CN110079126B - Preparation method of multilayer thin-sheet assembled zinc phosphate anti-corrosion pigment - Google Patents

Preparation method of multilayer thin-sheet assembled zinc phosphate anti-corrosion pigment Download PDF

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CN110079126B
CN110079126B CN201910376208.6A CN201910376208A CN110079126B CN 110079126 B CN110079126 B CN 110079126B CN 201910376208 A CN201910376208 A CN 201910376208A CN 110079126 B CN110079126 B CN 110079126B
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beaker
egg
zinc phosphate
deionized water
pigment
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CN110079126A (en
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杨小红
胡九一
丁龙飞
汪江杰
王瑞侠
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Chizhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/046—Compounds of zinc containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic 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
    • 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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention provides a preparation method of a zinc phosphate anti-corrosion pigment assembled by multiple layers of slices, which utilizes a bionic synthesis method, uses a biological template as a basic template to carry out reaction, and adds polyacrylamide as a template agent into a reaction system to prepare the zinc phosphate anti-corrosion pigment assembled by the slices. The zinc phosphate anti-corrosion pigment assembled by the multiple layers of sheets is prepared by a biomineralization method, so that the anti-corrosion performance of the zinc phosphate anti-corrosion pigment is remarkably improved, and the use cost of the zinc phosphate anti-corrosion pigment is greatly reduced; the addition of the polyacrylamide is beneficial to improving the dispersibility of the zinc phosphate anti-corrosion pigment and the compatibility of a system, thereby improving the anti-corrosion performance.

Description

Preparation method of multilayer thin-sheet assembled zinc phosphate anti-corrosion pigment
Technical Field
The invention relates to the technical field of anti-corrosion pigment preparation, in particular to a preparation method of a zinc phosphate anti-corrosion pigment assembled by multiple layers of sheets.
Background
The metal materials have high chemical activity and belong to active chemical elements. When metal materials are used, the metal materials are inevitably exposed to air, sunlight and water, so that the metal materials are easily subjected to chemical reactions with various substances, which is a cause of metal corrosion. There are many methods for avoiding corrosion of metallic materials, the most important, most widespread and most economical method being the paint masking method, known as "painting". The metal is shielded by the anticorrosive paint, so that the aim of corrosion resistance is fulfilled. The paint film formed by the coating after curing plays a role of physical barrier, and prevents the metal surface from contacting with corrosive substances, so that the metal is prevented from being corroded. Pigments are one of the important components in the basic formulation of primers, and they also have many different functions. For example, pigments are a color source of the coating, and the pigments can enhance the physical strength of the coating, increase the chemical stability of the coating, and the like. In the general sense, most pigments are solid inorganic substances, and these inorganic substances are difficult to dissolve in water and must be uniformly dispersed in the coating system by some special means to achieve the desired effect. Meanwhile, the pigments and organic components in the coating act together to achieve the purpose of metal corrosion prevention through an electrochemical barrier or a physical barrier.
So far, zinc chromate has been the most effective and most used anti-corrosive pigment in the large category of paint pigments. However, cr6+ ions are extremely toxic and carcinogenic, and therefore, their use is strictly limited by governments. In the modern society, the corrosion resistance of the coating and the environmental friendliness of the coating are very important, and the defects are not all right. With the continuing efforts of researchers, more and more materials have become available as anti-corrosive pigments. Among them, molybdate and phosphate compounds are considered to be the most likely to replace the conventional toxic pigments and to be used as novel anticorrosive pigments. Among the two types of compounds, phosphate has received more and more attention from the scientific research and industrial fields because of its advantages of low cost and low toxicity (50 times lower than that of Cr-containing compounds). As the research on phosphate has been increasing, its knowledge has been deepened. Although the advantages of phosphate as an anti-corrosive pigment are quite outstanding, it has a great disadvantage-the anti-corrosive properties are far from the same as those of zinc chromate. If the phosphate does not achieve the anticorrosive properties of zinc chromate, it is difficult to truly replace zinc chromate with an anticorrosive pigment for paint, which is widely used.
There are two factors that affect the corrosion resistance of phosphate-based corrosion inhibiting pigments, namely the morphology and size of the particles and the dispersibility of the particles. Under ordinary salt spray conditions, the use of zinc phosphate anti-corrosion pigments is most suitable because it can reduce the cost of use while ensuring the anti-corrosion effect. If zinc phosphate anti-corrosive pigments with greatly reduced particle size can be used, the anti-corrosive properties will be further improved. The zinc phosphate as new generation non-toxic anticorrosive pigment has great consumption, wide use range and high compatibility with various kinds of resin, may be used as the base material for anticorrosive paint of alkyd, phenolic, epoxy resin, etc. and may be used widely in anticorrosive paint industry to prepare non-toxic antirust pigment and water soluble paint for anticorrosive and to replace traditional toxic antirust zinc chromate pigment. However, the commercially available zinc phosphate tends to have poor dispersibility due to too large particle size, which affects the corrosion resistance.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects and defects of influence on the corrosion resistance caused by too large particle size and poor dispersibility of zinc phosphate in the prior art, the invention provides a preparation method of a multilayer sheet assembled zinc phosphate corrosion-resistant pigment, which aims at researching a simple synthesis method of various zinc phosphate powders with different shapes and appearances and preparing superfine zinc phosphate according to the defects and defects in practical use so as to obtain high-efficiency corrosion resistance, solve the problem of metal corrosion resistance and be applied and popularized in practical production.
(II) technical scheme
In order to realize the purpose, the invention is realized by the following technical scheme:
a preparation method of a zinc phosphate anti-corrosion pigment assembled by multilayer sheets comprises the following steps:
s1, taking a fresh egg, and removing yolk and egg white to obtain a relatively complete egg shell;
s2, taking one 250ml beaker, adding 100ml of deionized water and 25ml of glacial acetic acid, and heating to 40 ℃ and keeping;
s3, placing the eggshells obtained in the step S1 in a beaker for soaking, taking out the eggshells until the surfaces of the eggshells are soft, and cleaning the eggshells which are taken out by using clear water;
s4, adding deionized water into a 1000ml beaker, completely immersing the treated egg shells into the deionized water, keeping the egg shells moist, separating the egg shells from the egg membranes to obtain complete egg membranes, and cleaning the obtained egg membranes with the deionized water for later use;
s5, taking a 25ml conical bottle and a 50ml beaker, washing the conical bottle and the 50ml beaker respectively with deionized water, and adding 0.075-0.125 mol/L Zn (NO) into the conical bottle 3 ) 2 Adding (0.05-0.083) mol/L of Na into a beaker 2 HPO 4 Respectively adding (0.01-0.02) g of polyacrylamide template agent into the conical bottle and the beaker, and fully dissolving and stirring;
s6, wrapping the conical bottle mouth with the egg membrane prepared in the step S4, binding until no liquid overflows when the conical bottle is inverted, inverting the conical bottle and putting the conical bottle into a beaker, completely immersing the egg membrane into the solution and not contacting with the bottom of the beaker, fixing the conical bottle and the beaker, keeping the mutual positions unchanged, and standing and aging;
s7, ageing, then, respectively taking out white flocculent precipitates in the beaker and the conical bottle, washing the precipitates with deionized water, carrying out centrifugal separation, then washing with ethanol and acetone, and carrying out centrifugal separation;
and S8, repeating the step S7, washing with deionized water, performing centrifugal separation, washing with ethanol and acetone, performing centrifugal separation for three times to obtain a product, and drying the product at a low humidity of 40 ℃ to obtain the multilayer sheet assembled zinc phosphate anticorrosive pigment.
According to an embodiment of the present invention, in the step S1, a small opening of 0.5-1 square centimeter is opened at one end of the egg, and the yolk and the albumen are removed.
According to an embodiment of the present invention, the beaker water bath is heated to 40 ℃ and maintained in the step S2.
According to an embodiment of the present invention, 700ml of deionized water is added to the 1000ml beaker in the step S4.
According to an embodiment of the present invention, in the step S4, the whole egg shell is broken by using tweezers while the egg membrane is not damaged, and then the broken egg shell is separated from the egg membrane, so as to obtain the complete egg membrane.
According to an embodiment of the invention, said step S6 is left to stand and age for 2-3 days.
According to an embodiment of the present invention, the zinc phosphate anti-corrosion pigment obtained in step S7 is a sheet-shaped material with a central radial sheet shape and assembled from one sheet to another.
(III) advantageous effects
The invention has the beneficial effects that: a preparation method of a zinc phosphate anti-corrosion pigment assembled by multiple layers of slices utilizes a bionic synthesis method, uses a biological template as a basic template to carry out reaction, and adds polyacrylamide as a template agent into a reaction system to prepare the zinc phosphate anti-corrosion pigment assembled by the slices; the preparation method has the characteristics of simple equipment, high synthesis efficiency, low production cost, good product dispersibility and excellent corrosion resistance, and has wide market application prospect.
The invention has the following advantages:
1) The zinc phosphate anticorrosive pigment assembled by multiple layers of sheets is prepared by a biomineralization method, so that the anticorrosive performance of the zinc phosphate anticorrosive pigment is remarkably improved, and the use cost of the zinc phosphate anticorrosive pigment is greatly reduced.
2) The addition of the polyacrylamide is beneficial to improving the dispersibility of the zinc phosphate anti-corrosion pigment and the compatibility of a system, thereby improving the anti-corrosion performance.
3) The eggshell is used as the template, no pollution is produced in the preparation process, and the method is in line with the green and environment-friendly category.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of the method of the present invention;
FIG. 2 is an SEM photograph of a zinc phosphate multilayer sheet assembly prepared in example one;
FIG. 3 is an SEM photograph of a zinc phosphate multilayer sheet assembly prepared in example II;
FIG. 4 is an SEM photograph of a zinc phosphate multilayer sheet assembly prepared in example III;
fig. 5 is an SEM image of the zinc phosphate multilayer sheet assembly prepared by the comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
In order to improve the corrosion resistance of phosphate, many kinds of phosphate are developed, and researches for improving the corrosion resistance of phosphate through various modifications and various combinations are also increasing. The anticorrosion mechanism of the phosphate anticorrosion pigment is determined, and only through the research of the mechanism, the development difficulty of the environment-friendly high-performance anticorrosion pigment can be reduced, so that a basis is provided for developing anticorrosion paint which is suitable for industrial application, high in reaction activity and long in anticorrosion life.
Referring to fig. 1, a method for preparing a multilayer flake-assembled zinc phosphate anticorrosive pigment includes the following steps:
s1, taking a fresh egg, forming a small opening with a square centimeter at one end of the egg, and removing yolk and egg white to obtain a relatively complete egg shell;
s2, taking one 250ml beaker, adding 100ml of deionized water and 25ml of glacial acetic acid, heating to 40 ℃ in a water bath, and keeping;
s3, placing the eggshells obtained in the step S1 in a beaker for soaking, taking out the eggshells until the surfaces of the eggshells are soft, and cleaning the eggshells which are taken out by using clear water;
s4, adding 700ml of deionized water into a 1000ml beaker, completely immersing the treated egg shell into the deionized water, keeping the egg shell moist, breaking the whole egg shell by using a pair of tweezers on the premise of keeping the egg membrane undamaged, separating the broken egg shell from the egg membrane to obtain a complete egg membrane, and cleaning the obtained egg membrane by using the deionized water for later use;
s5, taking a 25ml conical shapeOne flask and one 50ml beaker are respectively washed by deionized water, and then Zn (NO) with the mol/L of 0.075-0.125 is added into the conical flask 3 ) 2 Adding (0.05-0.083) mol/L Na into a beaker 2 HPO 4 Respectively adding (0.01-0.02) g of polyacrylamide template into the conical bottle and the beaker, and fully dissolving and stirring;
s6, wrapping the conical bottle mouth with the egg membrane prepared in the step S4, binding until no liquid overflows when the conical bottle is inverted, inverting the conical bottle and putting the conical bottle into a beaker, completely immersing the egg membrane into the solution and not contacting with the bottom of the beaker, fixing the conical bottle and the beaker, keeping the mutual positions unchanged, and standing and aging for 2-3 days;
s7, after aging, white flocculent precipitates appear in the beaker and the conical bottle, and the obtained precipitates are respectively taken out, washed by deionized water, centrifugally separated, washed by ethanol and acetone and centrifugally separated;
and S8, repeating the step S7, washing with deionized water, performing centrifugal separation, washing with ethanol and acetone, performing centrifugal separation for three times to obtain a product, and drying the product at a low humidity of 40 ℃ to obtain the multilayer sheet assembled zinc phosphate anticorrosive pigment.
Example one
A preparation method of a multilayer thin-sheet assembled zinc phosphate anti-corrosion pigment comprises the following steps:
s1, taking a fresh egg, forming a small opening with a square centimeter at one end of the egg, and removing yolk and egg white to obtain a relatively complete egg shell;
s2, taking one 250ml beaker, adding 100ml of deionized water and 25ml of glacial acetic acid, heating to 40 ℃ in a water bath, and keeping;
s3, placing the eggshells obtained in the step S1 in a beaker for soaking, taking out the eggshells until the surfaces of the eggshells are soft, and cleaning the eggshells which are taken out by using clear water;
s4, adding 700ml of deionized water into a 1000ml beaker, completely immersing the treated egg shell into the deionized water, keeping the egg shell moist, breaking the whole egg shell by using a pair of tweezers on the premise of keeping the egg membrane undamaged, separating the broken egg shell from the egg membrane to obtain a complete egg membrane, and cleaning the obtained egg membrane by using the deionized water for later use;
s5, taking a 25ml conical bottle and a 50ml beaker, respectively, washing the conical bottle and the 50ml beaker by deionized water, and adding 0.075mol/L Zn (NO) into the conical bottle 3 ) 2 Adding 0.05mol/L of Na into a beaker 2 HPO 4 Respectively adding 0.01g of polyacrylamide template into the conical bottle and the beaker, and fully dissolving and stirring;
s6, wrapping the conical bottle mouth with the egg membrane prepared in the step S4, binding until no liquid overflows when the conical bottle is inverted, inverting the conical bottle and putting the conical bottle into a beaker, completely immersing the egg membrane into the solution and not contacting with the bottom of the beaker, fixing the conical bottle and the beaker, keeping the mutual positions unchanged, and standing and aging for 2 days;
s7, after aging, white flocculent precipitates appear in the beaker and the conical bottle, and the obtained precipitates are respectively taken out, washed by deionized water, centrifugally separated, washed by ethanol and acetone and centrifugally separated;
and S8, repeating the step S7, washing with deionized water, performing centrifugal separation, washing with ethanol and acetone, performing centrifugal separation for three times to obtain a product, and drying the product at a low humidity of 40 ℃ to obtain the multilayer sheet assembled zinc phosphate anticorrosive pigment.
Example two
A preparation method of a zinc phosphate anti-corrosion pigment assembled by multilayer sheets comprises the following steps:
s1, taking a fresh egg, forming a small opening with a square centimeter at one end of the egg, and removing yolk and egg white to obtain a relatively complete egg shell;
s2, taking one 250ml beaker, adding 100ml of deionized water and 25ml of glacial acetic acid, heating to 40 ℃ in a water bath, and keeping;
s3, soaking the eggshell obtained in the step S1 in a beaker, taking out the eggshell until the surface of the eggshell is soft, and cleaning the eggshell which is taken out with clear water;
s4, adding 700ml of deionized water into a 1000ml beaker, completely immersing the treated egg shell into the deionized water, keeping the egg shell moist, breaking the whole egg shell by using a pair of tweezers on the premise of keeping the egg membrane undamaged, separating the broken egg shell from the egg membrane to obtain a complete egg membrane, and cleaning the obtained egg membrane by using the deionized water for later use;
s5, taking a 25ml conical bottle and a 50ml beaker, washing the conical bottle and the 50ml beaker respectively with deionized water, and adding 0.125mol/L Zn (NO) into the conical bottle 3 ) 2 Adding 0.083mol/L Na into a beaker 2 HPO 4 Respectively adding 0.02g of polyacrylamide template agent into the conical bottle and the beaker, and fully dissolving and stirring;
s6, wrapping the conical bottle mouth with the egg membrane prepared in the step S4, binding until no liquid overflows when the conical bottle is inverted, inverting the conical bottle and putting the conical bottle into a beaker, completely immersing the egg membrane into the solution and not contacting with the bottom of the beaker, fixing the conical bottle and the beaker, keeping the mutual positions unchanged, and standing and aging for 3 days;
s7, after aging, white flocculent precipitates appear in the beaker and the conical bottle, and the obtained precipitates are respectively taken out, washed by deionized water, centrifugally separated, washed by ethanol and acetone and centrifugally separated;
and S8, repeating the step S7, washing with deionized water, performing centrifugal separation, washing with ethanol and acetone, performing centrifugal separation for three times to obtain a product, and drying the product at a low humidity of 40 ℃ to obtain the multilayer sheet assembled zinc phosphate anticorrosive pigment.
EXAMPLE III
A preparation method of a zinc phosphate anti-corrosion pigment assembled by multilayer sheets comprises the following steps:
s1, taking a fresh egg, forming a small opening with a square centimeter at one end of the egg, and removing yolk and egg white to obtain a relatively complete egg shell;
s2, taking one 250ml beaker, adding 100ml of deionized water and 25ml of glacial acetic acid, heating to 40 ℃ in a water bath, and keeping;
s3, placing the eggshells obtained in the step S1 in a beaker for soaking, taking out the eggshells until the surfaces of the eggshells are soft, and cleaning the eggshells which are taken out by using clear water;
s4, adding 700ml of deionized water into a 1000ml beaker, completely immersing the treated egg shell into the deionized water, keeping the egg shell moist, breaking the whole egg shell by using a pair of tweezers on the premise of keeping the egg membrane undamaged, separating the broken egg shell from the egg membrane to obtain a complete egg membrane, and cleaning the obtained egg membrane by using the deionized water for later use;
s5, taking a 25ml conical bottle and a 50ml beaker, respectively, washing the conical bottle and the 50ml beaker by using deionized water, and adding 0.1mol/L of Zn (NO) into the conical bottle 3 ) 2 Adding 0.067mol/L Na into a beaker 2 HPO 4 Respectively adding 0.015g of polyacrylamide template agent into the conical bottle and the beaker, and fully dissolving and stirring;
s6, wrapping the conical bottle mouth with the egg membrane prepared in the step S4, binding until no liquid overflows when the conical bottle is inverted, inverting the conical bottle and putting the conical bottle into a beaker, completely immersing the egg membrane into the solution and not contacting with the bottom of the beaker, fixing the conical bottle and the beaker, keeping the mutual positions unchanged, and standing and aging for 2 days;
s7, after aging, white flocculent precipitates appear in the beaker and the conical bottle, and the obtained precipitates are respectively taken out, washed by deionized water, centrifugally separated, washed by ethanol and acetone and centrifugally separated;
and S8, repeating the step S7, washing with deionized water, performing centrifugal separation, washing with ethanol and acetone, performing centrifugal separation for three times to obtain a product, and drying the product at a low humidity of 40 ℃ to obtain the multilayer sheet assembled zinc phosphate anticorrosive pigment.
Comparative example
Washing 25ml conical flask and 50ml beaker with deionized water, adding 0.100mol/L Zn (NO) 3 ) 2 Adding 0.067mol/L Na into a beaker 2 HPO 4 And the two are directly mixed to obtain the zinc phosphate. The comparative example was zinc phosphate random geometry.
FIG. 2, FIG. 3 and FIG. 4 show the results of the preparation of zinc phosphate powder with polyacrylamide template added, the product being in the form of a central radial sheet, a material with a special morphology assembled from one sheet to another, each sheet having a thickness of about 1 μm and a length of about 100. Mu.m, and all the paddles having a good crystallinity and growing completely. This shows that the addition of polyacrylamide can improve the crystal structure while controlling the crystal growth, and improve the specific surface area and corrosion resistance of zinc phosphate powder. FIG. 5 is a product of a comparative example in the absence of a template, apparently not in the form of a flake but in the form of a cube, the comparative example having prepared therein a zinc phosphate in a random geometry, and having a salt spray resistance of only 100 hours, which is only 70% of that of the product of the present invention.
In summary, in the embodiment of the present invention, the preparation method of the zinc phosphate anti-corrosive pigment assembled by multiple layers of sheets utilizes a biomimetic synthesis method, uses a biological template as a basic template to perform a reaction, and adds polyacrylamide as a template agent into a reaction system to prepare the zinc phosphate anti-corrosive pigment assembled by sheets; the preparation method has the characteristics of simple equipment, high synthesis efficiency, low production cost, good product dispersibility and excellent corrosion resistance, and has wide market application prospect. The invention has the following advantages: 1) The zinc phosphate anti-corrosion pigment assembled by multiple layers of sheets is prepared by a biomineralization method, so that the anti-corrosion performance of the zinc phosphate anti-corrosion pigment is remarkably improved, and the use cost of the zinc phosphate anti-corrosion pigment is greatly reduced; 2) The addition of the polyacrylamide is beneficial to improving the dispersibility of the zinc phosphate anti-corrosion pigment and the compatibility of a system, thereby improving the anti-corrosion performance; 3) The eggshell is used as the template, no pollution is generated in the preparation process, and the environment-friendly preparation method is in line with the environment-friendly category.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (7)

1. A preparation method of a zinc phosphate anti-corrosion pigment assembled by multiple layers of sheets is characterized by comprising the following steps:
s1, taking a fresh egg, and removing yolk and egg white to obtain a relatively complete egg shell;
s2, taking one 250ml beaker, adding 100ml of deionized water and 25ml of glacial acetic acid, and heating to 40 ℃ and keeping;
s3, placing the eggshells obtained in the step S1 in a beaker for soaking, taking out the eggshells until the surfaces of the eggshells are soft, and cleaning the eggshells which are taken out by using clear water;
s4, adding deionized water into a 1000ml beaker, completely immersing the treated egg shells into the deionized water, keeping the egg shells moist, separating the egg shells from the egg membranes to obtain complete egg membranes, and cleaning the obtained egg membranes with the deionized water for later use;
s5, taking a 25ml conical flask and a 50ml beaker, washing the conical flask with deionized water, and adding (0.075-0.125) mol/L Zn (NO) into the conical flask 3 ) 2 Adding (0.05-0.083) mol/L Na into a beaker 2 HPO 4 Respectively adding (0.01-0.02) g of polyacrylamide template into the conical flask and the beaker, and fully dissolving and stirring;
s6, wrapping the conical bottle mouth with the egg membrane prepared in the step S4, binding until no liquid overflows when the conical bottle is inverted, inverting the conical bottle and putting the conical bottle into a beaker, completely immersing the egg membrane into the solution, not contacting the bottom of the beaker, fixing the conical bottle and the beaker, keeping the mutual positions of the conical bottle and the beaker unchanged, and standing and aging;
s7, ageing, then, respectively taking out white flocculent precipitates in the beaker and the conical flask, washing the precipitates with deionized water, carrying out centrifugal separation, then washing with ethanol and acetone, and carrying out centrifugal separation;
and S8, repeating the step S7, washing with deionized water, performing centrifugal separation, washing with ethanol and acetone, performing centrifugal separation for three times to obtain a product, and drying the product at a low humidity of 40 ℃ to obtain the multilayer sheet assembled zinc phosphate anticorrosive pigment.
2. The method for preparing a zinc phosphate anticorrosive pigment for multilayer chip assembly according to claim 1, wherein the method comprises the following steps: in the step S1, a small opening of 0.5-1 square centimeter is opened at one end of the egg, and the yolk and the egg white are removed.
3. The method for preparing a zinc phosphate anticorrosive pigment for multilayer flake assembly according to claim 1, wherein the method comprises the following steps: the beaker water bath in step S2 is heated to 40 ℃ and maintained.
4. The method for preparing a zinc phosphate anticorrosive pigment for multilayer flake assembly according to claim 1, wherein the method comprises the following steps: 700ml of deionized water was added to the 1000ml beaker in step S4.
5. The method for preparing a zinc phosphate anticorrosive pigment for multilayer chip assembly according to claim 4, wherein the method comprises the following steps: in the step S4, the whole egg shell is broken by using tweezers on the premise of keeping the egg membrane undamaged, and then the broken egg shell is separated from the egg membrane to obtain the complete egg membrane.
6. The method for preparing a zinc phosphate anticorrosive pigment for multilayer flake assembly according to claim 1, wherein the method comprises the following steps: and S6, standing and aging for 2-3 days.
7. The method for preparing a zinc phosphate anticorrosive pigment for multilayer flake assembly according to claim 1, wherein the method comprises the following steps: the zinc phosphate anti-corrosion pigment obtained in the step S7 is a sheet-shaped material which is in a central radiation sheet shape and is assembled by one sheet.
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