CN112647064B

CN112647064B - Method for carbonizing surface of metal mesh

Info

Publication number: CN112647064B
Application number: CN202011485895.4A
Authority: CN
Inventors: 毕恒昌; 王淑英; 吴幸; 蔡春华
Original assignee: East China Normal University
Current assignee: East China Normal University
Priority date: 2020-12-16
Filing date: 2020-12-16
Publication date: 2022-08-30
Anticipated expiration: 2040-12-16
Also published as: CN112647064A

Abstract

The invention provides a method for carbonizing a metal net surface, and relates to the technical field of metal surface treatment. The method provided by the invention comprises the following steps: and soaking the metal net in an edible oil organic solution, taking out, naturally airing, and calcining to obtain the carbon-coated metal net. According to the invention, the edible oil is used as a carbon source, and the oxygen-containing functional groups in the edible oil are decomposed by calcining, so that only carbon is left, and the carbon-coated metal mesh is obtained, has wear-resistant and corrosion-resistant surface, can be used as a base material of a high polymer material and is firmly compounded with the high polymer material, and the preparation method is safe and simple, green and environment-friendly in process and low in cost.

Description

Carbonization method for metal mesh surface

Technical Field

The invention relates to the technical field of metal surface treatment, in particular to a method for carbonizing a metal net surface.

Background

There are many methods for modifying metal surface, such as oxidation, electroplating, chemical vapor deposition, physical vapor deposition, thermal spraying, dipping, etc. the modification by various methods makes the metal obtain corresponding characteristics, thereby meeting the use requirements. The method for carbonizing the metal surface comprises the steps of mixing carbide and a binding agent, coating the mixture on the metal surface, brazing and reinforcing, covering a special carbon layer on the metal surface, improving the wear resistance and corrosion resistance of the metal, performing a composite reaction with a high polymer material, and increasing the application range of the metal.

The conventional carbonization method is to perform CVD vapor deposition by using methane gas, or to perform high-temperature treatment after carbon powder and activated carbon are contacted with the metal surface. However, these methods have some problems, such as: the reaction temperature is very high, the use of methane gas has safety risk, the production cost is high, more waste gas is generated, the process method is complex and the like.

Disclosure of Invention

The invention aims to provide a method for carbonizing the surface of a metal net, which is safe, simple, low in cost, environment-friendly and pollution-free, and the metal net with a wear-resistant and corrosion-resistant special carbonized coating is obtained by carbonizing the surface of the metal net and can be used as a substrate material for compounding high polymer materials.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a method for carbonizing the surface of a metal net, which comprises the following steps:

and soaking the metal net in an edible oil organic solution, taking out, naturally airing, and calcining to obtain the carbon-coated metal net.

Preferably, the edible oil in the edible oil organic solution comprises one or more of soybean oil, peanut oil, corn oil, rapeseed oil, olive oil and sunflower seed oil.

Preferably, the organic solvent in the organic solution of edible oil comprises at least one of methanol, ethanol, hexane and heptane.

Preferably, the mass fraction of the edible oil in the edible oil organic solution is 5-95%.

Preferably, the soaking time is 10-600 seconds, and the temperature is room temperature.

Preferably, the calcining temperature is 300-1000 ℃; the heat preservation time is 1-4 h.

Preferably, the temperature rise rate from room temperature to the calcination temperature is 5-10 ℃/min.

Preferably, the calcination is carried out under protective atmosphere conditions.

Preferably, the carbon layer of the carbon-coated metal mesh has a thickness of 500nm to 5 μm.

Preferably, the carbon layer of the carbon-coated metal mesh consists of micro-carbon particles.

The invention provides a method for carbonizing the surface of a metal net, which comprises the following steps: and soaking the metal net in an edible oil organic solution, taking out, naturally airing, and calcining to obtain the carbon-coated metal net. According to the invention, the edible oil is used as a carbon source, and the oxygen-containing functional groups in the edible oil are decomposed by calcining, so that only carbon is left, and the carbon-coated metal mesh is obtained, has wear-resistant and corrosion-resistant surface, can be used as a substrate material of a high polymer material and is firmly compounded with the high polymer material, and the preparation method is safe and simple, green and environment-friendly in process and low in cost.

Drawings

FIG. 1 is a scanning electron micrograph of a carbon-coated metal mesh prepared in example 1;

FIG. 2 is a graph showing the results of an abrasion resistance test performed on the carbon-coated metal mesh prepared in example 1;

FIG. 3 is a graph showing the results of an acid and alkali corrosion resistance experiment performed on the carbon-coated metal mesh prepared in example 1;

FIG. 4 is a graph showing the results of an acid and alkali corrosion resistance experiment performed on a metal mesh of a comparative example.

Detailed Description

and soaking the metal net in an edible oil organic solution, taking out the metal net, naturally airing, and calcining to obtain the carbon-coated metal net.

The invention does not require any particular structure or composition of the expanded metal, and expanded metal known to those skilled in the art is suitable for use in the invention. In a specific embodiment of the present invention, the metal mesh is a stainless steel mesh, a copper mesh or a nickel mesh.

In the present invention, the metal mesh preferably further comprises a pretreatment before the soaking. In the present invention, the method of pretreatment preferably comprises: and (3) sequentially carrying out acid washing, water washing and drying on the metal mesh. In the invention, the washing liquid for acid washing is preferably dilute hydrochloric acid, and the mass concentration of the dilute hydrochloric acid is preferably 5%; the pickling mode is preferably soaking for 10 min. The invention has no special requirements on the specific processes of washing and drying, and can clean the washing liquid for pickling and fully dry the pickling liquid.

In the present invention, the preparation method of the organic solution of edible oil preferably comprises: mixing the edible oil with an organic solvent to obtain an edible oil organic solution. In the present invention, the mixing is preferably performed under stirring conditions.

In the invention, the edible oil in the edible oil organic solution preferably comprises one or more of soybean oil, peanut oil, rapeseed oil, olive oil, sunflower seed oil and corn oil; when the edible oil comprises a plurality of components, the invention has no special requirements on the mixture ratio of the components and can be used in any mixture ratio. In the invention, the mass fraction of the edible oil in the edible oil organic solution is preferably 5-95%, more preferably 10-90%, and particularly preferably 30%, 50%, 60%, 80%, 90%.

In the present invention, the organic solvent in the organic solution of edible oil preferably comprises at least one of methanol, ethanol, hexane and heptane; when the organic solvent comprises a plurality of components, the proportion of each component is not particularly required, and any proportion can be adopted. In a specific embodiment of the present invention, when the organic solvent is ethanol and heptane, the mass ratio of ethanol to heptane is preferably 1: 1; when the organic solvent is methanol and hexane, the mass ratio of the methanol to the hexane is 1: 3.

in the invention, the time for soaking the metal net in the edible oil organic solution is preferably 10-600 seconds, more preferably 15-50 seconds, and further preferably 20-35 seconds; the temperature is preferably room temperature.

In the present invention, the natural airing is preferably natural airing at room temperature under ventilation conditions. The invention leads the organic solvent to be fully volatilized through natural drying, and the edible oil is fully coated on the surface of the metal net.

In the invention, the calcining temperature is preferably 300-1000 ℃, more preferably 450-900 ℃, and further preferably 600-800 ℃; the heat preservation time is preferably 1-4 h, more preferably 1.5-3 h, and further preferably 2-3 h. In the calcining process, oxygen-containing functional groups in the edible oil are decomposed, and only carbon is left, so that the carbon-coated metal mesh is obtained.

In the invention, the heating rate from room temperature to the calcining temperature is preferably 5-10 ℃/min, more preferably 6-8 ℃/min, and even more preferably 6.5-7 ℃/min. The invention can gradually decompose the edible oil by controlling the heating rate, and avoid the damage to the uniformity of the carbon layer caused by violent gas generation.

In the present invention, the calcination is preferably performed under a protective atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere.

In the present invention, the carbon layer of the carbon-coated metal mesh preferably has a thickness of 500nm to 5 μm, more preferably 800nm to 2 μm. The invention controls the thickness of the carbon layer by controlling the mass fraction of the edible oil organic solution, and controls the thickness in the range, thereby being beneficial to coating the metal net carbon layer and not influencing the mesh size of the original metal net.

In the invention, the carbon layer of the carbon-coated metal net is preferably composed of micro carbon particles, so that the carbon-coated metal net has better wear resistance and corrosion resistance, and can improve the surface mechanical strength of the metal net; meanwhile, the carbon layer on the metal net can be tightly combined with the high molecular organic matter to be used as a substrate material for the solid carrying of the high molecular composite material.

In the existing products, methods such as a methane CVD method and activated carbon high-temperature curing are mostly used for coating carbon on the metal surface, and the methods have the problems of complex preparation method, environmental pollution, high cost, poor stability, high risk and the like. The carbon-coated metal mesh prepared by the invention has wear-resistant and corrosion-resistant surface, can be used as a substrate material of a high polymer material to be firmly compounded with the high polymer material, has the advantages of safety, simplicity, green and environment-friendly process and low cost, and has good commercial prospect in the technical field of special carbonization treatment of metal surfaces.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Adding 30g of soybean oil into a beaker, adding 70g of ethanol, stirring and uniformly dispersing to obtain a 30% edible oil organic solution;

soaking the stainless steel net in dilute hydrochloric acid with the mass concentration of 5% for 10min, washing with water, and drying to obtain a pretreated stainless steel net;

soaking the pretreated stainless steel mesh in 30% edible oil organic solution for 20s, taking out, and naturally drying at room temperature under ventilation conditions;

placing the dried stainless steel mesh in a tubular furnace, carrying out temperature programming calcination, introducing nitrogen for protection at normal pressure, wherein the process parameters of the temperature programming calcination are as follows: heating the mixture from room temperature to 300 ℃, and preserving heat for 1h when the temperature reaches a set value, wherein the set heating rate is 6 ℃/min, so as to obtain the carbon-coated metal mesh.

Example 2

Adding 50g of peanut oil into a beaker, adding 50g of methanol, stirring and dispersing uniformly to obtain 50% of edible oil organic solution;

soaking the pretreated stainless steel mesh in 50% edible oil organic solution for 60s, taking out, and naturally drying at room temperature under ventilation conditions;

placing the dried stainless steel mesh in a tubular furnace, carrying out temperature programming calcination, introducing nitrogen for protection at normal pressure, wherein the process parameters of the temperature programming calcination are as follows: and heating to 600 ℃ from room temperature, preserving the heat for 3 hours when the temperature reaches a set value, and setting the heating rate to be 8 ℃/min to obtain the carbon-coated metal mesh.

Example 3

Adding 80g of rapeseed oil into a beaker, adding 10g of ethanol and 10g of heptane, and uniformly stirring and dispersing to obtain an 80% edible oil organic solution;

soaking the pretreated stainless steel mesh in 80% edible oil organic solution for 40s, taking out, and naturally drying at room temperature under ventilation conditions;

placing the dried stainless steel mesh in a tubular furnace, carrying out temperature programming calcination, introducing nitrogen for protection at normal pressure, wherein the process parameters of the temperature programming calcination are as follows: heating to 800 ℃ from room temperature, and preserving heat for 2h when the temperature reaches a set value, wherein the set heating rate is 10 ℃/min, so as to obtain the carbon-coated metal mesh.

Example 4

Adding 60g of olive oil into a beaker, adding 10g of methanol and 30g of hexane, stirring and uniformly dispersing to obtain a 60% edible oil organic solution;

soaking the pretreated stainless steel mesh in 60% edible oil organic solution for 30s, taking out, and naturally drying at room temperature under ventilation conditions;

placing the dried stainless steel mesh in a tubular furnace, carrying out temperature programming calcination, introducing nitrogen for protection at normal pressure, wherein the process parameters of the temperature programming calcination are as follows: heating the mixture from room temperature to 450 ℃, and preserving heat for 1h when the temperature reaches a set value, wherein the set heating rate is 6.5 ℃/min, so as to obtain the carbon-coated metal mesh.

Example 5

Adding 90g of sunflower seed oil into a beaker, adding 10g of heptane, and uniformly stirring and dispersing to obtain 90% of edible oil organic solution;

soaking the pretreated stainless steel mesh in 90% edible oil organic solution for 30s, taking out, and naturally drying at room temperature under ventilation conditions;

placing the dried stainless steel mesh in a tubular furnace, carrying out temperature programming calcination, introducing nitrogen for protection at normal pressure, wherein the process parameters of the temperature programming calcination are as follows: heating the mixture from room temperature to 900 ℃, and preserving heat for 1.5h when the temperature reaches a set value, wherein the set heating rate is 7 ℃/min, so as to obtain the carbon-coated metal mesh.

Comparative example

Soaking the stainless steel net in dilute hydrochloric acid with the mass concentration of 5% for 10min, washing with water, and drying in the air to obtain a pretreated stainless steel net, wherein the pretreated stainless steel net is taken as a comparative example.

Test example 1

The scanning electron microscope image of the carbon-coated metal mesh prepared in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the metal wire surface of the carbon-coated metal mesh is tightly wrapped with a layer of rugged micro carbon particle layer, the carbon film has good wear resistance and corrosion resistance, the surface mechanical strength of the metal mesh can be improved, and meanwhile, the carbon layer on the metal mesh can be tightly combined with a high molecular organic matter to be used as a substrate material for fixing a high molecular composite material.

The scanning electron micrographs of the carbon-coated metal meshes obtained in examples 2 to 5 are similar to those in FIG. 1.

Test example 2

Abrasion resistance test: a 1000 mesh sandpaper was placed on a table, and then a 2cm × 10cm carbon-coated metal mesh prepared in example 1 was placed on the sandpaper, and then a 500g weight was placed on the metal mesh, and the carbon-coated metal mesh was horizontally pulled and slid on the sandpaper by 100cm, after which the abrasion of the carbon-coated metal mesh was observed under a microscope, as shown in fig. 2.

Acid and alkali corrosion resistance: preparing a sodium hydroxide solution with a pH value of 13, immersing the carbon-coated metal mesh prepared in example 1 in the sodium hydroxide solution for 24 hours, and performing an alkali resistance test, as shown in FIG. 3; a hydrochloric acid solution having a pH of 2 was prepared, and the carbon-coated metal mesh was immersed therein for 24 hours to perform an acid resistance test, similar to fig. 3.

As can be seen from fig. 2 and 3, the carbon layer on the surface of the carbon-coated metal mesh is not significantly changed, and shows excellent wear and corrosion resistance.

The results of the wear resistance test and the acid and alkali corrosion resistance of the carbon-coated metal mesh obtained in examples 2 to 5 are similar to those in FIGS. 2 to 3.

The stainless steel net of the comparative example was subjected to the acid resistance test according to the above-described acid and alkali resistance test, and the obtained stainless steel net was subjected to the scanning electron microscope image shown in fig. 4, which is similar to fig. 4. As is apparent from fig. 4, a plurality of pits appear on the wire mesh due to corrosion, and the corrosion phenomenon is severe.

Therefore, the wear resistance and the corrosion resistance of the metal mesh can be enhanced by adopting the method provided by the invention.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A method for carbonizing a surface of a metal mesh, comprising the steps of:

soaking the metal net in an edible oil organic solution, taking out, naturally drying, and calcining to obtain a carbon-coated metal net; the carbon-coated metal mesh is used as a substrate material for immobilizing the high-molecular composite material;

the thickness of the carbon layer of the carbon-coated metal net is 500 nm-5 mu m;

the carbon layer of the carbon-coated metal mesh consists of micro carbon particles;

the soaking time is 10-600 seconds, and the temperature is room temperature;

the calcining temperature is 300-1000 ℃; the heat preservation time is 1-4 h;

the temperature rise rate from the room temperature to the calcination temperature is 5-10 ℃/min.

2. The carbonization method according to claim 1, wherein the edible oil in the organic solution of edible oil comprises one or more of soybean oil, peanut oil, rapeseed oil, olive oil, sunflower seed oil and corn oil.

3. The carbonization method of claim 1, wherein the organic solvent in the organic solution of edible oil comprises at least one of methanol, ethanol, hexane, and heptane.

4. The carbonization method according to any one of claims 1 to 3, wherein the edible oil in the organic solution of edible oil is 5 to 95% by mass.

5. Carbonization method according to claim 1, characterized in that the calcination is carried out under protective atmosphere conditions.