CN114133778B - Corrosion-resistant material, method for producing same, and corrosion-resistant coating formed therefrom - Google Patents

Corrosion-resistant material, method for producing same, and corrosion-resistant coating formed therefrom Download PDF

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CN114133778B
CN114133778B CN202111550892.9A CN202111550892A CN114133778B CN 114133778 B CN114133778 B CN 114133778B CN 202111550892 A CN202111550892 A CN 202111550892A CN 114133778 B CN114133778 B CN 114133778B
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corrosion
iron
binder
particles
resistant material
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CN114133778A (en
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张明
瞿义生
王业友
袁华庭
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Wuhan Supor Cookware Co Ltd
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Wuhan Supor Cookware Co Ltd
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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/26—Cellulose ethers
    • C09D101/28—Alkyl ethers
    • C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
    • 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
    • C09D129/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

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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)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present inventive concept provides an anti-corrosion material, a method of preparing the same, and an anti-corrosion coating layer prepared by the anti-corrosion material. The corrosion-resistant material includes a plurality of corrosion-resistant particles, each of which includes an iron-based material and a non-metallic corrosion-resistant material covering at least a part of a surface of the iron-based material with a binder. The corrosion prevention layer formed by using the corrosion prevention material of the present inventive concept has an excellent corrosion prevention effect.

Description

Corrosion-resistant material, method for producing same, and corrosion-resistant coating formed therefrom
Technical Field
The present inventive concept relates to the field of corrosion protection, and more particularly, to a corrosion protection material, a method of preparing the same, and a corrosion protection coating formed therefrom.
Background
Corrosion protection technology is used in many fields, and more devices need to be provided with a corrosion protection layer. The existing anti-corrosion layer is generally composed of a transition layer and a sealing layer, wherein the transition layer mainly provides a bonding force with a substrate, the sealing layer mainly provides corrosion resistance, the single transition layer cannot form good corrosion resistance, and the single sealing layer cannot form good bonding force with the substrate, so that the transition layer and the sealing layer must be combined to form a main frame structure of the anti-corrosion layer. However, when a multi-layer corrosion prevention structure is provided, the thickness of the corrosion prevention layer is increased, and the corrosion prevention cost is increased.
Therefore, how to make the transition layer have corrosion prevention or corrosion resistance, so that the corrosion prevention effect can be achieved by using the corrosion prevention layer only including the transition layer without additionally providing a sealing layer, is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
To address one or more of the above-identified problems in the prior art, the present invention provides an anticorrosive material, a method of preparing the same, and an anticorrosive coating formed therefrom.
The corrosion prevention material according to the exemplary embodiment of the inventive concept includes a corrosion prevention material. The corrosion protection material may include a plurality of corrosion protection particles, and each of the corrosion protection particles includes an iron-based material and a non-metallic corrosion resistant material covering at least a part of a surface of the iron-based material by a binder.
In an exemplary embodiment, the iron-based material may include at least one of low carbon steel, high carbon steel, and cast iron.
In an exemplary embodiment, the non-metallic corrosion resistant material may include AT least one of such as titanium oxide, titanium nitride, ferroferric oxide, aluminum oxide, and AT-series powder (composite of titanium oxide and aluminum oxide). Non-metallic corrosion resistant materials may provide corrosion protection or resistance.
In an exemplary embodiment, the binder may include at least one of a cellulose-based binder and an alcohol-based binder.
In an exemplary embodiment, the weight of the non-metallic corrosion resistant material in each corrosion protection particle is 10% to 40% of the total weight of the iron-based material and the non-metallic corrosion resistant material included in the corrosion protection particle.
In exemplary embodiments, the weight of the binder in each corrosion protection particle may be 0.1% to 2% of the weight of the corrosion protection particle.
In an exemplary embodiment, the binder includes an alcohol binder, and the weight of the alcohol binder in each corrosion protection particle is 0.1% to 1% of the weight of the corrosion protection particle.
In an exemplary embodiment, the grain size of the iron-based material may be 5 times or more the grain size of the non-metallic corrosion resistant material. When the particle size of the non-metallic corrosion resistant material serving as the wrapping layer is smaller than that of the iron-based material, the pore structure of the wrapping layer is small in pore and low in porosity, and when the particle size of the iron-based material is more than 5 times of that of the non-metallic corrosion resistant material, the surface porosity of the formed corrosion resistant material is low, and the corrosion resistance is better.
The method of manufacturing an anticorrosive material according to an exemplary embodiment of the inventive concept may include the steps of: providing an iron-based material, a non-metallic corrosion resistant material and a binder; preparing a slurry from an iron-based material, a non-metallic corrosion-resistant material and a binder; and subjecting the slurry to a spray drying process to obtain an anticorrosive material comprising a plurality of anticorrosive particles, wherein each anticorrosive particle comprises an iron-based material and a non-metallic corrosion resistant material covering at least a part of the surface of the iron-based material with a binder.
In exemplary embodiments, the method of preparing the corrosion protection material may further include the step of sintering the corrosion protection material after the spray drying process.
In an exemplary embodiment, in the preparing of the iron-based material, the non-metallic corrosion resistant material, and the binder into the slurry, the weight of solids in the slurry may be 20% to 70% of the total weight of the slurry.
The corrosion prevention coating layer according to the exemplary embodiment of the inventive concept may be formed on the surface of the base material of the cooker by the spray coating method from the above-described corrosion prevention material.
Through the above brief description of the inventive concept, it is possible to provide an anticorrosive coating formed on the surface of a base material of a cooker by using an anticorrosive material prepared by using an iron-based material, a binder, and a non-metallic corrosion resistant material. The corrosion prevention coating layer prepared by the method of the inventive concept has low manufacturing costs, and has a small thickness and excellent corrosion prevention properties due to a single-layered structure.
Detailed Description
The present invention will now be described more fully hereinafter with reference to exemplary embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. .
The surface of a base material such as a cooker is often easily corroded (e.g., rusted) by an electrochemical reaction due to the influence of a cooking environment, etc., and therefore, in order to prevent the base material of the cooker from being corroded, a corrosion prevention layer is provided on the surface of the base material.
The Chinese patent application with the application number of 201821887926.7 discloses an antirust iron pan, which comprises a base material, a transition layer and a sealing layer, wherein the transition layer is located on the surface of the base material, the sealing layer is located on the surface of the transition layer, and the sealing layer is a thermal spraying coating. The transition layer mainly provides binding force with the base material, the sealing layer mainly provides corrosion resistance, the single transition layer cannot form good corrosion resistance, and the single sealing layer cannot form good binding force with the base material, so that the transition layer and the sealing layer are combined to form a main body frame structure of the antirust layer. However, it is noted that the technique has a three-layer structure, and thus has complicated process conditions, and the formed three-layer structure increases the weight of the pot. In addition, since the iron-based material itself is easily rusted, even after the stainless steel is thermally sprayed, the corrosion resistance of the stainless steel is greatly reduced due to the oxidation of Cr in the material at high temperature, and there is no corrosion prevention effect, so this technique does not select the iron-based material as the corrosion prevention material to perform the thermal spraying.
However, iron-based materials have been favored by consumers because of their advantages such as low cost and wide sources, and particularly, ferrous iron which is easily absorbed by human body can be formed in the use of cookware to supplement iron elements necessary for human body. Therefore, how to manufacture an anticorrosive material using an iron-based material and how to spray the anticorrosive material on the surface of a base material of cookware by a spray coating method to be used as an anticorrosive coating having a thin thickness has been a problem that those skilled in the art have desired to solve.
Aiming at the technical problems, the invention is designed to combine an iron-based material, a non-metallic corrosion-resistant material and a binder to form corrosion-resistant particles through a granulation process, and spray the prepared corrosion-resistant particles to form a single-layer corrosion-resistant layer, so that the corrosion-resistant layer can independently have corrosion-resistant and corrosion-resistant functions without additionally arranging a sealing layer, and the low-cost iron-based material can be used as a spray material, and simultaneously, the requirements of consumers on the traditional Chinese iron cooking utensils are met.
Hereinafter, the present inventive concept will be described in detail with reference to exemplary embodiments.
The corrosion prevention material according to an exemplary embodiment of the inventive concept may include a plurality of corrosion prevention particles, and each of the corrosion prevention particles includes an iron-based material and a non-metallic corrosion resistant material covering at least a part of a surface of the iron-based material by a binder.
According to exemplary embodiments, the iron-based material as a base material or a matrix material of the corrosion prevention particles may include at least one of iron-based materials such as low carbon steel, high carbon steel, cast iron, and the like, and may preferably have a rounded shape of a spherical shape or a spheroidal shape (e.g., an elliptical shape) to facilitate the sufficient utilization of the iron-based material and the adhesion between the iron-based materials having small-sized particle diameters and the adhesion of the iron-based material by the non-metallic corrosion resistant material. When the iron-based material is in a shape with an edge, etc., the edge portion is not easily coated with the non-metallic corrosion resistant material, so that the edge portion is exposed to the outside, thereby reducing the corrosion resistance of the corrosion resistant material, whereas the spherical or spheroidal (e.g., elliptical) iron-based material has no edge portion, so that the non-metallic corrosion resistant material can coat the iron-based material well, thereby preventing the corrosion resistance of the corrosion resistant material from being reduced. However, the concept of the present invention is not limited thereto, and those skilled in the art can select an appropriate fe-based material and its shape according to actual needs, so that at least one of the selected fe-based materials may have a shape with corners or sharp points.
The non-metallic corrosion resistant material according to example embodiments may be attached (e.g., coated) on at least a portion of a surface of the iron-based material in the form of particles by a binder. Here, the expression "at least a partial surface" may mean that the iron-based material in the form of particles may not be completely coated with the non-metallic corrosion resistant material but may be partially exposed.
According to an exemplary embodiment, the non-metallic corrosion resistant material may include AT least one of such as titanium oxide, titanium nitride, titanium carbide, magnetite, alumina, and AT-series powder (composite of titanium oxide and alumina). Here, the AT-series powder is a composite material of titanium oxide and aluminum oxide (instead of simply physically mixing titanium oxide and aluminum oxide (for example, the black titanium oxide is prepared by subjecting titanium white to electrofusion electrolysis to obtain black titanium oxide, while the AT-series powder is prepared by simply physically mixing aluminum oxide and titanium white prior to electrofusion electrolysis, and then subjecting them to ignition electrolysis to obtain a composite material structure of black titanium oxide and aluminum oxide connected together)). However, the concept of the present invention is not limited thereto, and those skilled in the art can select other non-metallic corrosion resistant materials than the above materials according to actual needs.
According to an exemplary embodiment, the weight of the non-metallic corrosion resistant material in the corrosion protection particles may be 10% to 40% of the total weight of the iron-based material and the non-metallic corrosion resistant material included in the corrosion protection particles, for example, preferably, 15% to 35%, more preferably, 20% to 30%; when the proportion of the non-metal corrosion-resistant material in the iron-based material and the non-metal corrosion-resistant material contained in the corrosion-resistant particles is more than 40% by weight, the proportion of the iron-based material is less, so that the content of iron in the corrosion-resistant material is less, on one hand, the original purpose of preparing the corrosion-resistant material by using the iron-based material is violated, and on the other hand, the deformation amount of the non-metal corrosion-resistant material in the spraying process is less than that of a metal material (such as the iron-based material), so that the binding force between the non-metal corrosion-resistant material and the base material is lower than that between the metal material and the base material, and therefore, when the content of the iron-based material is too small, a good binding force between the non-metal corrosion-resistant material and the base material cannot be provided; when the proportion of the non-metallic corrosion resistant material in the iron-based material and the non-metallic corrosion resistant material included in the corrosion-resistant particles is less than 10% by weight, the corrosion resistance of the formed corrosion-resistant layer is easily seriously reduced due to the excessive content of the iron-based material, and the corrosion-resistant layer does not play a role in corrosion prevention or corrosion resistance.
In addition, because the non-metallic corrosion-resistant material needs to be wrapped on the outer surface of the iron-based material, the particle size of the iron-based material can be larger than that of the non-metallic corrosion-resistant material. For example, the particle size of the iron-based material may be 5 times or more the particle size of the non-metallic material because: the pore structure of the non-metallic corrosion resistant material as the coating layer is required to be small in pores and low in porosity, so that the particle size of the non-metallic corrosion resistant material is required to be smaller than that of the iron-based material, and comprehensive research finally finds that when the ratio of the particle size of the iron-based material to the particle size of the non-metallic corrosion resistant material is greater than or equal to 5, the surface porosity of the corrosion-resistant layer formed by the corrosion-resistant material is low, and the corrosion resistance is better.
The binder is used to bond the ferrous material to the non-metallic corrosion resistant material. The binder according to an exemplary embodiment may include at least one of a cellulose-based binder and an alcohol-based binder. Here, the cellulose-based binder may include at least one of cellulose-based binders such as a hydroxymethylcellulose-based binder, a hydroxyethylcellulose-based binder, a hydroxypropylmethylcellulose-based binder, and the like, and the alcohol-based binder may include at least one of alcohol-based binders such as a polyvinyl alcohol-based binder, a polypropylene alcohol-based binder, a higher alcohol-based binder containing six carbon atoms or more, and the like. However, the inventive concept is not particularly limited to the kind of the binder, and a person skilled in the art may select an appropriate binder according to actual needs.
According to exemplary embodiments, the weight of the binder in the corrosion protection particles may be 0.1% to 2% of the weight of the corrosion protection particles, for example, preferably, 0.2% to 1.8%, more preferably, 0.5% to 1.5%.
When the binder comprises an alcohol binder, the weight of the alcohol binder in the corrosion protection particles may be 0.1 to 1% of the total weight of the corrosion protection particles, for example, preferably, 0.2 to 0.8%, more preferably, 0.5 to 0.7%. This is because the alcohol binder is volatile, and is volatile during the process of preparing the anticorrosive coating, such as thermal spraying, leaving pores, so that the smaller the binder, the better, the smaller the binder, the lower the porosity, but the binder required for the base granulation needs to be satisfied; when the weight ratio is less than 0.1%, the proportion of the binder is small, resulting in poor adhesion properties to easily cause breakage of the corrosion-resistant particles; in addition, when the weight ratio is more than 1%, the porosity of the corrosion prevention layer formed by such corrosion prevention particles is high, resulting in a decrease in corrosion resistance.
Furthermore, when the binder comprises a cellulosic binder, the weight of cellulosic binder in the corrosion protection particles may be between 0.1% and 2% of the total weight of the corrosion protection particles, since the cellulosic binder will eventually be retained in the coating, and: when the weight ratio is less than 0.1%, the proportion of the binder is small, resulting in poor adhesion properties to easily cause breakage of the corrosion-resistant particles; in addition, when the weight ratio is more than 2%, the binder accounts for a relatively high proportion, so that agglomeration after subsequent spray sintering is easily caused, and finally, the production efficiency is reduced.
The corrosion prevention material composed of the iron-based material, the non-metallic corrosion resistant material, and the binder, which is contemplated by the present invention, is described above in detail with reference to the exemplary embodiments. When the corrosion prevention material is formed on the surface of a base material (e.g., iron-based material) through a layer forming process such as a cold spray process, a thermal spray process, etc., it is possible to form a corrosion prevention layer having excellent properties, thereby improving the lifespan of the cooker.
Hereinafter, a method of manufacturing the corrosion prevention material of the inventive concept will be described in detail with reference to exemplary embodiments.
The method of manufacturing a corrosion prevention material according to an exemplary embodiment of the inventive concept may include: providing an iron-based material, a non-metallic corrosion resistant material and a binder; preparing an iron-based material, a non-metal corrosion-resistant material and a binder into slurry; the slurry is subjected to a spray drying process, thereby obtaining an anticorrosive material comprising a plurality of anticorrosive particles.
According to an exemplary embodiment, the step of providing the iron-based material, the non-metallic corrosion resistant material, and the binder may include preparing the iron-based material, the non-metallic corrosion resistant material, and the binder, respectively. The iron-based material may include at least one of iron-based materials such as low carbon steel, high carbon steel, cast iron, and the like. The non-metallic corrosion resistant material may include AT least one of such as titanium oxide, titanium nitride, ferroferric oxide, aluminum oxide, and AT-series powder (composite material of titanium oxide and aluminum oxide). Here, the particle size of the iron-based material may be 5 times or more the particle size of the non-metallic material, and the particle size of the iron-based material may be in the range of 20 to 80 μm, and the particle size of the non-metallic corrosion resistant material may be in the range of 1 to 10 μm, so that the non-metallic corrosion resistant material may be better coated on the surface of the iron-based material. Further, the binder may include at least one of a cellulose-based binder and an alcohol-based binder. The cellulose-based binder may include at least one of cellulose-based binders such as hydroxymethylcellulose-based binders, hydroxyethylcellulose-based binders, hydroxypropylmethylcellulose-based binders, and the like, and the alcohol-based binder may include at least one of alcohol-based binders such as polyvinyl alcohol-based binders, polypropylene alcohol-based binders, higher alcohol-based binders containing six carbon atoms or more, and the like. The inventive concept is not so limited.
In addition, in order to ensure that the particle sizes of the provided iron-based material and the non-metal corrosion-resistant material are not greatly different as much as possible, the step of providing the iron-based material and the non-metal corrosion-resistant material can also comprise the step of grinding the iron-based material and the non-metal material, so that the subsequent processes of pulping, spraying and the like are facilitated. However, the inventive concept is not limited thereto, and the grinding step may be omitted.
After preparing the iron-based material, the non-metallic corrosion resistant material, and the binder, a pulping process may be performed. In the pulping process, the binder may be prepared into a slurry, and the iron-based material and the non-metallic corrosion resistant material may be added together or separately to the slurry to obtain a slurry. Here, the iron-based material and the non-metallic corrosion resistant material may be mixed and then added to the slurry in the form of a mixture, or the iron-based material and the non-metallic corrosion resistant material may be simultaneously added to the slurry separately, or the iron-based material and the non-metallic corrosion resistant material may be added to the slurry separately and sequentially. The inventive concept is not limited to the order of charging the iron-based material and the non-metallic corrosion resistant material.
According to an exemplary embodiment of the inventive concept, the slurry may include a binder, a dispersant, an antifoaming agent, and deionized water. Here, as described above, the binder may include a cellulose-based binder, an alcohol-based binder, etc., the defoaming agent may include polyether-modified silicone oil or organic silicone oil, and the dispersing agent may include citric acid or triethylhexylphosphoric acid. However, the inventive concept is not limited to the components of the antifoaming agent and the dispersing agent, and since the dispersing agent and the antifoaming agent are used as the auxiliary agent in order to more uniformly disperse the iron-based material and the non-metallic corrosion resistant material in the slurry, a person skilled in the art can select a suitable auxiliary agent according to the prior art, and the components of the auxiliary agent are not limited to the antifoaming agent and the dispersing agent described above.
According to an exemplary embodiment, the slurry may include 0.1% to 4% of a binder, 0.5% to 1% of a dispersant, 1% to 2% of a defoaming agent, and the balance deionized water, in weight percent. According to exemplary embodiments, the weight ratio of the dispersant and the defoamer, respectively, in the slurry is proportional to the weight ratio of the binder, that is, the higher the content of the binder, the higher the weight ratio of the dispersant and the defoamer. Since the particle size of the iron-based material is small, the smaller the particle size is, the larger the surface area is for the same mass of iron-based material, and thus, more non-metallic corrosion resistant material is required. For example, when the weight ratio of the cellulose-based binder in the corrosion prevention particles is less than 0.1% or when the weight ratio of the alcohol-based binder in the corrosion prevention particles is less than 0.1%, the content of the cellulose-based binder or the alcohol-based binder is small, the non-metallic corrosion resistant material is not well bound to the iron-based material, and thus granulation cannot be efficiently performed; when the weight ratio of the alcohol binder in the anti-corrosion particles is more than 1%, the content of the alcohol binder is higher, and the porosity of an anti-corrosion coating formed by the anti-corrosion material through a spraying method is higher, so that the anti-corrosion effect is influenced; when the weight ratio of the cellulose binder in the anti-corrosion particles is more than 2%, agglomeration after subsequent spray sintering is easily caused, and finally, the production efficiency is reduced. When the binder comprises an alcohol binder, the weight of the alcohol binder in the corrosion protection particles may be between 0.1% and 1% of the total weight of the corrosion protection particles, and when the binder comprises a cellulose binder, the weight of the cellulose binder in the corrosion protection particles may be between 0.1% and 2% of the total weight of the corrosion protection particles.
After the slurry is prepared, the iron-based material, the non-metallic corrosion resistant material, and the slurry may be mixed to obtain a slurry. According to an exemplary embodiment, an iron-based material and a non-metallic corrosion resistant material in a weight ratio ranging from 9 to 3. In the above slurry, the more the content of the slurry, the less the weight ratio of the solid, but when the weight ratio of the solid in the slurry is less than 20%, the granulation time is long and the cost is too high; when the weight ratio of the solid in the slurry is more than 70%, the content of the solid is high, the slurry in the slurry is low, and the subsequent spraying process cannot be stably performed, which may affect the production stability.
After the slurry is prepared, the slurry may be spray dried. For example, the slurry may be transferred to a high-speed slinging disc at 6000 to 10000 rpm and then thrown out by the high-speed rotating slinging disc to form droplets, and then the droplets may be blown into a drying tower at 100 to 400 ℃ by hot air at 60 to 100 ℃ so that the droplets blown into the tower stay for 5 to 15 seconds during the descending process to form solid particles such as spherical particles coated with the non-metallic corrosion resistant material on the iron-based material. Here, lower hot air can reduce binder loss, such that more binder remains in the resulting corrosion protection particles. In addition, since the particle size of the raw material particles is small and the particle size of the composite particles formed after the binder is adhered is also relatively small, the powder can be thrown out at a relatively low rotation speed (6000 rpm to 15000 rpm).
After spray drying, the corrosion-resistant particles of the non-metallic corrosion-resistant material coated iron-based material can be obtained. However, such particles may have moisture present, and therefore, in order to remove the moisture present therein, the corrosion prevention particles may be subjected to a sintering process. Specifically, the temperature is raised at a constant temperature-raising rate and held for a constant time to complete the sintering. The sintering curve can be established according to the physical properties of the raw material powder. Due to the small particle size of the formed composite material particles, the required effect can be achieved by a slower heating speed and a shorter heat preservation time, for example, the heating speed can be 5-20 ℃/min, the final temperature can be 120-200 ℃, and the heat preservation time can be 1-30 h. According to a specific example, the temperature rising speed is 5-10 ℃/min, the final temperature can be 200 ℃, and the heat preservation time is 3-10 h.
After the steps, the final anti-corrosion particles can be obtained. The corrosion protection particles may then be sieved to obtain particles of different size intervals.
By using the corrosion prevention material including the plurality of corrosion prevention particles formed according to the above process, a corrosion prevention layer having excellent corrosion prevention properties may be formed on a surface of a substrate (e.g., an inner surface and/or an outer surface of cookware) using a layer forming process such as a spray process (e.g., a cold spray process, a thermal spray process). However, the inventive concept is not limited to the selection of various parameters of the spray coating process.
In the following, the advantageous effects of the inventive concept will be described in detail in connection with specific examples.
Example 1
Low carbon steel particles and titanium oxide particles are provided, wherein the low carbon steel particles have a particle size of 60 μm and the titanium oxide particles have a particle size of 10 μm, and hydroxymethyl cellulose is provided as a binder.
Hydroxymethyl cellulose, citric acid, polyether modified silicone oil, and deionized water were mixed to prepare a slurry. In the slurry, according to weight percentage, the hydroxymethyl cellulose accounts for 1.5 percent, the citric acid accounts for 0.7 percent, the polyether modified silicone oil accounts for 1.6 percent, and the balance is deionized water.
The low carbon steel particles and the titanium oxide particles are mixed with the above slurry to prepare a slurry. Wherein the weight ratio of the low carbon steel particles to the titanium oxide particles is 6.
And carrying out spray drying treatment on the slurry. Specifically, the slurry is conveyed to a high-speed liquid throwing disc with 9000 revolutions per minute, the slurry is thrown out by the high-speed liquid throwing disc rotating at high speed to form drops, and then the drops are blown into a drying tower with the temperature of 80 ℃ by hot air at 300 ℃, so that the drops blown into the drying tower fall after staying for 8-10 seconds to form initial particles.
After spray drying, the primary particles are sintered. Here, the sintering mechanism is: the initial temperature was 25 ℃, the temperature was raised to 200 ℃ at a ramp rate of 8 ℃/min and held at 200 ℃ for 8h to complete the sintering.
And sintering to obtain the anti-corrosion particles, wherein the binder accounts for 1.5wt% of the anti-corrosion particles, and the mass ratio of the low-carbon steel to the titanium oxide is 6.
The corrosion protection particles are then sieved to obtain particles having a particle size in the range of 60 μm to 80 μm.
The surface of the inner wall of the iron pan was thermally sprayed by a thermal spraying process using the above-obtained corrosion prevention particles having a particle size in the range of 60 to 80 μm, thereby obtaining a corrosion prevention layer having a thickness of 100 μm formed thereon. Here, the following thermal spray parameters were employed: current: 350A; voltage: 55V; main gas (argon) flow: 2200L/H; hydrogen flow rate: 50L/H; powder feeding gas flow: 400L/H; powder feeding amount: 55g/min; spray distance (gun nozzle to workpiece distance): 18cm; spraying angle: 60 degrees; temperature of the workpiece: at 25 ℃.
Example 2
The difference from example 1 is that: the non-metallic corrosion resistant material is titanium nitride.
Example 3
The difference from example 1 is that: the non-metallic corrosion resistant material is alumina.
Example 4
The difference from example 1 is that: the mass ratio of the low-carbon steel to the titanium oxide is 8.5;
example 5
The difference from example 1 is that: the mass ratio of the low-carbon steel to the titanium oxide is 2;
example 6
The difference from example 1 is that: the particle size of the low carbon steel particles was 80 μm and the particle size of the titanium oxide particles was 10 μm.
Example 7
The difference from example 1 is that: the proportion of the hydroxymethyl cellulose is 1.8wt%.
Example 8
The difference from example 1 is that: the proportion of the hydroxymethyl cellulose is 0.3wt%.
Example 9
The difference from example 1 is that: the adhesive is polyvinyl alcohol accounting for 0.2wt%
Example 10
The difference from example 1 is that: the adhesive is polyvinyl alcohol accounting for 0.9wt%
Comparative example 1
The difference from example 1 is that: the mass ratio of the low-carbon steel to the titanium oxide is 9.5.
Comparative example 2
The difference from example 1 is that: the particle size of the low carbon steel particles was 60 μm, and the particle size of the titanium oxide particles was 16 μm.
Comparative example 3
The difference from example 1 is that: the adhesive is polyvinyl alcohol which accounts for 1.1wt%
Comparative example 4
The difference from example 1 is that: low carbon steel particles having a particle size of 60 μm and titanium oxide particles having a particle size of 10 μm were directly mixed, and then the inner wall surface of the iron pan was thermally sprayed by the thermal spraying process of example 1, thereby obtaining an anti-corrosion layer having a thickness of 100 μm formed on the inner wall surface of the iron pan.
The corrosion prevention layers obtained in examples 1 to 10 and comparative examples 1 to 4 above were subjected to rust prevention tests according to the test standards: referring to a corrosion resistance testing method of a plating pot in GB/T32432, the longer the time is, the better the corrosion resistance is. 0.5H was recorded once and the test results are shown in table 1 below.
TABLE 1
Figure BDA0003417546680000111
As can be seen from table 1, the anticorrosive coatings of examples 1 to 10 according to the inventive concept all had better anticorrosive effects than the anticorrosive coatings of comparative examples 1 to 4, and in particular, the anticorrosive coatings of examples 1 to 10 prepared by the granulation method according to the inventive concept had far better anticorrosive effects than the anticorrosive coating of comparative example 4 prepared by directly mixing the iron-based material and the non-metallic corrosion resistant material, and in addition, the results of table 1 also showed: under the premise that the weight ratio of the iron-based material to the non-metal corrosion-resistant material is in a range of 9-3; on the premise that a cellulose binder is used and the weight ratio of the cellulose binder in the anti-corrosion particles is in the range of 0.1-2%, the larger the ratio is, the better the corrosion resistance is; and on the premise that an alcohol binder is used and the weight ratio of the alcohol binder in the anti-corrosion particles is in the range of 0.1-1%, the smaller the ratio, the better the corrosion resistance.
Therefore, according to the embodiment of the disclosure, the iron-based material, the non-metallic corrosion resistant material and the binder are adopted to prepare the corrosion resistant material through a granulation method. The anticorrosive material can be formed on the surface of the base material of the cooker through a spraying process, so that an anticorrosive coating is formed, the iron-based material can be used as the thermal spraying anticorrosive material, the cost is low, and the iron-based anticorrosive material can also meet the favor of people on iron cookers. In addition, the corrosion prevention coating layer manufactured by the thermal spraying method of the corrosion prevention material according to the exemplary embodiment has a single-layer structure, and the coating thickness is relatively small, while improving the production efficiency and reducing the production cost, compared to the existing corrosion prevention layer composed of two layers, i.e., the transition layer and the sealing layer.
Although the present invention has been described with reference to the above embodiments, it will be understood by those skilled in the art or persons having general knowledge in the art that various modifications and changes may be made to the present invention without departing from the spirit and technical field of the present invention described in the claims.
Therefore, the technical scope of the invention should not be limited to what is described in the detailed description of the invention, and the claimed invention should be defined by the claims.

Claims (5)

1. An anti-corrosion material, characterized in that the anti-corrosion material comprises a plurality of anti-corrosion particles,
wherein each of the corrosion prevention particles includes an iron-based material and a non-metallic corrosion resistant material covering at least a part of a surface of the iron-based material with a binder,
wherein the iron-based material comprises AT least one of low-carbon steel, high-carbon steel and cast iron, the non-metallic corrosion-resistant material comprises AT least one of titanium dioxide, titanium nitride, titanium carbide, ferroferric oxide, aluminum oxide and AT series powder prepared by performing electric melting electrolysis on the aluminum oxide and titanium dioxide, the binder comprises AT least one of cellulose binder and alcohol binder,
wherein the weight of the non-metallic corrosion resistant material in each of the corrosion prevention particles is 10 to 40% of the total weight of the iron-based material and the non-metallic corrosion resistant material included in the corrosion prevention particles,
wherein the weight of the binder in each anti-corrosion particle is 0.1% to 2% of the weight of the anti-corrosion particle, and when an alcohol binder is employed, the weight of the alcohol binder in each anti-corrosion particle is 0.1% to 1% of the weight of the anti-corrosion particle, and
wherein the particle size of the iron-based material is 5 times or more of the particle size of the non-metallic corrosion resistant material.
2. A method of producing an anti-corrosion material according to claim 1, characterized in that the method comprises the steps of:
providing an iron-based material, a non-metallic corrosion resistant material and a binder;
preparing an iron-based material, a non-metal corrosion-resistant material and a binder into slurry;
the slurry is subjected to a spray drying process, thereby obtaining an anticorrosive material comprising a plurality of anticorrosive particles.
3. The method of claim 2 further comprising the step of sintering the corrosion protection material after the spray drying process.
4. The method of claim 2, wherein the weight of solids in the slurry is between 20% and 70% of the total weight of the slurry.
5. An anticorrosive coating, characterized in that the anticorrosive coating is formed on the surface of a base material of a cooker by the spray coating method from the anticorrosive material of claim 1.
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