CN114736553B

CN114736553B - Composite antirust material, preparation method thereof, coating and metal product

Info

Publication number: CN114736553B
Application number: CN202110019895.3A
Authority: CN
Inventors: 周泉竹; 林敏静; 王朋朋; 唐婕; 林锦盛; 黄友元
Original assignee: Shenzhen Betray New Material Technology Co ltd
Current assignee: Shenzhen Betray New Material Technology Co ltd
Priority date: 2021-01-07
Filing date: 2021-01-07
Publication date: 2023-09-01
Anticipated expiration: 2041-01-07
Also published as: CN114736553A

Abstract

The application provides a composite antirust material, a preparation method thereof, a coating and a metal product. The composite antirust material comprises a core layer and a shell layer coated on the surface of the core layer; the core layer comprises graphite alkyne and aluminum tripolyphosphate, and the shell layer comprises graphene. The preparation method of the composite antirust material comprises the following steps: mixing raw materials including aluminum salt, graphite alkyne oxide and water, and performing a first reaction to obtain a complexing system; mixing materials comprising a phosphorus-containing substance and the complexing system, and performing a second reaction to obtain a glue solution; mixing materials comprising graphene quantum dots and the glue solution, and performing a third reaction to obtain a composite intermediate; and heating and reducing the composite intermediate in a non-oxidizing atmosphere to obtain the composite antirust material. The coating comprises the composite antirust material. A metal article comprising a rust inhibitive coating, said rust inhibitive coating comprising said coating. The composite antirust material provided by the application has good antirust effect and long service life.

Description

Composite antirust material, preparation method thereof, coating and metal product

Technical Field

The application relates to the field of material chemistry, in particular to a composite antirust material, a preparation method thereof, a coating and a metal product.

Background

In the paint industry, conventional anti-rust pigments such as chromates and molybdates are excellent in anti-corrosion performance and widely used in paints, but as environmental awareness is raised, attention and improvement of the environment are being paid. The traditional antirust pigment contains chromium, lead and other heavy metals, and is easy to cause environmental pollution in the production and construction of the coating.

In the prior art, there is a technology of using aluminum tripolyphosphate as an antirust agent; for example, one or more of zinc modifier, magnesium modifier, calcium modifier and silicon modifier are adopted to modify aluminum tripolyphosphate, aluminum tripolyphosphate and modifier are mixed in water to form slurry, and grinding is carried out to obtain modified aluminum tripolyphosphate. However, the physical composite mode has weak acting force, the formed composite material has poor coating property, and the rust resistance of the composite material cannot be obviously improved. The zinc carbonate is also used as a raw material for crushing and modifying aluminum tripolyphosphate, but the zinc carbonate is difficult to uniformly disperse into a viscous mixed solution, and the decomposed zinc oxide and the aluminum tripolyphosphate are in point contact, so that the surface modification of the aluminum tripolyphosphate cannot be realized. There is also a technology of modifying by using graphene, but the existing form of graphene in the prepared composite material is still in a flaky isolated form, zinc oxide and aluminum tripolyphosphate are loaded on the surface, and the composite material cannot reduce the strong acidity of the surface of the aluminum tripolyphosphate, so that the subsequent coating formula system is influenced to a certain extent.

Therefore, searching for an environment-friendly and efficient antirust material becomes a problem to be solved urgently.

Disclosure of Invention

The application aims to provide a composite antirust material, a preparation method thereof, a coating and a metal product, so as to solve the problems.

In order to achieve the above purpose, the application adopts the following technical scheme:

a composite antirust material comprises a core layer and a shell layer coated on the surface of the core layer;

the core layer comprises graphite alkyne and aluminum tripolyphosphate, and the shell layer comprises graphene.

In one possible embodiment, in the core layer, the aluminum tripolyphosphate coats the surface of the graphite alkyne.

The preparation method of the composite antirust material comprises the following steps:

mixing raw materials including aluminum salt, graphite alkyne oxide and water, and performing a first reaction to obtain a complexing system;

mixing materials comprising a phosphorus-containing substance and the complexing system, and performing a second reaction to obtain a glue solution;

mixing materials comprising graphene quantum dots and the glue solution, and performing a third reaction to obtain a composite intermediate;

and heating and reducing the composite intermediate in a non-oxidizing atmosphere to obtain the composite antirust material.

In one possible embodiment, the aluminum salt includes at least one of aluminum chloride, aluminum sulfate, aluminum nitrate, and aluminum hydroxide;

in a possible embodiment, the graphite alkyne oxide has a size of from 1nm to 100nm;

in a possible embodiment, the oxygen content of the graphite alkyne oxide is from 5wt% to 20wt%;

in one possible embodiment, the mass ratio of the aluminum salt to the graphite alkyne oxide is 1: (1-5);

in a possible embodiment, the time of the first reaction is from 10min to 60min.

In one possible embodiment, the phosphorus-containing material comprises at least one of phosphoric acid and a phosphate salt;

in one possible embodiment, the phosphate comprises at least one of sodium phosphate, ammonium phosphate, and sodium dihydrogen phosphate;

in one possible embodiment, the temperature of the second reaction is from 60 ℃ to 120 ℃;

in one possible embodiment, the molar ratio of the aluminum salt to the phosphorus-containing species is 1: (2-5);

in a possible embodiment, the second reaction is carried out under stirring.

In one possible embodiment, the graphene quantum dots have a size of 1nm to 20nm;

in one possible embodiment, the oxygen content of the graphene quantum dots is 10wt% to 60wt%;

in one possible embodiment, the temperature of the third reaction is from 250 ℃ to 500 ℃;

in one possible embodiment, the mass ratio of the aluminum salt to the graphene quantum dots is 1: (1-10).

In one possible embodiment, the temperature of the heated reduction is 500 ℃ to 1000 ℃;

in one possible embodiment, the non-oxidizing atmosphere comprises at least one of hydrogen, nitrogen, and a noble gas.

In a possible embodiment, the third reaction further comprises, after completion:

washing and drying reactants to obtain the composite intermediate;

in a possible embodiment, the solvent used for the washing comprises water;

in one possible embodiment, the drying is performed under vacuum.

A coating comprises the composite antirust material.

In a possible embodiment, the coating comprises the following raw materials in percentage by mass:

the composite antirust material comprises, by weight, 0.2% -5% of a composite antirust material, 10% -30% of epoxy resin, 35% -60% of zinc powder, 15% -30% of a pigment, 5% -10% of a curing agent, 0.2% -2% of an auxiliary agent and 2% -8% of a solvent.

A metal article comprising a rust inhibitive coating, said rust inhibitive coating comprising said coating.

Compared with the prior art, the application has the beneficial effects that:

according to the composite antirust material provided by the application, the graphene is used for coating the graphite alkyne and the aluminum tripolyphosphate, and the long-term utilization efficiency of the aluminum tripolyphosphate is effectively improved by utilizing the photoelectrocatalysis characteristic of the graphite alkyne, so that the antirust effect and the service life of the composite antirust material are improved; the aluminum tripolyphosphate is subjected to surface modification by using graphene, the speed of releasing pyrophosphate by the aluminum tripolyphosphate is controlled by using the structural defect of the graphene, and the surface acidity of the aluminum tripolyphosphate can be obviously passivated by coating the graphene, so that the composite antirust material can be effectively and uniformly dispersed into a coating system, and the occurrence of a flash rust phenomenon is avoided;

according to the preparation method of the composite antirust material, an in-situ synthesis method is adopted, graphite alkyne is used as a reaction template, positively charged aluminum ions are uniformly adsorbed on the surface of the graphite alkyne through the action of charges, a chemical reaction grows from adsorption sites and forms nano aluminum phosphate crystals, nano aluminum tripolyphosphate is obtained through condensation, and compared with micron-sized aluminum tripolyphosphate, the antirust capacity is greatly improved; the graphene quantum dots are used as a carbon coating agent, so that surface modification can be performed on aluminum tripolyphosphate, and zero-dimensional graphene quantum dots can be self-assembled on the surface of aluminum tripolyphosphate to form a two-dimensional graphene film; the nano graphite alkyne obtained by heating and reducing the graphite alkyne oxide has good photoelectric catalytic property, and can effectively improve the long-term utilization efficiency of aluminum tripolyphosphate, thereby improving the rust-proof life of the composite rust-proof pigment; the preparation method provided by the application has the advantages of simple synthesis process, wide raw material sources, green pollution-free performance price ratio and wide market application prospect;

the coating provided by the application can obtain excellent antirust effect by adding the composite antirust material provided by the application;

the metal product provided by the application has an antirust function and prolonged service life by arranging the antirust coating containing the paint.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.

FIG. 1 is a schematic flow chart of a method for preparing a composite rust preventive material provided in example 1;

FIG. 2 is a schematic structural view of the composite rust preventive material obtained in example 1;

FIG. 3 is an SEM image of a composite rust inhibitive material obtained in example 1;

FIG. 4 is a Raman spectrum of the composite rust preventive material obtained in example 2;

FIG. 5 is a photograph of example 3 and comparative examples 1-3 at 1300h of salt spray test.

Reference numerals:

1-a graphitic alkyne layer; a layer of 2-aluminum tripolyphosphate; 3-graphene layer.

Detailed Description

The term as used herein:

"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.

When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.

In these examples, the parts and percentages are by mass unless otherwise indicated.

"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.

"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).

Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The application provides a composite antirust material, which comprises a core layer and a shell layer coated on the surface of the core layer;

Aluminum tripolyphosphate is an ideal substitute for the traditional toxic antirust material, can generate pyrophosphate with strong chelating ability through hydrolysis, and is chelated with the metal surface to form a compact complex passivation film, so that the diffusion of corrosive media to the metal direction is prevented, and the corrosion of the metal is slowed down. However, the corrosion resistance of pure aluminum tripolyphosphate is not very remarkable, and the main reason is that aluminum tripolyphosphate is a solid acid, has high acidity and can damage the stability of the system when being directly used in a coating system. And because the solubility of the aluminum tripolyphosphate is small, the corrosion resistance is low in the early stage of use, and the flash rust problem is easy to occur.

Graphene has excellent barrier property, high mechanical property and stable physicochemical property, and is prepared from carbon atoms and sp ² The hexagonal two-dimensional carbon nanomaterial with honeycomb lattice and the compact base surface of the hexagonal two-dimensional carbon nanomaterial can block most gases and ionic liquids, has a good shielding effect, and can form a compact physical isolation layer by coating a graphene coating on the metal surface, so that the permeation path of corrosive media is prolonged; meanwhile, the graphene has stable physicochemical properties, can resist acid and alkali, and is a key filler for heavy anti-corrosion paint and special paint. The graphene quantum dot is a nano graphene sheet with the transverse dimension smaller than 100nm, the structural edge of the nano graphene sheet contains rich functional group active sites, and the basal plane is complete sp ² A planar structure. Since the size of the graphene quantum dot is smaller than the Bohr excitation radius of the graphene quantum dot, the graphene quantum dot has a strong quantum confinement effect and shows an energy level effect similar to that of a semiconductor quantum dot. Meanwhile, the graphene quantum dot has high specific surface area, multi-functional group active sites, energy level effect and no toxicity, so that the graphene quantum dot can be used as an excellent coating agent for aluminum tripolyphosphate.

The graphite alkyne is a compound composed of sp (alkyne bond), sp ² The two hybridized carbon atoms form two-dimensional plane network structure all-carbon molecule, which is the first artificial non-natural carbon allotrope. The self-contained unique chemical structure and special physical and chemical properties, such as rich carbon chemical bonds, large conjugation, wide-surface spacing, excellent chemical stability and the like. The preparation method comprises the steps of taking graphite alkyne oxide as a raw material, utilizing the charge effect between the graphite alkyne oxide and aluminum ions to obtain complex macromolecules, reacting the complex macromolecules with phosphorus-containing substances, coating graphene quantum dots, and then heating and reducing to obtain a nano graphite alkyne core, thereby obtaining the nano graphite alkyneIs provided.

The application also provides a preparation method of the composite antirust material, which comprises the following steps:

mixing materials including phosphorus-containing substances and a complexing system, and performing a second reaction to obtain a glue solution;

mixing materials including graphene quantum dots and glue solution, and performing a third reaction to obtain a composite intermediate;

and (3) heating and reducing the composite intermediate in a non-oxidizing atmosphere to obtain the composite antirust material.

The aluminum ions with positive charges and the graphite alkyne oxide with negative charges are combined with each other through the charge action to obtain a complexing macromolecule solution; mixing a phosphate solution with a complexing macromolecule solution, and reacting aluminum ions with phosphate radical by taking graphite alkyne oxide as a template to obtain nano-sized aluminum phosphate in situ; mixing the reacted mixed solution with graphene quantum dots to perform condensation reaction, and obtaining a composite intermediate of graphite alkyne oxide/aluminum tripolyphosphate/graphene quantum dots in situ; and (3) carrying out heating reduction on the composite intermediate to finally obtain the nano graphite alkyne/aluminum tripolyphosphate/graphene composite antirust pigment.

the choice of aluminum salt mainly takes into account the water solubility of the substance to be selected.

In one possible embodiment, the size of the graphite alkyne oxide is from 1nm to 100nm;

in one possible embodiment, the oxygen content of the graphite alkyne oxide is from 5wt% to 20wt%;

in one possible embodiment, the mass ratio of aluminum salt to graphite alkyne oxide is 1: (1-5);

in one possible embodiment, the time for the first reaction is from 10min to 60min.

The graphite alkyne oxide is not directly used, so that the complex action between the charges on the surface of the graphite alkyne oxide and aluminum ions is utilized, and the graphite alkyne does not have charges per se or does not have charge action with the aluminum ions. The control of the oxygen content of the graphite alkyne oxide and the mass ratio of the aluminum salt to the graphite alkyne oxide is mainly used for controlling the complexation between aluminum ions and the graphite alkyne oxide under the action of charges and controlling the proportion of the graphite alkyne and aluminum tripolyphosphate in a subsequently formed nuclear layer.

Alternatively, the size of the graphite alkyne oxide can be any value between 1nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, and 1nm-100nm; the oxygen content of the graphite alkyne oxide can be any value between 5wt%, 10wt%, 15wt%, 20wt%, and 5wt% to 20wt%; the mass ratio of the aluminum salt to the graphite alkyne oxide can be 1: 1. 1: 2. 1: 3. 1: 4. 1:5 and 1: any value between (1-5); the time of the first reaction may be any value between 10min, 20min, 30min, 40min, 50min, 60min, and 10min-60min.

The mass ratio of the aluminum salt to the graphite alkyne oxide is 1: in the range of (1-5), a structure in which the inner core is graphite alkyne and the outer layer is aluminum tripolyphosphate can be formed, the structure is favorable for protecting the independent structure of the graphite alkyne, and meanwhile, the graphite alkyne can catalyze the aluminum tripolyphosphate from the inside, so that the high-efficiency utilization of the aluminum tripolyphosphate is realized.

In one possible embodiment, the phosphorus-containing species includes at least one of phosphoric acid and a phosphate salt;

in one possible embodiment, the molar ratio of aluminum salt to phosphorus-containing species is 1: (2-5);

in one possible embodiment, the second reaction is carried out under stirring.

The temperature of the second reaction and the molar ratio of the aluminum salt to the phosphorus-containing substance are controlled to control the process of in-situ obtaining aluminum tripolyphosphate on the surface of graphite alkyne oxide, so that a nuclear layer with a regular structure is obtained.

Alternatively, the temperature of the second reaction may be any value between 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 60 ℃ -120 ℃; the molar ratio of aluminum salt to phosphorus-containing species may be 1: 2. 1: 3. 1: 4. 1:5 and 1: any value between (2-5).

in one possible embodiment, the mass ratio of aluminum salt to graphene quantum dots is 1: (1-10).

The oxygen content of the graphene quantum dots, the temperature of the third reaction and the mass ratio of the aluminum salt to the graphene quantum dots are controlled to properly modify the surface of aluminum tripolyphosphate, so that the zero-dimensional graphene quantum dots can be self-assembled on the surface of the aluminum tripolyphosphate to form a two-dimensional graphene film.

Alternatively, the size of the graphene quantum dots may be any value between 1nm, 5nm, 10nm, 15nm, 20nm, and 1nm-20nm; the oxygen content of the graphene quantum dots may be any value between 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, and 10wt% -60wt%; the temperature of the third reaction may be any value between 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and 250 ℃ to 500 ℃; the mass ratio of the aluminum salt to the graphene quantum dots can be as follows: any value between (1-10).

The defect degree of the graphene film can be controlled by regulating different heating reduction temperatures, which is beneficial to controlling the chemical release rate of aluminum tripolyphosphate.

Alternatively, the temperature of the heat reduction may be any value between 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ and 500 ℃ to 1000 ℃.

In one possible embodiment, the third reaction further comprises, after completion:

washing and drying reactants to obtain a composite intermediate;

in one possible embodiment, the solvent used for washing comprises water;

in one possible embodiment, the drying is performed under vacuum.

The application also provides a coating, which comprises the composite antirust material.

In one possible embodiment, the raw materials of the coating material comprise, in mass percent:

0.2 to 5 percent of composite antirust material, 10 to 30 percent of epoxy resin, 35 to 60 percent of zinc powder, 15 to 30 percent of pigment, 5 to 10 percent of curing agent, 0.2 to 2 percent of auxiliary agent and 2 to 8 percent of solvent.

Alternatively, the content of the composite rust inhibitive material in the raw material of the coating may be any value between 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and 0.2% to 5%; the epoxy resin content may be any value between 10%, 15%, 20%, 25%, 30% and 10% -30%; the zinc powder content may be any value between 35%, 40%, 45%, 50%, 55%, 60% and 35% -60%; the pigment content may be any value between 15%, 20%, 25%, 30% and 15% -30%; the content of the curing agent may be any value between 5%, 6%, 7%, 8%, 9%, 10% and 5% to 10%; the content of the auxiliary agent can be any value between 0.2%, 0.5%, 1%, 1.5%, 2% and 0.2% -2%; the solvent content may be any value between 2%, 3%, 4%, 5%, 6%, 7%, 8% and 2% -8%.

The application also provides a metal product comprising the antirust coating, wherein the antirust coating comprises a paint.

Example 1

FIG. 1 is a flow chart of a preparation method of the composite antirust material provided in the embodiment.

Weighing graphite oxide alkyne powder with the size range of 1-10nm, the oxygen content of 5wt% and the mass of 34.215g, adding the graphite oxide alkyne powder into 5.0L deionized water, and uniformly dispersing to obtain a graphite oxide alkyne aqueous solution; 34.215g of aluminum sulfate (corresponding to an amount of aluminum sulfate material of 0.1 mol) was weighed and dissolved in 5.0L of deionized water; slowly adding the aluminum sulfate solution into the graphite alkyne aqueous solution under the condition of continuous stirring, and continuously stirring for 60 minutes to fully react to obtain a complex macromolecule solution; 0.2mol of phosphoric acid is weighed and dispersed in 1.0L of deionized water to form a stable phosphoric acid solution, and the phosphoric acid solution is slowly added into the complexing macromolecular solution under the condition of continuously stirring and heating to 60 ℃ until the reaction is complete; adding 34.215g of graphene quantum dots with the mass of 1-8nm and the oxygen content of 10wt% into the semitransparent sticky substance with complete reaction, condensing at a high temperature at 500 ℃, washing the condensed white latex substance by using deionized water, and drying in vacuum to obtain a composite intermediate; and under the protection of argon, carrying out high-temperature thermal reduction on the composite intermediate at the temperature of 1000 ℃ to obtain the nano graphite alkyne/aluminum tripolyphosphate/graphene composite antirust material.

Fig. 2 is a schematic structural diagram of the composite antirust material obtained in this embodiment, which includes a graphite alkyne layer 1, an aluminum tripolyphosphate layer 2, and a graphene layer 3.

Fig. 3 is an SEM image of the nano-graphite alkyne/aluminum tripolyphosphate/graphene composite antirust material obtained in this example.

As can be seen from fig. 3, the prepared nano aluminum tripolyphosphate is distributed in a granular form, a semitransparent film is coated on the surface of the aluminum tripolyphosphate, the nano aluminum tripolyphosphate is tightly connected with graphene, and the structure enables the antirust performance to be remarkably improved.

The composite antirust material is prepared into a coating according to the following formula (mass percent):

5% of composite antirust material, 10% of E20 epoxy resin, 35% of zinc powder, 10% of antirust pigment, 20% of extender pigment, 2% of auxiliary agent, 8% of organic solvent and 10% of polyamide curing agent.

The preparation method can be a conventional method, and is exemplified by:

mixing the materials in the low-speed dispersion state (3-5 m/s) according to the sequence of E20 epoxy resin, solvent, auxiliary agent, zinc powder, rust-proof pigment, extender pigment and composite rust-proof material; then high-speed dispersing (8-10 m/s) for 15-20 min, grinding for 1-2 times, controlling outlet fineness below 50 μm, and controlling dispersing temperature below 65deg.C.

The paint is prepared into a paint film, and the impedance value of the paint film is up to 23570ohm cm after 72 hours ² The impedance at 72h is only 7200ohm cm compared with the rust-proof pigment directly compounding nano aluminum phosphate and graphene ² The performance of the composite antirust pigment prepared by the in-situ method is improved by 327 percent. According to GB/T1771-2007/ISO 7253:1996, up to 2400 hours.

Example 2

Weighing graphite alkyne oxide powder with the size range of 80-100nm, the oxygen content of 20wt% and the mass of 75.02g, adding the graphite alkyne oxide powder into deionized water with the volume of 5.0L, and uniformly dispersing to obtain a graphite alkyne oxide aqueous solution; 3.751g of aluminum nitrate (0.01 mol per aluminum nitrate mass) was weighed and dissolved in 1.0L of deionized water; slowly adding the aluminum nitrate solution into the graphite alkyne aqueous solution under the condition of continuous stirring, and continuously stirring for 10 minutes to fully react to obtain a complex macromolecule solution; weighing 0.05mol of sodium phosphate, dispersing in 1.0L of deionized water to form a stable sodium phosphate solution, and slowly adding the sodium phosphate solution into the complexing macromolecular solution under the conditions of continuously stirring and heating to 120 ℃ until the reaction is complete; adding 37.51g of graphene quantum dots with the mass of 13-20nm and the oxygen content of 60wt% into the semitransparent sticky substance with complete reaction, carrying out high-temperature condensation reaction at 250 ℃, washing the condensed white latex substance by using deionized water, and carrying out vacuum drying to obtain a composite intermediate; and under the protection of nitrogen, carrying out high-temperature thermal reduction on the composite intermediate at the temperature of 500 ℃ to obtain the nano graphite alkyne/aluminum tripolyphosphate/graphene composite antirust material.

The raman spectrum of the nano-graphite alkyne/aluminum tripolyphosphate/graphene composite antirust material obtained in the embodiment is shown in fig. 4.

From fig. 4, it can be seen that the prepared nano graphite alkyne/aluminum tripolyphosphate/graphene composite antirust material has obvious D peak and G peak, weaker 2D peak, the appearance of the 2D peak indicates that the zero-dimensional graphene quantum dot self-assembles into a two-dimensional graphene film at high temperature, and the strong D peak indicates that the formed graphene film has a large number of structural defects.

Example 3

Weighing graphite alkyne oxide powder with the size range of 20-40nm, the oxygen content of 10wt% and the mass of 78.000g, adding the graphite alkyne oxide powder into deionized water with the volume of 5.0L, and uniformly dispersing to obtain a graphite alkyne oxide aqueous solution; 7.800g of aluminum hydroxide (corresponding to an amount of 0.1mol of aluminum hydroxide substance) was weighed and dissolved in 1.0L of deionized water; slowly adding the aluminum hydroxide solution into the graphite alkyne aqueous solution under the condition of continuous stirring, and continuously stirring for 30 minutes to fully react to obtain a complex macromolecule solution; weighing 0.3mol of ammonium phosphate, dispersing in 1.0L of deionized water to form a stable ammonium phosphate solution, and slowly adding the ammonium phosphate solution into the complexing macromolecular solution under the conditions of continuous stirring and heating at 90 ℃ until the reaction is complete; adding 39.000g of graphene quantum dots with the mass of 5-13nm and the oxygen content of 20wt% into the completely-reacted white sticky material, carrying out high-temperature condensation reaction at 300 ℃, washing the condensed latex material by using deionized water, and carrying out vacuum drying to obtain a composite intermediate; and under the protection of argon, carrying out high-temperature thermal reduction on the composite intermediate at 800 ℃ to obtain the nano graphite alkyne/aluminum tripolyphosphate/graphene composite antirust material.

The composite antirust material is prepared into a coating according to the coating formula of the example 1 and is prepared into a paint film, and the resistance value of the composite antirust material at 72h is still up to 26245ohm cm ² 。

Fig. 5 is a photograph of the salt spray test 1300h of example 3 and comparative example of the present application. Wherein number 1 is a photograph of the salt spray test performed in example 3.

As can be seen from the salt spray photograph of fig. 5, the salt spray test 1300h of the nano graphite alkyne/aluminum tripolyphosphate/graphene composite antirust material coating obtained in the embodiment has significantly better corrosion resistance than that of the comparative example. The final salt spray test time can reach 2500h, and the salt spray time of the nano aluminum tripolyphosphate/graphene composite antirust pigment coating provided in comparative example 1 is only 1300h, which shows that the antirust performance of the composite antirust material provided by the application is improved by 1.9 times.

Example 4

Weighing graphite alkyne oxide powder with the size range of 50-70nm, the carbon content of 15wt% and the mass of 133.34g, adding the graphite alkyne oxide powder into deionized water with the volume of 5.0L, and uniformly dispersing to obtain a graphite alkyne oxide aqueous solution; 13.334g of aluminum chloride (corresponding to an amount of 0.1mol of aluminum chloride substance) was weighed and dissolved in 1.0L of deionized water; slowly adding the aluminum chloride solution into the graphite alkyne oxide aqueous solution under the condition of continuous stirring, and continuously stirring for 30 minutes to fully react to obtain a complex macromolecule solution; weighing 0.4mol of sodium dihydrogen phosphate, dispersing in 1.0L of deionized water to form a stable sodium dihydrogen phosphate solution, and slowly adding the sodium dihydrogen phosphate solution into the complexing macromolecular solution under the conditions of continuous stirring and heating to 100 ℃ until the reaction is complete; adding 26.668g of graphene quantum dots with the mass of 9-17nm and the oxygen content of 40wt% into the completely reacted sticky material, carrying out high-temperature condensation reaction at 400 ℃, washing the condensed latex material by using deionized water, and carrying out vacuum drying to obtain a composite intermediate; and under the protection of nitrogen, carrying out high-temperature thermal reduction on the composite intermediate at 600 ℃ to obtain the nano graphite alkyne/aluminum tripolyphosphate/graphene composite antirust material.

The composite antirust material is prepared into a coating according to the coating formula of the example 1 and is prepared into a paint film, and the impedance value of the composite antirust material at 72h is up to 21136ohm cm ² The salt fog test time can reach 2000h.

Based on the raw material proportion and the process, the influence of the thermal reduction temperature on the defect degree of the graphene film coated on the surface of the aluminum tripolyphosphate and the influence on the antirust performance of the coating are systematically studied, and are shown in table 1.

TABLE 1 correspondence table of defect level and coating performance of self-assembled graphene at different thermal reduction temperatures

Thermal reduction temperature/. Degree.C	D peak/G peak intensity ratio	Salt spray resistant time (h)
			500	1.06	1750
600	1.03	2000
			700	1.01	2300
800	0.88	2500
			900	0.73	2350
1000	0.68	2180

From the data in table 1 above, from the corresponding data of the intensity ratio of D peak to G peak of the raman spectrum to the thermal reduction temperature, it can be seen that the defect level of the self-assembled graphene film gradually decreases with the increase of the thermal reduction temperature; however, the rust resistance of the coating tends to decrease after increasing with increasing thermal reduction temperature, and at 800 ℃, the resistance is maximum and the salt spray resistance time is longest.

Comparative example 1

7.800g of aluminum hydroxide (corresponding to an amount of 0.1mol of aluminum hydroxide substance) was weighed and dissolved in 1.0L of deionized water; slowly adding an aluminum hydroxide solution into a graphene quantum dot aqueous solution (5 liters) with the mass of 39.000g, the size of 5-13nm and the oxygen content of 20wt% under the condition of continuous stirring, and stirring for 30 minutes to fully react to obtain a complex macromolecular solution; weighing 0.3mol of ammonium phosphate, dispersing in 1.0L of deionized water to form a stable ammonium phosphate solution, slowly adding the ammonium phosphate solution into the complexing macromolecular solution under the conditions of continuous stirring and heating at 90 ℃ until the reaction is complete, carrying out high-temperature condensation reaction on the solution under the condition of 300 ℃, washing the condensed emulsion by using deionized water, and vacuum drying to obtain a composite intermediate; and under the protection of argon, carrying out high-temperature thermal reduction on the composite intermediate at 800 ℃ to obtain the nano aluminum tripolyphosphate/graphene composite material.

Comparative example 2

The commercial nanometer aluminum tripolyphosphate/zinc oxide antirust material is used as a control. The rust-proof material is purchased from Shijia village Xinsheng chemical industry Co.

Comparative example 3

The commercial nanometer aluminum tripolyphosphate/polyacrylamide antirust material is used as a control. The rust-proof material is purchased from Shijia village Xinsheng chemical industry Co.

Based on the amount of the paint formulation provided in example 1, the composite rust inhibitive material obtained in example 1 was replaced with the composite rust inhibitive material obtained in example 3, the rust inhibitive material provided in comparative example 1, the rust inhibitive material provided in comparative example 2, and the rust inhibitive material provided in comparative example 3, respectively, and the corresponding paints were prepared and subjected to a 72-hour impedance test and a salt spray test, the results of which are shown in Table 2 below:

table 2 comparison of rust inhibitive ability of coatings made of different rust inhibitive materials

As shown in the table 2, the composite antirust material obtained in the embodiment 3 of the application has the highest 72h impedance and the longest salt spray resistance time, which indicates that the composite antirust material provided by the application has the strongest antirust and corrosion resistance.

Fig. 5 is a photograph of the salt spray test 1300h of example 3 and comparative example of the present application. Wherein, the photograph No. 1 is the photograph of the salt spray test of the example 3, the photograph of the salt spray test of the comparative example 1, the photograph of the salt spray test of the comparative example 2, and the photograph of the salt spray test of the comparative example 3. From the graph, the salt spray resistance of the composite antirust material obtained in the embodiment 3 of the application is optimal.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application 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 scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims

1. The composite antirust material is characterized by comprising a core layer and a shell layer coated on the surface of the core layer;

the core layer comprises graphite alkyne and aluminum tripolyphosphate, and the shell layer comprises graphene;

2. The composite rust inhibitive material of claim 1, wherein in the core layer, the aluminum tripolyphosphate coats the surface of the graphite alkyne.

3. The composite rust inhibitive material according to claim 1, wherein the aluminum salt comprises at least one of aluminum chloride, aluminum sulfate, aluminum nitrate and aluminum hydroxide;

and/or the size of the graphite alkyne oxide is 1nm-100nm;

and/or the oxygen content of the graphite alkyne oxide is 5-20wt%;

and/or the mass ratio of the aluminum salt to the graphite alkyne oxide is 1: (1-5);

and/or the time of the first reaction is 10min-60min.

4. The composite rust inhibitive material of claim 1, wherein the phosphorus-containing substance comprises at least one of phosphoric acid and a phosphate salt;

and/or the phosphate comprises at least one of sodium phosphate, ammonium phosphate and sodium dihydrogen phosphate;

and/or, the temperature of the second reaction is 60-120 ℃;

and/or the molar ratio of the aluminum salt to the phosphorus-containing substance is 1: (2-5);

and/or, the second reaction is carried out under stirring.

5. The composite rust preventive material according to claim 1, characterized in that the graphene quantum dots have a size of 1nm to 20nm;

and/or the oxygen content of the graphene quantum dots is 10-60 wt%;

and/or, the temperature of the third reaction is 250-500 ℃;

and/or the mass ratio of the aluminum salt to the graphene quantum dots is 1: (1-10).

6. The composite rust inhibitive material according to any one of claims 1 to 5, wherein the temperature of the heat reduction is 500 ℃ to 1000 ℃;

and/or the non-oxidizing atmosphere comprises at least one of hydrogen, nitrogen, and a rare gas;

and/or, after the third reaction is finished, the method further comprises:

washing and drying reactants to obtain the composite intermediate;

and/or the solvent used for washing comprises water;

and/or, the drying is performed under vacuum.

7. A coating comprising the composite rust inhibitive material of any of claims 1 to 6.

8. The coating according to claim 7, wherein the raw materials comprise, in mass percent:

9. A metal article comprising a rust inhibitive coating comprising the coating of claim 7 or 8.