CN112375482A - Chromium-free water-based paint and preparation method and application thereof - Google Patents

Chromium-free water-based paint and preparation method and application thereof Download PDF

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Publication number
CN112375482A
CN112375482A CN202011371743.1A CN202011371743A CN112375482A CN 112375482 A CN112375482 A CN 112375482A CN 202011371743 A CN202011371743 A CN 202011371743A CN 112375482 A CN112375482 A CN 112375482A
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water
chromium
powder
emulsion
based paint
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Inventor
高延敏
郑润
杨红洲
孙存思
***
姜荪
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Jiangsu University of Science and Technology
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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D125/00—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 an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • 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
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0812—Aluminium
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a chromium-free water-based paint. The paint consists of 20-30% of A, 5-15% of B, 5-10% of Al powder, 25-50% of Zn powder, 10-30% of water-based resin or emulsion and 5-20% of water. Wherein A is methyl phthalic acid, ZrCl4And 3-aminopropionic acid; b is obtained by the reaction of a silane coupling agent and sorbic acid. The preparation method of the coating comprises the following steps: uniformly mixing A and B; then adding other components into the mixture, and fully stirringMixing, and mixing. The water-based paint avoids the use of chromium and is environment-friendly; strong corrosion resistance, good stability, long storage time and no precipitation in the shelf life.

Description

Chromium-free water-based paint and preparation method and application thereof
Technical Field
The invention belongs to a metal surface treatment process, and particularly relates to a chromium-free water-based paint, and a preparation method and application thereof.
Background
Fasteners are key materials used as engineering and infrastructure, and are a class of mechanical parts that function as a fastening connection and are used in a very wide variety of applications. The fastener has wide application industry, and can be seen on various mechanical equipment, vehicles, ships, railways, bridges and other articles. Its service life directly affects the safe and stable production of the equipment, where the key to determining such stability and safety is the coating (paint) of the metal fastener surface. The general paint is composed of adhesive, surface passivator, surface coating initiator and addition of Cr, Al, Zn and other salts. In particular, metal chromates, which perform the dual function of film-forming material and passivation in the coating, have the effect of improving corrosion resistance, decoration, and protection of metal fasteners. However, the chromate compound contains a heavy metal salt Cr, and is prohibited from being used because it easily pollutes the environment.
The present invention and the existing literature are that the dual action of Cr salt is decomposed, some substances (such as silicon, zirconium, epoxy resin, amino resin, etc.) are used for film formation, and other salts (such as tungsten salt, molybdenum salt, etc.) are used for sharing the passivation effect of chromium salt. However, due to the complexity of the composition, Al and Zn in water are susceptible to corrosion during storage to generate gas and swell. Other metal and salt passivators lose their coating function due to their instability and precipitation in water. Therefore, it is a challenging problem to adopt a special method to ensure the stability of the material and prevent Al and Zn from being corroded to generate puffing.
Disclosure of Invention
One of the purposes of the invention is to provide a chromium-free water-based paint. The specific technical scheme is as follows:
a chromium-free water-based paint comprises the following components in percentage by mass: 20-30% of A, 5-15% of B, 5-10% of Al powder, 25-50% of Zn powder, 10-30% of water-based resin or emulsion and 5-20% of water; the A has passivation and film forming effects and has the following structure:
Figure BDA0002806283500000011
wherein M is a metal element Zr or Ti, R is an alkyl group having 1 to 3 carbon atoms, L1is-OH, -COOH or-NH2，L2is-OH, -COOH or-NH2，L1And L2May be the same;
the B is an emulsifier and has the following structure:
Figure BDA0002806283500000021
preferably, the aqueous resin or emulsion is an acrylic emulsion, an epoxy resin, a polyurethane emulsion or a styrene-acrylic emulsion.
Preferably, the mass ratio of the Al powder to the Zn powder is 1: 5.
Preferably, said L1And L2Are all-COOH.
Preferably, the aqueous resin or emulsion is a polyurethane emulsion.
The preparation method of A is as follows:
firstly, methyl phthalic acid and ZrCl are mixed4And 3-aminopropionic acid (NH)2-CH2-CH2-COOH) in a molar ratio of 1:1:2, heating to 85-95 ℃, stirring, and reacting for 5h to obtain a substance A.
The preparation method of B is as follows:
adding a silane coupling agent and sorbic acid (the molar ratio is 1:1) into a synthesis device, stirring, and reacting at the temperature of 85-95 ℃ for 5 hours to obtain a substance B. The preparation process comprises the following steps:
Figure BDA0002806283500000022
the invention also aims to provide a preparation method of the chromium-free water-based paint. The specific technical scheme is as follows:
the preparation method of the chromium-free water-based paint comprises the following steps:
(1) weighing the A and the B according to the mass percentage, stirring and uniformly mixing;
(2) and (2) respectively weighing Al powder, Zn powder, water-based resin or emulsion and water according to the mass percentage, adding the Al powder, the Zn powder, the water-based resin or emulsion and the water into the substances obtained in the step (1), fully stirring and uniformly mixing to obtain the chromium-free water-based paint.
The invention also aims to provide application of the chromium-free water-based paint. The specific technical scheme is as follows:
the chromium-free water-based paint is used for surface corrosion prevention of fasteners.
The invention has the beneficial effects that:
(1) the material A is adopted to replace chromate, so that the dual functions of film forming and passivation are achieved in the coating, the use of chromium is avoided, and the coating becomes an environment-friendly coating.
(2) The zinc and the aluminum in the paint can be prevented from being corroded for a long time, the stability is good, and the paint can be stored for a long time.
(3) The material B is used as an emulsifier, so that the uniformity of the coating is greatly improved, and no precipitate is generated in the shelf life.
(4) Corrosion resistance, and when the film thickness is 10 mu m, the salt corrosion resistance can reach 1000 hours.
Drawings
FIG. 1 is an electrochemical impedance spectrum of the coating composition obtained in example 1;
FIG. 2 is an electrochemical impedance spectrum of the coating composition obtained in example 2;
FIG. 3 is an electrochemical impedance spectrum of the coating composition obtained in example 3;
FIG. 4 is an electrochemical impedance spectrum of the coating composition obtained in example 4.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
1. Formulation of the composition
Preparing the following components in percentage by mass:
Figure BDA0002806283500000031
2. methods of making and using
(1) Preparation of substance a: firstly, methyl phthalic acid and ZrCl are mixed4And 3-aminopropionic acid (NH)2-CH2-CH2-COOH) in a molar ratio of 1:1:2, heating to 85 ℃, stirring, reacting for 5h to obtain substance A, and storing at room temperature for later use.
(2) Preparation of substance B: adding a silane coupling agent and sorbic acid (the molar ratio is 1:1) into a synthesis device, stirring, reacting for 5 hours at 90 ℃ to obtain a substance B, and storing at room temperature for later use.
(3) Preparing a chromium-free water-based paint: 1) weighing the A and the B according to the mass percentage, stirring and uniformly mixing; 2) respectively weighing Al powder, Zn powder, water-based resin or emulsion and water according to the mass percentage, adding the Al powder, the Zn powder, the water-based resin or emulsion and the water into the substances obtained in the step 1), fully stirring and uniformly mixing to obtain the chromium-free water-based paint.
3. Testing
The chromium-free water-based paint obtained in the embodiment is coated on a bolt with a nominal diameter of M16 and a matched nut, when the film thickness is 10 mu M, the salt spray resistance experiment of the coating can reach 600h, and the adhesive force is grade 1; after 600h of salt spray corrosion, a friction coefficient test is carried out, and the friction coefficient is 0.08.
The chromium-free water-based paint obtained in the example was coated on a tinplate, and an electrochemical impedance test was performed after air-drying, and the result is shown in fig. 1.
As can be seen from fig. 1, the Nyquist plot shows an approximate semicircular arc, and the low-frequency region coating resistance value is about Rc ═ 4.3 × 108Ωcm2This means that the coating has good protection function, effectively prevents the corrosion medium from corroding the metal substrate, thereby ensuring that the metal substrate obtains better protection effect.
Example 2
1. Formulation of the composition
Preparing the following components in percentage by mass:
Figure BDA0002806283500000041
2. methods of making and using
(1) Preparation of substance a: firstly, methyl phthalic acid and ZrCl are mixed4And 3-aminopropionic acid (NH)2-CH2-CH2-COOH) in a molar ratio of 1:1:2, heating to 90 ℃, stirring, reacting for 5h to obtain a substance A, and storing at room temperature for later use.
(2) Preparation of substance B: adding a silane coupling agent and sorbic acid (the molar ratio is 1:1) into a synthesis device, stirring, reacting for 5 hours at 90 ℃ to obtain a substance B, and storing at room temperature for later use.
(3) Preparing a chromium-free water-based paint: 1) weighing the A and the B according to the mass percentage, stirring and uniformly mixing; 2) respectively weighing Al powder, Zn powder, water-based resin or emulsion and water according to the mass percentage, adding the Al powder, the Zn powder, the water-based resin or emulsion and the water into the substances obtained in the step 1), fully stirring and uniformly mixing to obtain the chromium-free water-based paint.
3. Testing
The chromium-free water-based paint obtained in the embodiment is coated on a bolt with a nominal diameter of M16 and a matched nut, when the film thickness is 10 mu M, the salt spray resistance experiment of the coating can reach 800h, and the adhesive force is grade 1; and (3) carrying out a friction coefficient test after 800h of salt spray corrosion, wherein the friction coefficient is 0.08.
The chromium-free water-based paint obtained in the example was coated on a tinplate, and an electrochemical impedance test was performed after air-drying, and the result is shown in fig. 2.
As can be seen from fig. 2, the Nyquist plot shows an approximate semicircular arc, and the low-frequency region coating resistance value is about Rc ═ 4.5 × 108Ωcm2This means that the coating has good protection function, effectively prevents the corrosion medium from corroding the metal substrate, thereby ensuring that the metal substrate obtains better protection effect.
Example 3
1. Formulation of the composition
Preparing the following components in percentage by mass:
Figure BDA0002806283500000051
2. methods of making and using
(1) Preparation of substance a: firstly, methyl phthalic acid and ZrCl are mixed4And 3-aminopropionic acid (NH)2-CH2-CH2-COOH) in a molar ratio of 1:1:2, heating to 85 ℃, stirring, reacting for 5h to obtain substance A, and storing at room temperature for later use.
(2) Preparation of substance B: adding a silane coupling agent and sorbic acid (the molar ratio is 1:1) into a synthesis device, stirring, reacting for 5 hours at 90 ℃ to obtain a substance B, and storing at room temperature for later use.
(3) Preparing a chromium-free water-based paint: 1) weighing the A and the B according to the mass percentage, stirring and uniformly mixing; 2) respectively weighing Al powder, Zn powder, water-based resin or emulsion and water according to the mass percentage, adding the Al powder, the Zn powder, the water-based resin or emulsion and the water into the substances obtained in the step 1), fully stirring and uniformly mixing to obtain the chromium-free water-based paint.
3. Testing
The chromium-free water-based paint obtained in the embodiment is coated on a bolt with a nominal diameter of M16 and a matched nut, when the film thickness is 10 mu M, the salt spray resistance experiment of the coating can reach 800h, and the adhesive force is grade 1; and (3) carrying out a friction coefficient test after 800h of salt spray corrosion, wherein the friction coefficient is 0.08.
The chromium-free water-based paint obtained in this example was coated on a tinplate, and an electrochemical impedance test was performed after air-drying, and the result is shown in fig. 3.
As can be seen from fig. 3, the Nyquist plot shows an approximate semicircular arc, and the low-frequency region coating resistance value is about Rc — 3.2 × 108Ωcm2This means that the coating has good protection function, effectively prevents the corrosion medium from corroding the metal substrate, thereby ensuring that the metal substrate obtains better protection effect.
Example 4
1. Formulation of the composition
Preparing the following components in percentage by mass:
Figure BDA0002806283500000061
2. methods of making and using
(1) Preparation of substance a: firstly, methyl phthalic acid and ZrCl are mixed4And 3-aminopropionic acid (NH)2-CH2-CH2-COOH) in a molar ratio of 1:1:2, heating to 85 ℃, stirring, reacting for 5h to obtain substance A, and storing at room temperature for later use.
(2) Preparation of substance B: adding a silane coupling agent and sorbic acid (the molar ratio is 1:1) into a synthesis device, stirring, reacting for 5 hours at 85 ℃ to obtain a substance B, and storing at room temperature for later use.
(3) Preparing a chromium-free water-based paint: 1) weighing the A and the B according to the mass percentage, stirring and uniformly mixing; 2) respectively weighing Al powder, Zn powder, water-based resin or emulsion and water according to the mass percentage, adding the Al powder, the Zn powder, the water-based resin or emulsion and the water into the substances obtained in the step 1), fully stirring and uniformly mixing to obtain the chromium-free water-based paint.
3. Testing
The chromium-free water-based paint obtained in the embodiment is coated on a bolt with a nominal diameter of M16 and a matched nut, when the film thickness is 10 mu M, the salt spray resistance experiment of the coating can reach 1000h, and the adhesive force is grade 1; and (5) carrying out a friction coefficient test after 1000h of salt spray corrosion, wherein the friction coefficient is 0.09.
The chromium-free water-based paint obtained in this example was coated on a tinplate, and an electrochemical impedance test was performed after air-drying, and the result is shown in fig. 4.
As can be seen from fig. 4, the Nyquist plot shows an approximate semicircular arc, and the low-frequency region coating resistance value is about Rc ═ 8.8 × 108Ωcm2This means that the coating has good protection function, effectively prevents the corrosion medium from corroding the metal substrate, thereby ensuring that the metal substrate obtains better protection effect.

Claims (7)

1. The chromium-free water-based paint is characterized by comprising the following components in percentage by mass: 20-30% of A, 5-15% of B, 5-10% of Al powder, 25-50% of Zn powder, 10-30% of water-based resin or emulsion and 5-20% of water; the structure of A is as follows:
Figure FDA0002806283490000011
wherein M is a metal element Zr or Ti, R is an alkyl group having 1 to 3 carbon atoms, L1is-OH, -COOH or-NH2，L2is-OH, -COOH or-NH2，L1And L2May be the same;
the structure of B is as follows:
Figure FDA0002806283490000012
2. the chromium-free aqueous coating according to claim 1, wherein the aqueous resin or emulsion is an acrylic emulsion, an epoxy resin, a polyurethane emulsion or a styrene-acrylic emulsion.
3. The chromium-free water-based paint according to claim 1, wherein the mass ratio of the Al powder to the Zn powder is 1: 5.
4. The chromium-free waterborne coating of claim 1 wherein L is1And L2Are all-COOH.
5. The chromium-free aqueous coating according to claim 1 wherein the aqueous resin or emulsion is a polyurethane emulsion.
6. The method for preparing a chromium-free water-based paint according to any one of claims 1 to 3, comprising the steps of:
(1) weighing the A and the B according to the mass percentage, stirring and uniformly mixing;
(2) and (2) respectively weighing Al powder, Zn powder, water-based resin or emulsion and water according to the mass percentage, adding the Al powder, the Zn powder, the water-based resin or emulsion and the water into the substances obtained in the step (1), fully stirring and uniformly mixing to obtain the chromium-free water-based paint.
7. The chromium-free water-based paint according to any one of claims 1 to 3 for surface corrosion prevention of fasteners.
CN202011371743.1A 2020-11-30 2020-11-30 Chromium-free water-based paint and preparation method and application thereof Pending CN112375482A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006069376A2 (en) * 2004-12-22 2006-06-29 University Of Cincinnati Improved superprimer
CN105925178A (en) * 2016-05-13 2016-09-07 江苏科技大学 Water-based organic and inorganic hybrid anticorrosive paint composition and preparing method thereof
CN109111775A (en) * 2018-07-27 2019-01-01 广东工业大学 A kind of Chrome-free Zn-Al coating and a kind of Chrome-free Zn-Al coating
CN110551433A (en) * 2019-09-18 2019-12-10 河北晨阳工贸集团有限公司 Water-based metal coating and preparation method thereof
CN110713777A (en) * 2019-10-17 2020-01-21 江苏科技大学 Water-based ceramic anticorrosive paint composition and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006069376A2 (en) * 2004-12-22 2006-06-29 University Of Cincinnati Improved superprimer
CN105925178A (en) * 2016-05-13 2016-09-07 江苏科技大学 Water-based organic and inorganic hybrid anticorrosive paint composition and preparing method thereof
CN109111775A (en) * 2018-07-27 2019-01-01 广东工业大学 A kind of Chrome-free Zn-Al coating and a kind of Chrome-free Zn-Al coating
CN110551433A (en) * 2019-09-18 2019-12-10 河北晨阳工贸集团有限公司 Water-based metal coating and preparation method thereof
CN110713777A (en) * 2019-10-17 2020-01-21 江苏科技大学 Water-based ceramic anticorrosive paint composition and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
任洁: "《无机化学 上 理论部分》", 30 July 2015, 东华大学出版社 *
山下晋三: "《交联剂手册》", 30 July 1990, 化学工业出版社 *

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Application publication date: 20210219