CN105602372A - Magnesium alloy surface protective high-hardness corrosion resistance composite coating and preparation method thereof - Google Patents

Magnesium alloy surface protective high-hardness corrosion resistance composite coating and preparation method thereof Download PDF

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Publication number
CN105602372A
CN105602372A CN201610091110.2A CN201610091110A CN105602372A CN 105602372 A CN105602372 A CN 105602372A CN 201610091110 A CN201610091110 A CN 201610091110A CN 105602372 A CN105602372 A CN 105602372A
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China
Prior art keywords
coating
composite coating
boron nitride
cubic boron
magnesium alloy
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CN201610091110.2A
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Chinese (zh)
Inventor
游国强
闫鹏
段平安
张恒
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Chongqing University
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Chongqing University
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Priority to CN201610091110.2A priority Critical patent/CN105602372A/en
Publication of CN105602372A publication Critical patent/CN105602372A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention discloses a magnesium alloy surface protective high-hardness corrosion resistance composite coating and a preparation method thereof. The composite coating is prepared from nanometer cubic boron nitride particles and an organic coating, wherein the mass percent of the nanometer cubic boron nitride particles is 1-20wt%. The preparation method of the composite coating comprises the steps that the nanometer cubic boron nitride is placed into a water solution containing a dispersing agent, and mechanical stirring and ultrasonic dispersion are carried out for 0.5-2 h; then the dispersed water solution containing the nanometer cubic boron nitride is added into the organic coating, the mixture is mechanically stirred to be uniform and ultrasonically dispersed for 0.5-2 h, and therefore the composite coating is obtained; after the coating is prepared, the surface of a magnesium alloy part which is conventionally pretreated is coated with the composite coating through a conventional spraying method. A coating layer obtained through the composite coating has high wear resistance and corrosion resistance.

Description

High-hardness corrosion-resistant composite coating of magnesium alloy surface protective and preparation method thereof
Technical field
The invention belongs to technical field of magnesium alloy surface treatment, be specifically related to high-hardness corrosion-resistant composite coating that a kind of magnesium alloy surface protective uses and preparation method thereof.
Background technology
Magnesium alloy density is low, have that specific strength and specific stiffness are high, heat-conductivity conducting function admirable, damping vibration attenuation and electromagnetic wave shielding good, be easy to shape and the advantages such as reclaiming, have broad application prospects in fields such as land vehicle, 3C Product, handheld tool, Aero-Space and defence and militaries, be the lightweight material having a high potential, be described as " green material of 21 century ".
But magnesium alloy standard electrode potential is negative (2.36V) extremely, and the oxide-film forming after autoxidation in atmosphere is loose porous, does not substantially possess protective effect, poor corrosion resistance. In practical application, Magnesium Alloys Components needs to carry out surfacecti proteon processing more. Magnesium alloy surface protective treatment technology comparatively ripe and that have engineering to apply mainly comprises at present: chemical composition coating, chemistry and plating, anodic oxidation, differential arc oxidation, organic coating etc.
Chemical composition coating: what chemical transformation technique was comparatively ripe is chromate transformation approach and phosphate conversion method. The former is owing to using poisonous and hazardous chromate, and there be limited evidence currently of uses; The latter's cost is low, and conversion film function admirable, but generally thinner can not meet the comparatively anticorrosion and wearability requirement of magnesium alloy under harsh conditions of reality, how as the prime coats of subsequent treatment.
Chemical plating and plating: chemical plating is taking nickel plating as main, although gained coating has good mechanical property, corrosion resistance, the stability of chemical nickel-plating solution is not high and process conditions are wayward. Once chemical deposit is damaged or have defect, destroys there is serious galvanic corrosion. Although good at Mg alloy surface Direct Electroplating coating performance, electroplating technology complexity, and often there is plating leakage problem.
Anodic oxidation: anode oxide film have strong with metallic matrix adhesion, electrical insulating property good, excellent optical performance, heat shock resistance, the advantage such as wear-resistant, corrosion-resistant, but Anodic Film On Magnesium Alloy layer growth speed is slow, the combination of rete and matrix and Performance Ratio aluminium alloy are poor, and in electrolyte, generally contain poisonous complex compound and fluoride.
Differential arc oxidation: micro-arc oxidation films has that porosity film low, that generate is combined with base closely, quality is hard, be evenly distributed, high corrosion resistance and wearability, but cost is high, is restricted in engineering is applied.
Organic coating: it is simple, with low cost that organic coating has technique, significantly improves the advantages such as decay resistance is the magnesium alloy surface protective processing method generally using at present; The method can be used separately, also can be combined with said method, first Magnesium Alloys Components is carried out to chemical composition coating, anodic oxidation, differential arc oxidation, coating processing, as prime coat, then carries out application with organic coating, and protection effect is better. Conventional organic coating has at present: epoxy resin, acrylic acid, organosilicon, fluorine carbon paint etc., when bottoming processing and application are proper, can obtain good antiseptic effect; But, use the coating hardness prepared of above-mentioned coating on the low side, wear-resisting and scratch resistance ability a little less than, be difficult to meet the service demand that has friction, collides with.
Summary of the invention
The above-mentioned weak point that the object of the invention is to overcome conventional organic coating, provides high-hardness corrosion-resistant composite coating of a kind of magnesium alloy surface protective and preparation method thereof. There is higher wearability and corrosion resistance by the coating that this composite coating obtains, can meet the requirement of shelter of magnesium alloy part in severe rugged environment.
For achieving the above object, technical solution of the present invention is as follows:
1. this composite coating for adding nano cubic boron nitride particle in organic coating; The mass percent of the nano cubic boron nitride particle adding is 1～20wt%.
2. the machine coating that added is the one in epoxy resin, acrylic acid, organosilicon, fluorine carbon paint.
3. the preparation method of this composite coating is: nano cubic boron nitride is placed in the aqueous solution containing appropriate dispersant by (1), and mechanical agitation ultrasonic wave disperse 0.5～2h; (2) the above-mentioned scattered aqueous solution containing nano cubic boron nitride is joined in organic coating, the even also ultrasonic wave of mechanical agitation disperses 0.5～2h, obtains composite coating.
Advantage of the present invention and beneficial effect are as follows:
(1) coating forming at magnesium alloy component surface spraying composite coating by the inventive method, has higher wearability and corrosion resistance;
(2) this composite coating preparation technology is simple, and production efficiency is high, is applicable to large-scale production and promotes the use of;
(3) applicability of the present invention is wider, is almost applicable to magnesium alloy and the conventional organic coating of all trades mark.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Material is prepared: by AZ31 magnesium alloy cutting polishing and through pretreatment such as surface sand-blasting, machine glazed finish, electrochemical deoilings.
Composite coating preparation: first get 5g nano cubic boron nitride and be placed in the aqueous solution of 10ml containing appropriate calgon dispersant, mechanical agitation ultrasonic wave disperse 0.5h, then the scattered aqueous solution containing nano cubic boron nitride is added in 85g acrylic acid organic coating, mechanical agitation ultrasonic wave disperse 0.5h, obtain the composite coating that nano cubic boron nitride content is 5wt%.
Composite coating spraying: adopt aerial spraying method to carry out routine spraying, obtain complete coating after solidifying.
It is smooth that the present embodiment is applied above-mentioned composite coating spraying gained Mg alloy surface, is uniformly dispersed. Be 40um through measuring its thickness, pencil hardness test tested for hardness is 5H, and resisting salt fog corrosion reaches as high as 700h.
Embodiment 2
Material is prepared: by AM60 magnesium alloy cutting polishing and through pretreatment such as surface sand-blasting, machine glazed finish, electrochemical deoilings.
Composite coating preparation: first get 10g nano cubic boron nitride and be placed in the aqueous solution of 10ml containing appropriate DBSA dispersant, mechanical agitation ultrasonic wave disperse 1h, then the scattered aqueous solution containing nano cubic boron nitride is placed in to 80g epoxy resin organic coating, the even also ultrasonic wave of mechanical agitation disperses 1h, obtains the composite coating that nano cubic boron nitride content is 10wt%.
Composite coating spraying: adopt aerial spraying method to carry out routine spraying, obtain complete coating after solidifying.
It is superior in quality that the present embodiment is applied above-mentioned composite coating spraying gained Mg alloy surface. Be 50um through measuring its thickness, pencil hardness test tested for hardness is 6H, and resisting salt fog corrosion reaches as high as 900h.
Embodiment 3
Material is prepared: by AZ91 magnesium alloy cutting polishing and through pretreatment such as surface sand-blasting, machine glazed finish, electrochemical deoilings.
Composite coating preparation: first get 15g nano cubic boron nitride and be placed in the aqueous solution of 10ml containing triethanolamine dispersant, mechanical agitation ultrasonic wave disperse 2h, then the scattered aqueous solution containing nano cubic boron nitride is placed in to 75g fluorine carbon paint organic coating, the even also ultrasonic wave of mechanical agitation disperses 2h, obtains the composite coating that nano cubic boron nitride content is 15wt%.
Composite coating spraying: adopt aerial spraying method to carry out routine spraying, obtain complete coating after solidifying.
It is superior in quality that the present embodiment is applied above-mentioned composite coating spraying gained Mg alloy surface. Be 55um through measuring its thickness, pencil hardness test tested for hardness is 8H, and resisting salt fog corrosion reaches as high as 900h.
In addition, be to be understood that, although this description is described according to embodiment, but be not that each embodiment only comprises an independently technical scheme, this narrating mode of description is only for clarity sake, those skilled in the art should make description as a whole, and the technical scheme in each embodiment also can, through appropriately combined, form other embodiments that it will be appreciated by those skilled in the art that.

Claims (3)

1. magnesium alloy surface protective high-hardness corrosion-resistant composite coating, is characterized in that: in organic coating, add nano cubic boron nitride particle, the mass percent of the nano cubic boron nitride particle adding is 1～20wt%.
2. high rigidity, anticorrosive composite paint for magnesium alloy surface protective according to claim 1, is characterized in that: described organic coating is the one in epoxy resin, acrylic acid, organosilicon and fluorine carbon paint.
3. the preparation method of high-hardness corrosion-resistant composite coating for magnesium alloy surface protective, is characterized in that: its preparation process is as follows:
(1) nano cubic boron nitride is placed in to the aqueous solution containing appropriate dispersant, mechanical agitation ultrasonic wave disperse 0.5～2h;
(2) the above-mentioned scattered aqueous solution containing nano cubic boron nitride is joined in organic coating, the even also ultrasonic wave of mechanical agitation disperses 0.5～2h, obtains composite coating.
CN201610091110.2A 2016-02-18 2016-02-18 Magnesium alloy surface protective high-hardness corrosion resistance composite coating and preparation method thereof Pending CN105602372A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106118374A (en) * 2016-08-04 2016-11-16 浙江无奇涂料有限公司 A kind of high hardness magnesium alloy anti-corrosive powder paint
CN106349771A (en) * 2016-09-19 2017-01-25 中国科学院宁波材料技术与工程研究所 Substrate surface cavitation-resistant erosion-resistant coating and preparation method thereof
CN109810622A (en) * 2019-01-07 2019-05-28 淮阴工学院 The preparation method of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating and its film
CN110358408A (en) * 2019-07-30 2019-10-22 华北理工大学 A kind of CBN composite coating and CBN composite coating layer cutter and its preparation method and application
CN116656206A (en) * 2023-05-16 2023-08-29 武汉理工大学 Wear-resistant anticorrosive paint with self-healing capability and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1701096A (en) * 2002-11-25 2005-11-23 3M创新有限公司 Curable emulsions and abrasive articles therefrom
CN1777656A (en) * 2003-04-30 2006-05-24 国家淀粉及化学投资控股公司 Waterbased high abrasion resistant coating
CN1950416A (en) * 2004-05-07 2007-04-18 Ppg工业俄亥俄公司 Film-forming compositions substantially free of organic solvent, multi-layer composite coatings and related methods
CN101292001A (en) * 2005-09-14 2008-10-22 Ppg工业俄亥俄公司 Multi-component, waterborne coating compositions, related coatings and methods

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1701096A (en) * 2002-11-25 2005-11-23 3M创新有限公司 Curable emulsions and abrasive articles therefrom
CN1777656A (en) * 2003-04-30 2006-05-24 国家淀粉及化学投资控股公司 Waterbased high abrasion resistant coating
CN1950416A (en) * 2004-05-07 2007-04-18 Ppg工业俄亥俄公司 Film-forming compositions substantially free of organic solvent, multi-layer composite coatings and related methods
CN101292001A (en) * 2005-09-14 2008-10-22 Ppg工业俄亥俄公司 Multi-component, waterborne coating compositions, related coatings and methods

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106118374A (en) * 2016-08-04 2016-11-16 浙江无奇涂料有限公司 A kind of high hardness magnesium alloy anti-corrosive powder paint
CN106349771A (en) * 2016-09-19 2017-01-25 中国科学院宁波材料技术与工程研究所 Substrate surface cavitation-resistant erosion-resistant coating and preparation method thereof
CN106349771B (en) * 2016-09-19 2021-03-26 中国科学院宁波材料技术与工程研究所 Cavitation-resistant erosion-resistant coating on surface of substrate and preparation method thereof
CN109810622A (en) * 2019-01-07 2019-05-28 淮阴工学院 The preparation method of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating and its film
CN110358408A (en) * 2019-07-30 2019-10-22 华北理工大学 A kind of CBN composite coating and CBN composite coating layer cutter and its preparation method and application
CN110358408B (en) * 2019-07-30 2021-02-23 华北理工大学 CBN composite coating, CBN composite coating cutter, and preparation method and application of CBN composite coating cutter
CN116656206A (en) * 2023-05-16 2023-08-29 武汉理工大学 Wear-resistant anticorrosive paint with self-healing capability and preparation method and application thereof

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