent red rust resistance and surface conductivity of the parts at the same time.
  • the invention further provides an aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet, wherein the aqueous inorganic surface treatment agent can satisfy the rapid deep drawing processing of the progressive die in the micro-motor field, and at the same time, has excellent red rust resistance and surface conduction of the parts. Performance for galvanized steel sheets.
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet for coating onto a surface of a galvanized steel sheet to form an inorganic film according to the present invention characterized in that
  • the total solids in its aqueous solution contain the following ingredients:
  • the hydrophobic monoorganosilane coupling agent contains X hydrophobic groups (X is 1 or 2) and 4-X reactive groups;
  • the system crosslinking agent is one or more of orthosilicate, titanate or a diorganosilane coupling agent having a bridging structure;
  • the water-soluble nano sol has a mass fraction of 20-30%
  • the orthosilicate-modified graphene oxide is a dark brown n-propanol suspension, wherein the orthosilicate-modified graphene oxide has a mass fraction of 1-5%;
  • F a water-soluble fluorine-containing compound, wherein the fluorine element is in an amount of 1 to 4 parts by weight in the inorganic film;
  • G a water-soluble phosphorus-containing compound, wherein the phosphorus element is 0.5-4 parts by weight in the inorganic film;
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention characterized in that
  • the hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) may be -CH 3 (methyl), -C 2 H 5 (ethyl), -C 3 H 7 (propyl), -C 6 H 5 (phenyl), -CF 3 (perfluoromethyl), -C 2 F 5 (perfluoroethyl), -C 3 F 7 (perfluoropropyl), -C 5 F 11 (perfluoro One or two of pentyl), -C 7 F 15 (perfluoroheptyl) or -C 9 F 19 (perfluorodecyl); a reactive group in the hydrophobic monoorganosilane coupling agent It may be -OCH 3 (methoxy), -OC 2 H 5 (ethoxy), vinyl, propenyl, epoxy, amino, hydroxy, carboxyl, amide or 2,3-epoxypropoxy Up to three of them; the sum of the number of hydrophobic groups and the number of reactive groups in the
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention characterized in that
  • the system cross-linking agent (B) may be an orthosilicate having 4 reactive groups, and has 4 reactivity.
  • the reactive group in the orthosilicate may be methoxy Any one of a group, an ethoxy group, a propoxy group or a butoxy group;
  • the reactive group in the titanate may be an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl group
  • the bridging structure of the bis-organosilane coupling agent is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups;
  • the reactive group may be any one of a methoxy group, an ethoxy group or a propoxy group.
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention characterized in that
  • the aqueous nanosol (C) is an aqueous inorganic oxide or a metal oxide sol; the aqueous nanosol may be one of an aqueous silica sol, an aqueous titania sol, an aqueous zirconia sol or an aqueous alumina sol or A variety.
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention characterized in that
  • the surface-modified high-density polyethylene particles (D) have a particle diameter of between 0.1 and 0.5 ⁇ m; the surface-modifying group has reactivity, specifically an amino group, a hydroxyl group, a carboxyl group, an epoxy group or a urethane group. One or more of them;
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention characterized in that
  • the number of layers of the orthosilicate-modified graphene oxide (E) layer is between 1-5 layers (thickness is between 0.35 nm and 1.75 nm); the size of the orthosilicate-modified graphene oxide is Between 2-5 microns, the aspect ratio of graphene is between 1100-14000; the orthosilicate in the orthosilicate-modified graphene oxide may be methyl orthosilicate, tetraethyl orthosilicate, positive One or more of propyl silicate or butyl orthosilicate; the orthosilicate-modified graphene oxide has a carbon oxide atom number ratio of ⁇ 3 and a silicon element content of 5-12%.
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention characterized in that
  • the water-soluble fluorine-containing compound (F) is a fluorine-containing metal salt or a fluorine-containing acid.
  • the water-soluble fluorine-containing compound may be sodium fluoride, ammonium fluorotitanate, sodium fluorosilicate or hexafluorocarbon.
  • titanic acid and fluorosilicic acid are examples of titanic acid and fluorosilicic acid.
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention characterized in that
  • the water-soluble phosphorus-containing compound (G) is a phosphate or a phosphoric acid.
  • the water-soluble phosphorus-containing compound may be orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, or the like.
  • One or more of aluminum polyphosphate and ammonium polyphosphate may be orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, or the like.
  • aluminum polyphosphate and ammonium polyphosphate may be orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, or the like.
  • aluminum polyphosphate and ammonium polyphosphate may be orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, trimeric metaphosphoric acid, ammonium phosphate, or the like.
  • aluminum polyphosphate and ammonium polyphosphate may be ortho
  • An aqueous inorganic surface treatment agent for surface treatment of a galvanized steel sheet according to the present invention characterized in that
  • the water-soluble metal salt compound (H) is one or more of a titanium salt, a cerium salt, a cerium salt, a molybdenum salt, a tungsten salt, a cobalt salt and a zirconium salt.
  • the titanium salt may be fluorine.
  • the cerium salt may be cerium nitrate, cerium sulfate, or a fluorinated cerium salt, or cerium ammonium
  • the cerium salt may be one or more of cerium chloride, cerium sulfate and cerium nitrate
  • the molybdenum salt may be one of ammonium molybdate, magnesium molybdate or sodium molybdate Or a plurality of
  • the tungsten salt may be one or more of ammonium tungstate, magnesium tungstate, ammonium paratungstate or ammonium metatungstate
  • the cobalt salt may be an inorganic cobalt salt such as cobalt nitrate, cobalt sulfate or cobalt chloride, or It may be one or more of cobalt naphthenate, cobalt oxa
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the hydrophobic monoorganosilane coupling agent (A) in the aqueous inorganic surface treatment agent may be a mixture of one or more of the above monoorganosilanes, and is a main film-forming substance of the aqueous inorganic surface treatment agent of the present invention.
  • the inorganic film formed by using the hydrophobic monoorganosilane coupling agent (A) as a main component has strong cohesive energy, and the cohesive effect of the inorganic film is remarkable.
  • the strong cohesive inorganic film can maintain the integrity of the film when the mold is severely rubbed, and prevent the inorganic film from peeling off or falling off, thus ensuring the parts are in the grade.
  • the die has a good appearance after multiple stamping, and can also reduce the number of clearing lines of the stamping line and improve the production efficiency of the stamping line.
  • the hydrophobic monoorganosilane coupling agent (A) in the present invention itself has remarkable hydrophobic properties, but the reactive group contained in the monoorganosiloxane may react with water to form an excellent hydrophilic property.
  • hydrophilic group such as a hydroxyl group, a carboxyl group or an amino group
  • hydrophobic monoorganosilane coupling agent (A) can be in an aqueous system Stable dissolution or dispersion.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the inorganic film In order for the formed inorganic film to have excellent corrosion resistance, it is required that the inorganic film has a high degree of crosslinking.
  • the main film-forming substance in the inorganic film the hydrophobic monoorganosilane coupling agent (A) needs to be cross-linkable with other components in the film such as the system crosslinking agent (B) and the aqueous nano-sol (C), thereby Increase the crosslink density of the film. Therefore, in order to ensure excellent reactivity of the hydrophobic monoorganosilane coupling agent (A) used in the present invention, the hydrophobic monoorganosilane coupling agent (A) must contain two or more. Reactive group.
  • the reactive group may be one or more of -OCH 3 (methoxy) and -OC 2 H 5 (ethoxy) which are first reacted with water to form a hydroxyl group and then reacted with other substances (B and C). Or one or more of an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an amide group, and a 2,3-epoxypropoxy group capable of directly reacting with other substances (B and C); One or more of a vinyl group and a propenyl group in which polymerization occurs.
  • the non-broken inorganic film or zinc powder adheres to the surface of the part, that is, the surface of the part is required to have "non-stick” characteristics, corresponding to the surface of the steel plate and only the inorganic film exists.
  • the possibility of "non-stick” features After painstaking research and many attempts, it was found that the hydrophobic monoorganosilane coupling agent was formed by introducing a hydrophobic group into a conventional monoorganosilane coupling agent to form a hydrophobic monoorganosilane coupling agent (A).
  • the hydrophobic group in (A) can migrate to the surface of the film during the curing process of the film, forming a very thin hydrophobic layer on the surface of the inorganic film, thereby reducing the surface polarity and Gibbs free energy of the inorganic film, and reducing the inorganic film pair.
  • the adhesion of zinc powder, impurities and broken film makes the surface of the inorganic film have "non-stick" characteristics, so as to ensure that the surface of the part is cleaned after rapid deep drawing of the progressive die, and no broken inorganic film or zinc powder adheres to the surface of the part.
  • an inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent
  • the hydrophobic monoorganic silane coupling agent (A) should have both a reactive group and a hydrophobic group, and the sum of the number of reactive groups and the number of hydrophobic groups should be 4.
  • the number of reactive groups should be greater than or equal to two (ie, Is available for two or three). Therefore, the number of hydrophobic groups capable of providing "non-stick" characteristics to the hydrophobic monoorganosilane coupling agent (A) is (the number of 4-reactive groups), which is indicative of the hydrophobic monoorganosilane of the present invention.
  • the number of hydrophobic groups in the coupling agent (A) may be one or two.
  • the hydrophobic group in the above hydrophobic monoorganosilane coupling agent (A) may be a short-chain hydrocarbon group such as -CH 3 (methyl), -C 2 H 5 (ethyl), -C 3 H 7 (propyl) Or -C 6 H 5 (phenyl); may also be a fluorine-containing hydrophobic group such as -CF 3 (perfluoromethyl), -C 2 F 5 (perfluoroethyl), -C 3 F 7 ( Perfluoropropyl), -C 5 F 11 (perfluoropentyl), -C 7 F 15 (perfluoroheptyl) or -C 9 F 19 (perfluorodecyl).
  • the hydrophobic group in the hydrophobic monoorganic silane coupling agent (A) in the present invention may be any one or any two of the above groups.
  • the inorganic surface-treated galvanized steel sheet according to the present invention the preparation method thereof and the aqueous inorganic surface treatment agent,
  • the hydrophobic monoorganosilane coupling agent (A) structure should have both a reactive group (two or three) and a hydrophobic group (one or two), and the number of reactive groups and hydrophobicity The sum of the number of groups is 4.
  • a trimethoxymethylsilane coupling agent, a triethoxymethylsilane coupling agent, a tripropoxymethylsilane coupling agent, a trimethoxyethylsilane coupling agent, and a triethoxy group are mentioned.
  • the hydrophobic monoorganosilane coupling agent (A) is contained in an amount of 40 to 60 parts by weight in the inorganic film. If it is less than 40 parts, the corrosion resistance and "non-stick" characteristics of the inorganic film are poor, and the poor corrosion resistance of the inorganic film may affect the red rust resistance of the stamped parts; the "non-stick” characteristics may cause the surface adhesion of the parts after punching. More impurities, affecting the appearance of parts after stamping. If it is more than 60 parts, the ductility of the inorganic film is deteriorated, and the inorganic film is liable to be cracked and peeled off during the molding process, resulting in a decrease in film formability.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the system cross-linking agent (B) used in the present invention has a large number of reactive groups which can be chemically bonded to the metal substrate and other components in the inorganic film, which can not only improve the inorganic film and the metal substrate. Adhesion, at the same time, can enhance the crosslink density of the inorganic film to enhance the corrosion resistance and stamping formability of the inorganic film, so that the parts after stamping have excellent red rust resistance and surface appearance.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the system crosslinking agent (B) in the present invention may be one or more of a orthosilicate, a titanate or a diorganosilane coupling agent having a bridging structure; and 4 of the orthosilicates a reactive group, wherein the reactive group may be any one of a methoxy group, an ethoxy group, a propoxy group or a n-butoxy group; the titanate has four reactive groups, and the reaction thereof
  • the group may be one or more of an isopropyl ester group, a phosphoryloxy group, a benzenesulfonyloxy group or a n-butyl ester group;
  • the double organosilane coupling agent means two in the same molecular structure
  • the silane structure has 6 reactive groups on one molecule, and the number of reactive groups is larger than that of the conventional monoorganosilane coupling agent.
  • the bis-organosilane coupling agent of the invention has a bridging structure, and the bridging structure is composed of 2-4 methylene groups, amino groups or 2-4 fluorenyl groups; the reactive group of the bis-organosilane coupling agent may be Any one of a methoxy group, an ethoxy group or a propoxy group.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the orthosilicate used in the system cross-linking agent (B) in the present invention may be methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate or isopropyl orthosilicate.
  • the titanate used in the system cross-linking agent (B) in the present invention may be tetraisopropyl orthotitanate, isopropyl tris(dioctylphosphoryloxy) titanate, Isopropyl trioleic acid oxy titanate, tetraisopropyl bis(dioctylphosphite oxy) titanate, bis(dioctyloxypyrophosphate) ethylene titanate, different One or more of propyl tris(dodecylbenzenesulfonyl) titanate, tetra-tert-butyl orthotitanate or diisopropyl bis(triethanolamine)titanate; system crosslinker in the present invention (B)
  • the diorganosilane coupling agent used may be 1,2-bistrimethoxysilylethane, 1,2-bisethoxysilylethane, bis-( ⁇ -triethoxy) One or more of sily
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the system crosslinking agent (B) is contained in an amount of 10 to 30 parts by weight in the inorganic film. If it is less than 10 parts, the crosslinking density of the inorganic film will be greatly reduced, thereby affecting the corrosion resistance of the inorganic film, and finally The red rust resistance of the stamped parts is poor. If it is higher than 30 parts, due to the compatibility of the selected system cross-linking agent with water, more system cross-linking agents will affect the stability of the aqueous inorganic surface treatment agent, which will result in obvious treatment agent after a long time. The stratification phenomenon causes a large decrease in the overall performance of the aqueous inorganic surface treatment agent.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the water-soluble nano sol (C) used in the present invention is preferably a water-soluble colloid having a particle diameter of 5 to 50 nm, and the kind thereof may be an aqueous inorganic oxide or a metal oxide sol, and specifically may be aqueous two.
  • the crosslinking density of the inorganic film can be further increased by a large number of reactive groups in the aqueous nanosol, thereby enhancing the corrosion resistance of the inorganic film.
  • the fine particles formed by baking and solidifying the aqueous nano-sol have higher hardness, which can effectively improve the scratch resistance of the inorganic film and avoid surface scratches on the parts after stamping.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the water-soluble nano sol (C) used in the present invention may be an aqueous silica sol such as SNOWTEX-40, SNOWTEX-50, SNOWTEX-C, SNOWTEX-N, SNOWTEX-O, SNOWTEX-OL, SNOWTEX of Nissan Chemical Co., Ltd.
  • the water-soluble nano sol (C) used in the present invention may also be an aqueous titanium dioxide sol, such as Shenzhen Yoshida Chemical MTI-2080; Shanghai EFUT- GY01, EFUT-GY02, EFUT-GY03, etc.; the water-soluble nano sol (C) used in the present invention may also be an aqueous zirconia sol, such as VK-RJ80 of Xuancheng Jingrui, GT-360 of Yizheng Technology, UG03W, UG-R10W and UR-R30W of Suzhou
  • Aqueous nano-solutions used in the present invention As the gum (C), any one or any of the above aqueous silica sol, aqueous titania sol, aqueous zirconia sol or aqueous alumina sol can be used.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the aqueous nanosol (C) in the present invention accounts for 5 to 15 parts by weight in the inorganic film. If it is less than 5 parts, the surface hardness of the inorganic film is greatly lowered, thereby affecting the scratch resistance of the inorganic film, resulting in the inorganic film being easily damaged during the press forming process. If it is more than 15 parts, the nanotechnology in the inorganic film is too much, and the ductility of the film is deteriorated, resulting in a decrease in film formability.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the surface-modified high-density polyethylene particles (D) used in the present invention are commercially available solid lubricating particles.
  • This type of lubricating agent has the characteristics of low surface energy, high lubricity and high surface hardness. It can form a hard lubricating layer on the surface of the inorganic film, which not only improves the scratch resistance of the inorganic film, but also enhances the inorganic film.
  • the surface is smooth, and the purpose of strengthening the stamping formability of the inorganic film is achieved, so that it can meet the requirements of rapid deep drawing processing of the progressive die in the field of micro-motors.
  • progressive die stamping usually exceeds 10 passes, and each pass of stamping causes frictional wear on the inorganic film of the present invention.
  • the inorganic film of the present invention is required. It should have strong scratch resistance and ensure the integrity and excellent appearance of the film during the multi-pass stamping process.
  • a small amount of surface aggregation also needs to be uniformly dispersed inside the inorganic film, so that the inorganic film has excellent scratch resistance in the entire thickness direction, thereby ensuring that the inorganic film can meet the multi-pass stamping requirements of the progressive die.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the surface-modified high-density polyethylene particles (D) used in the present invention are solid lubricating particles having a reactive group grafted on the surface, specifically one of an amino group, a hydroxyl group, a carboxyl group, an epoxy group or a urethane group.
  • the hydroxyl group and the carboxyl group can be obtained by immersing the high-density polyethylene particles in a strong oxidizing solution; the amino group and the urethane group can be passed through ethylenediamine, hexamethylenediamine or urethane with a high density The surface of the polyethylene particles is grafted; the epoxy group can be obtained by surface grafting of glycidyl methacrylate or allyl glycidyl ether with high density polyethylene particles.
  • the above reactive group can react with the organosilane coupling agent in the treatment liquid to form a covalent bond, which not only strengthens the bonding strength between the high-density polyethylene particles and the inorganic film, but also binds the high-density polyethylene particles, thereby ensuring
  • the high-density polyethylene particles can be uniformly dispersed in the inorganic film, and can provide excellent anti-wear properties in the entire thickness direction of the inorganic film, and improve the press workability and scratch resistance of the inorganic film.
  • chemical bonding between the high-density polyethylene particles and the film can delay the penetration of the corrosive medium along the surface of the high-density polyethylene particles into the film, and reduce the negative influence of the addition of the high-density polyethylene particles on the corrosion resistance of the inorganic film.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the surface-modified high-density polyethylene particles (D) used in the present invention have a particle diameter in the range of 0.1 to 0.5 ⁇ m, and if less than 0.1 ⁇ m, the surface-modified high-density polyethylene particles (D) do not occur in the inorganic film.
  • the surface-modified high-density polyethylene particles (D) are too large, and most of the particles are exposed on the surface of the film, and when subjected to punching friction, large particles are easily detached As a result, the press workability of the film is drastically lowered.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the surface-modified high-density polyethylene particles (D) used in the present invention are 10-25 parts by weight in the inorganic film. If less than 10 parts, the surface of the inorganic film is insufficient in lubricity and scratch resistance; if more than 25 parts, too much surface-modified high-density polyethylene particles (D) are present in the inorganic film, and the corrosive medium may be along the surface.
  • the modified high-density polyethylene particles (D) interface penetrates into the inorganic film to reduce the corrosion resistance of the inorganic film.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the inorganic surface-treated galvanized steel sheet of the invention needs to have good surface electrical conductivity, and can discharge the static electricity generated during the actual operation of the stamped and formed parts through the surface thereof, thereby preventing a large amount of static electricity from being zero.
  • the surface area of the piece is concentrated, which affects the safety and electromagnetic properties of the part and affects the normal use of the part.
  • the above graphene sheet layer needs to be stably present in the aqueous inorganic surface treatment agent for a long period of time, and no agglomeration, precipitation, and precipitation occur.
  • the graphene sheets due to the large van der Waals force between the sheets, the graphene sheets are particularly prone to agglomeration between the graphene sheets, and are not easily dispersed uniformly in the aqueous inorganic surface treatment agent. Therefore, it is necessary to modify the surface of the above graphene sheets. By introducing other substances to destroy the surface van der Waals force, the graphene sheets are peeled off from each other, so that they can be stably present in the aqueous inorganic surface treatment agent for a long time.
  • the graphene surface-modified substance is further limited.
  • the main component of the aqueous inorganic surface treatment agent of the present invention is mostly a silicon-containing substance such as a hydrophobic monoorganosilane coupling agent (A), a system crosslinking agent (B), and a water-soluble nano sol (C)
  • the present invention uses the orthosilicate as a modifying substance and propanol as a solvent to surface the graphene sheet layer. modified.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the graphene sheet layer used in the present invention has a sheet structure and may be a single layer or a plurality of layers.
  • the number of sheets is preferably 5 or less (the thickness of the sheet is between 0.35 and 1.75 nm).
  • the graphene sheet layer used in the present invention has a sheet diameter of 2 to 5 ⁇ m and a graphene diameter to thickness ratio of 1100 to 14,000.
  • the surface of the graphene sheet layer used in the present invention is modified with orthosilicate, and a method known for its use can be used.
  • the graphite oxide can be ultrasonically dispersed for 1 hour by immersing the graphite oxide in a strong oxidizing solution (such as a concentrated sulfuric acid/potassium permanganate mixed solution, a concentrated sulfuric acid/concentrated nitric acid mixed solution) at 70-80 ° C, and then filtered. And washed with a large amount of deionized water to neutral, to obtain a graphene oxide sheet; further, the graphene oxide sheet, orthosilicate and propanol were stirred and mixed at 100 ° C for 24 h and then filtered. The silicate-modified graphene oxide is obtained; secondly, propanol is used, and the orthosilicate-modified graphene oxide is diluted to a mass fraction of 1-5%.
  • a strong oxidizing solution such as a concentrated sulfuric acid/potassium per
  • the orthosilicate-modified graphene oxide used in the present invention may be a tetrasilicate orthosilicate, a tetraethyl orthosilicate or a butyl orthosilicate. One or more.
  • the orthosilicate-modified graphene oxide has a carbon oxide atom number ratio of ⁇ 3, and the silicon element content is between 5-12%.
  • the orthosilicate-modified graphene oxide surface grafted orthosilicate of the invention not only can improve the dispersion stability coefficient of graphene oxide in the aqueous inorganic surface treatment agent system, prevent agglomeration or precipitation thereof, and can also enhance graphite oxide.
  • the sheet-structured graphene oxide is uniformly dispersed inside the inorganic film, and when the corrosive medium penetrates into the inorganic film, the graphene oxide sheet layer can increase the permeation path of the corrosive medium, thereby providing excellent physical protection. Greatly improve the corrosion resistance of the film.
  • the graphene oxide sheet is carbon-carbon covalently bonded between the atoms, has excellent mechanical properties, and has good resistance to wear and damage of external objects, thereby improving the scratch resistance of the inorganic film. effect.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the orthosilicate-modified graphene oxide used in the present invention is calculated by using graphene oxide in an amount of 0.05 to 0.5 parts by weight in the inorganic film. If less than 0.05 parts, that is, when the graphene oxide is less, the graphene oxide has no obvious improvement on the surface conductivity of the inorganic film; if it is higher than 0.5 part, that is, when the graphene oxide is more, the inorganic film is affected by the graphene oxide. Dark, affecting the appearance. At the same time, a large amount of graphene oxide is also prone to agglomeration, which reduces the surface quality of the inorganic film.
  • the fluorine-containing compound used in the present invention is water-soluble, and may be a fluorine-containing metal salt or a fluorine-containing acid.
  • the fluorine-containing compound may be one or more of sodium fluoride, ammonium fluorotitanate, sodium fluorosilicate, hexafluorotitanate, and fluorosilicic acid.
  • the mass fraction in the inorganic film is from 1 to 4 parts, calculated as the fluorine element in the fluorine-containing compound.
  • the corrosion resistance of the inorganic film may decrease; if the mass fraction of fluorine is more than 4 parts, that is, the fluorine compound When more, the stability of the aqueous inorganic surface treatment agent may be deteriorated.
  • the phosphorus-containing compound used in the present invention is water-soluble, and may be a phosphate or a phosphoric acid.
  • the phosphorus-containing compound may be one or more of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, three-way metaphosphoric acid, ammonium phosphate, aluminum tripolyphosphate, and ammonium polyphosphate.
  • the amount of the mass fraction in the inorganic film is from 0.5 to 4 parts, calculated as the phosphorus element in the phosphorus-containing compound.
  • the mass fraction of phosphorus is less than 0.5 parts, that is, when there are less phosphorus compounds, there is no effect of addition, and the corrosion resistance of the inorganic film may decrease; if the mass fraction of phosphorus is more than 4 parts, That is to say, when there are many phosphorus-containing compounds, the adhesion of the inorganic film may be deteriorated.
  • the metal salt compound used in the present invention is a water-soluble salt, and may be one or more of a titanium salt, a phosphonium salt, a phosphonium salt, a molybdenum salt, a tungsten salt, a cobalt salt, and a zirconium salt.
  • the titanium salt may be one or more of ammonium fluorotitanate, hexafluorotitanate, titanium orthosulfate, titanium oxysulfate or titanium chloride;
  • the cerium salt may be cerium nitrate, cerium sulfate, or a fluorine-containing cerium salt or one or more of cerium ammonium composite salts;
  • the cerium salt may be one or more of cerium chloride, cerium sulfate and cerium nitrate;
  • the molybdenum salt may be ammonium molybdate or molybdic acid One or more of magnesium or sodium molybdate;
  • the tungsten salt may be one or more of ammonium tungstate, magnesium tungstate, ammonium paratungstate or ammonium metatungstate;
  • the cobalt salt may be cobalt nitrate, cobalt sulfate or chlorine
  • the inorganic cobalt salt such as cobalt may also be one or more of co
  • the metal salt compound can react with the galvanic layer on the surface of the galvanized steel sheet and the hydroxyl groups of other components in the aqueous inorganic surface treatment agent to form a metal bond having a high bond energy, forming a thin structure dense metal on the surface of the galvanized layer.
  • the salt conversion film physically shields the direct contact between the steel plate and the corrosive medium, reduces the possibility of corrosion of the steel plate, and significantly improves the anti-film erosion resistance of the steel plate.
  • the amount of the mass in the film is 0.1 to 2.5 parts, calculated as the metal element.
  • the mass fraction of the rare earth element is less than 0.1 part, that is, when the metal salt compound is small, there is no effect of addition, and the corrosion resistance and adhesion of the inorganic film may be lowered; if the mass fraction of the rare earth element is more than 2.5 parts When the metal salt-containing compound is contained, the stability of the aqueous inorganic surface treatment agent may be deteriorated, which may affect the quality of the inorganic surface-treated galvanized steel sheet.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the invention provides a method for manufacturing an environmentally-friendly inorganic surface-treated galvanized steel sheet which can satisfy the rapid deep-drawing processing of the progressive die in the micro-motor field and has excellent red rust resistance and surface electrical conductivity.
  • the drying temperature of the steel plate is between 60-120 °C. If it is lower than 60 °C, the crosslinking reaction of the inorganic film is insufficient, which may cause the properties of the inorganic film to decrease. If it is higher than 120 °C, the middle part of the aqueous inorganic surface treatment agent is grouped. Sub-performance changes may affect the film formation effect.
  • An inorganic surface-treated galvanized steel sheet according to the present invention a preparation method thereof and an aqueous inorganic surface treatment agent,
  • the water inorganic surface treatment agent of the invention is applied on the surface of a galvanized steel sheet, and the dry film thickness thereof is between 0.3 and 1 micrometer.
  • the inorganic film may be thinned, which may cause the stamping processability of the inorganic film.
  • the red rust resistance is reduced, and when the inorganic film thickness exceeds 1 micrometer, the surface treatment cost per unit area is increased.
  • the heat drying method of the aqueous inorganic surface treatment agent applied to the surface of the galvanized steel sheet is not particularly limited, and may be hot air heating, induction heating, infrared heating or the like.
  • the size, shape, and the like of the galvanized steel sheet are not particularly limited in the present invention.
  • the galvanized steel sheet which can be used in the present invention may be an electroplated pure zinc steel sheet, a hot dip galvanized pure steel sheet, a hot dip galvanized aluminum steel sheet, or an alloyed hot dip galvanized steel sheet.
  • the aqueous inorganic surface treatment agent of the present invention can form an inorganic film on the surface of the galvanized steel sheet by coating and low temperature rapid curing (less than 100 ° C), and the galvanized steel sheet coated with the inorganic film It is required to meet the requirements of rapid die-cutting of the progressive die, such as non-clamping, part appearance, dimensional accuracy and surface cleanliness, as well as excellent red rust resistance, surface conductivity and non-adhesive properties of the film. .
  • stamping without clamping requires that the parts can be naturally separated from the die by gravity after rapid stamping (the stamping parts cannot be naturally detached if the stamped parts are stuck on the die of a certain stage of the progressive die), Therefore, the parts that are naturally detached automatically enter the next stamping station under the tapping traction; the appearance of the parts after stamping requires no surface defects such as stamping blackening, stamping and brightening, stamping and scratching, and black dot stripping on the surface of the stamped part.
  • the surface of the parts is white, no broken film or zinc powder is attached to the surface; the red rust resistance of the parts mainly refers to the red rust on the surface of the stamped parts to evaluate the corrosion resistance of the parts. The excellent red rust resistance ensures that the materials can be used barely.
  • Post-coating; surface conductivity mainly means that the surface of the galvanized steel sheet coated with the inorganic film should have certain electrical conductivity to ensure the grounding safety and electromagnetic characteristics of the molded part.
  • the present invention uses a hydrophobic monoorganosilane coupling agent having both a hydrophobic group and a reactive group as a main film-forming substance, and the inorganic film further has a hydrophobic and low surface on the basis of excellent red rust resistance.
  • the ability to achieve the "non-stick" nature of the inorganic film allows it to maintain excellent surface cleanliness after rapid deep drawing of the progressive die.
  • the invention adopts a system cross-linking agent having a plurality of reactive groups and a water-soluble nano sol, further strengthens the degree of cross-linking of the inorganic film in three dimensions, thereby making the inorganic film resistant to red rust, hardness and abrasion resistance. The performance has been greatly improved.
  • the reactive group in the surface-modified high-density polyethylene particles of the present invention can react with various main components in the treatment liquid to form a covalent bond, which can not only strengthen the bonding strength between the high-density polyethylene particles and the inorganic film. It is also capable of restraining high-density polyethylene particles, thereby ensuring that high-density polyethylene particles can be uniformly dispersed in the inorganic film, providing excellent wear resistance in the entire thickness direction of the inorganic film, improving the punching processability and scratch resistance of the inorganic film. performance.
  • the present invention uses a graphitic structure of 5 layers or less of graphene oxide, and grafts orthosilicate on the surface thereof, improves the dispersion stability of graphene oxide in an aqueous inorganic surface treatment agent system, and enhances graphene oxide and water.
  • the conductive network enhances the effect of graphene oxide on the surface conductivity of the inorganic film.
  • the aqueous inorganic surface treatment agent of the invention does not contain chromium, and is an environmentally-friendly surface treatment agent.
  • the galvanized steel sheet can satisfy the rapid deep-drawing processing of the progressive die in the field of micro-motors, and at the same time Excellent parts with red rust resistance and surface conductivity.
  • the types of substrates used are shown in Table 1.
  • mild steel having a thickness of 0.5 mm was used.
  • the aqueous inorganic surface treatment agent for forming an inorganic film is a hydrophobic type monoorganosilane coupling agent (Table 2), a system crosslinking agent (Table 3), a water-soluble nano sol (Table 4), and a surface-modified high-density polymerization.
  • Ethylene particles Table 5
  • orthosilicate-modified graphene oxide Table 6
  • water-soluble fluoride Table 7
  • water-soluble phosphide Table 8
  • water-soluble metal salt compounds Table 9
  • A11 1H,1H,2H,2H-perfluorodecyltriethoxysilane coupling agent A12 1H,1H,2H,2H-perfluorooctyltrimethoxysilane coupling agent A13 1H,1H,2H,2H-perfluorooctyltriethoxysilane coupling agent A14 Methylphenyldiethoxysilane A15 Fluoromethylethoxydimethoxysilane A16 Fluoroethyltriethoxysilane A17 3-fluoropropylmethyldiethoxysilane
  • test sample was sampled and tested according to the following test methods, thereby obtaining the evaluation obtained.
  • the test data for each property is listed in Table 11. Among them, the test to evaluate its performance parameters is as follows:
  • the salt spray test was carried out on the flat plate.
  • the test standard was ASTMB117, and the test time was 120 hours.
  • the evaluation criteria were:
  • ⁇ : white rust area ratio is less than 5%
  • ⁇ White rust area ratio is greater than 5% and less than 10%
  • ⁇ : white rust area ratio is greater than 10% and less than 50%
  • ⁇ : white rust area ratio is greater than 50%
  • the Erikson cupping instrument was used to carry out the 8 mm cup process, and the salt spray test was carried out on the cup portion.
  • the test standard was ASTM B117, and the test time was 72 hours. Evaluation criteria:
  • ⁇ The area ratio of white rust in the cup is less than 5%.
  • ⁇ white rust area ratio of cup protrusion is more than 5% and less than 10%
  • the white rust area ratio of the cup portion is greater than 10% and less than 50%.
  • ⁇ white rust area ratio of cup protrusion is greater than 50%
  • the salt spray test was carried out on the flat plate.
  • the test standard was ASTMB117, and the time when red rust began to appear was recorded.
  • the evaluation criteria were:
  • the sample was prepared by the drawbead method.
  • the experimental conditions were as follows: the pressure under the fixed bead was 7 KN, the diameter of the indenter was 9.6 mm, and the drawing speed was 200 mm/min. After the drawing test was completed, the surface of the sample was cleaned by blowing the surface of the sample with a hair dryer for 5 seconds. evaluation standard:
  • the surface resistance of the upper and lower surfaces was measured by the four-needle method, and 10 points were measured on the upper and lower surfaces, and the average surface resistance at 20 points was calculated. evaluation standard:
  • the average surface resistance is less than 0.1 milliohms
  • the average surface resistance is greater than 0.1 milliohms and less than 0.5 milliohms
  • the average surface resistance is greater than 0.5 milliohms and less than 1 milliohm
  • the average surface resistance is greater than 1 milliohm
  • a utility knife is used to draw 100 small cells on the surface of the coating film, the size is 1 mm 2 , and the depth should be smoothed through the paint film layer to reach the surface of the steel plate. After peeling off with a glass tape, the residual number of the paint film was observed, and the more the residual number, the better the coatability of the steel plate to the ink.
  • Example 23 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 24 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 25 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 26 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 27 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 28 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 29 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 30 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 31 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 32 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 33 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 34 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 35 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 36 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 37
  • Example 56 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 57 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 58 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 59 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 60 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 61 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 62 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 63 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 64 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 65 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 66 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 67 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 68 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 69 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Table 11 lists the performance parameters of the test panels after application of the aqueous inorganic surface treatment agents in Examples 1-100 and Comparative Examples 1-15.
  • the surface-modified high-density polyethylene particles (D) were not contained in the aqueous inorganic surface treatment agent of Comparative Example 3 and Comparative Example 8, and therefore, the press formability of the inorganic film of the galvanized steel sheet coated with the aqueous inorganic surface treatment agent And wear resistance is poor.
  • the inorganic film in Comparative Example 11 was low in thickness, resulting in poor overall performance.
  • the baking curing temperature was low, resulting in the inorganic film not being completely cured, so that the inorganic film was inferior in overall performance.

Abstract

L'invention concerne une feuille d'acier galvanisée traitée en surface inorganique respectueuse de l'environnement, son procédé de préparation et un agent de traitement de surface inorganique aqueux associé, apte à satisfaire les exigences de traitement rapide à emboutissage profond de matrices progressives dans le domaine des micromoteurs, et à présenter un excellent rendement de résistance à la rouille rouge et une excellente conductivité de surface pour des pièces et des éléments. Un agent de traitement de surface inorganique aqueux comprend un unique agent de réticulation en présence de silane organique contenant des groupes hydrophobes, un agent de réticulation de système, un nanosol soluble dans l'eau, des particules de polyéthylène haute densité modifiées en surface, du graphène oxydé modifié par orthosilicate de tétraéthyle, un composé fluoré soluble dans l'eau, un composé phosphoreux soluble dans l'eau et un composé de sel métallique soluble dans l'eau qui sont revêtus et durcis sur la surface d'une feuille d'acier galvanisée; la feuille d'acier galvanisée traitée en surface inorganique obtenue présente un excellente rendement de résistance à la rouille rouge, une excellente conductivité de surface, un excellent rendement de lubrification de surface et un excellente rendement de résistance au noircissement, et peut satisfaire les exigences d'un traitement à emboutissage profond rapide et d'un service nu de matrices progressives, et la feuille d'acier galvanisée traitée en surface inorganique est particulièrement applicable au domaine des micromoteurs.
PCT/CN2017/098430 2016-08-24 2017-08-22 Feuille d'acier galvanisée traitée en surface inorganique, son procédé de préparation, et agent de traitement de surface inorganique aqueux associé WO2018036465A1 (fr)

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