A polymer-reinforced nanocarbon material-metal composite material and its preparation method

Abstract

The present invention provides a polymer-reinforced nano-carbon material-metal composite material and a preparation method thereof, characterized in that the raw materials of the polymer-reinforced nano-carbon material-metal composite material, measured by weight, include: 40-70 parts of nano-carbon material, 20-50 parts of metal composite material, 5-10 parts of polymer compound, and 1-3 parts of reinforcing agent; the polymer-reinforced nano-carbon material-metal composite material is modified by the polymer compound on the nano-carbon material and the metal composite material, the polymer compound improves the strength and modulus of the nano-carbon material and the metal composite material, the polymer compound is cross-linked between the nano-carbon material and the metal composite material to increase the elongation at break, and after carbonization, the benzene ring structure thereof is also conducive to further improving the thermal conductivity, hardness, and thermal expansion performance of the polymer-reinforced nano-carbon material-metal composite material, and has good application prospects.

Description

Technical Field

[0001] The present invention relates to the field of nano-carbon materials, and in particular to a polymer-reinforced nano-carbon material-metal composite material and a preparation method thereof. Background Art

[0002] Pipeline systems play a vital role in numerous industrial sectors, such as petrochemicals, energy distribution, and heating and cooling. They transport fluids or gases, and their performance directly impacts the efficiency, safety, and reliability of the entire industrial process. As modern industry evolves toward high temperatures, high pressures, and high efficiency, increasingly stringent requirements are placed on the thermal conductivity, hardness, and thermal expansion properties of pipeline materials. Traditional pipeline materials are gradually exposing their limitations in meeting these challenges, and the emergence of carbon nanotubes (CNTs) has created new opportunities for improving pipeline performance. As a nanomaterial with exceptional performance, CNTs' unique structure endows them with exceptional properties in various aspects, including mechanics, electricity, thermal energy, and chemistry.

[0003] Many traditional pipe materials, such as ordinary carbon steel, stainless steel and other metal materials, although they have a certain thermal conductivity, their thermal conductivity is relatively limited. In some application scenarios that require efficient heat dissipation or rapid heat transfer, such as high-temperature steam transmission pipelines, heat exchanger pipelines, etc., this low thermal conductivity will cause heat to not be dissipated or transferred in time, resulting in energy loss and local overheating of the pipeline, affecting the service life of the pipeline and the operating efficiency of the system. Non-metallic pipe materials such as plastic pipes (such as polyethylene, polypropylene, etc.) have even lower thermal conductivity, usually between 0.2-0.5W / (m·K). In pipe applications involving the need to exchange heat with the outside world, the low thermal conductivity of plastic pipes will seriously hinder the transfer of heat, making the heat exchange process slow and insufficient, and unable to meet the needs of some industries with high requirements for heat exchange efficiency.

[0004] Traditional metal piping materials have certain shortcomings in terms of hardness. For example, ordinary carbon steel has a relatively low hardness, with a Brinell hardness generally between 150-200 HB. It is easily deformed, scratched, or corroded when subjected to external impact, abrasion, or high-pressure fluid erosion. When transporting fluids containing solid particles or under high flow conditions, the inner wall of carbon steel pipes is easily worn, resulting in thinning of the pipe wall thickness, reducing the pipe's load-bearing capacity and safety. Although some alloy materials, such as chromium-molybdenum alloy steel, have higher hardness, they are often accompanied by problems such as high cost and difficulty in processing.

[0005] Metal pipe materials will expand thermally when the temperature changes. For example, the linear expansion coefficient of carbon steel is about 10-12×10 -6 / ℃, the linear expansion coefficient of stainless steel is 16-18×10 -6 / °C. In long-distance pipeline transportation or applications subject to frequent and drastic temperature fluctuations, such as geothermal pipelines and chemical reaction pipelines, this thermal expansion can generate significant thermal stress. If thermal expansion of the pipeline is not effectively compensated, it can cause pipeline deformation, loosening of joints, or even rupture, leading to leakage accidents and serious harm to industrial production and the environment. Non-metallic piping materials also experience thermal expansion issues, and some plastic pipes have a higher thermal expansion coefficient than metals.

[0006] In response to the problems existing in the prior art, this application aims to solve the problems of insufficient thermal conductivity, hardness and thermal expansion performance of pipeline materials. Summary of the Invention

[0007] Purpose of the invention: The purpose of the present invention is to provide a polymer reinforced nano-carbon material-metal composite material and a preparation method thereof, wherein the nano-carbon material and the metal composite material are modified by a polymer compound, and the polymer compound improves the strength and modulus of the nano-carbon material and the metal composite material, and improves the thermal conductivity, hardness and thermal expansion performance of the polymer reinforced nano-carbon material-metal composite material.

[0008] The technical solution of the present invention:

[0009] The present invention provides a polymer reinforced nano-carbon material-metal composite material, characterized in that the raw materials of the polymer reinforced nano-carbon material-metal composite material include, by weight, 40-70 parts of nano-carbon material, 20-50 parts of metal composite material, 5-10 parts of polymer compound, and 1-3 parts of reinforcing agent.

[0010] Furthermore, the nano-carbon material is a mixture of one or more of carbon nanotubes, carbon nanospheres, and graphite.

[0011] Furthermore, the preparation of the metal composite material includes the following steps:

[0012] S1: Add metal powders in a certain proportion to a ball mill, add an appropriate amount of ethanol and mix by ball milling for 0.5-1 hour to obtain a uniformly mixed metal composite powder, dry the metal composite powder in a vacuum drying oven at a drying temperature of 40-60°C, remove the ethanol and set aside;

[0013] S2: mixing the metal composite powder dried in step S1 with phenolic resin in a certain proportion, and kneading the mixture in a mixer to obtain a kneaded mixture;

[0014] S3: placing the mixed mixture prepared in step S2 into a mold and performing hot pressing on a hot press at a temperature of 180-200°C, a pressure of 20-30 MPa, and a holding time of 1-2 hours;

[0015] S4: Sintering the sample formed by hot pressing in step S3 under a nitrogen atmosphere at a sintering temperature of 1600-1800° C. for 2-3 hours to obtain a metal composite material.

[0016] Furthermore, the metal powder in step S1 is a mixture of one or more of nickel, chromium, titanium, silver, tungsten, molybdenum, and manganese.

[0017] Furthermore, in step S2, the mass ratio of the metal composite powder to the phenolic resin is 3-5:1.

[0018] Furthermore, the preparation of the polymer compound comprises the following steps:

[0019] S1: Add 2-hydroxybenzaldehyde and dimethylformamide into a three-necked flask, then add aspartic acid and tetrabutyl titanate, and stir evenly;

[0020] S2: Raise the temperature of step S1 to 100-120°C for 10-16 hours;

[0021] S3: After the reaction in step S2 is completed, the reaction solution is cooled to room temperature and then poured into cold water to precipitate the polymer. The obtained polymer precipitate is filtered, washed with deionized water, and then dried in a vacuum drying oven to constant weight at a drying temperature of 50-60°C and a drying time of 12-24 hours to obtain a polymer compound.

[0022] Furthermore, the mass ratio of the 2-hydroxybenzaldehyde to aspartic acid is 0.8-1:1.

[0023] Furthermore, the addition amount of tetrabutyl titanate is 2-5% of the total mass of 2-hydroxybenzaldehyde and aspartic acid.

[0024] Furthermore, the strengthening aid is a mixture of one or more of silicon dioxide, calcium oxide, and calcium sulfate.

[0025] The present invention also provides a method for preparing a polymer reinforced nano-carbon material-metal composite material, which is characterized by comprising the following steps:

[0026] (1) adding nano-carbon materials into a reactor, and then adding an acidic mixed solution to pretreat the nano-carbon materials;

[0027] (2) adding the nano-carbon material, metal composite material and strengthening agent pretreated in step (1) to chlorosulfonic acid, controlling the temperature at 0-10° C. and stirring for 1-3 hours to form a uniform composite carbon nanotube dispersion;

[0028] (3) adding the polymer compound to the composite carbon nanotube dispersion prepared in step (2), stirring and mixing to form a uniform spinning solution;

[0029] (4) pouring the prepared spinning solution into the liquid storage tank of the spinning equipment and extruding it into the coagulation bath through the spinneret for wet spinning;

[0030] (5) subjecting the fiber obtained by wet spinning in step (4) to high-temperature carbonization treatment under the protection of an inert atmosphere;

[0031] (6) After the high-temperature carbonization treatment in step (5), the temperature is raised again and then kept warm for a period of time to obtain the polymer-reinforced nano-carbon material-metal composite material.

[0032] Furthermore, the acidic mixed solution in step (1) is a mixture of concentrated sulfuric acid and concentrated nitric acid.

[0033] Furthermore, the mass ratio of the acidic mixed solution to the nano-carbon material is 5-10:1.

[0034] Furthermore, the stirring speed in step (3) is 500-1500 rpm, and the stirring time is 3-6 hours.

[0035] Furthermore, the coagulation bath in step (4) is an aqueous solution of water and inorganic salts, the temperature is 20-40° C., the extrusion pressure is 0.1-0.5 MPa, and the drawing speed is 1-5 m / min.

[0036] Furthermore, the inorganic salt in step (4) is one or more of calcium chloride and sodium sulfate.

[0037] Furthermore, the heating rate of step (5) is 5-10°C / min, the carbonization temperature is 800-1500°C, and the holding time is 1-3 hours.

[0038] Furthermore, the step (6) is further heated to a temperature of 2000-3000° C. and a holding time of 0.5-2 hours.

[0039] The present invention provides a polymer-reinforced nano-carbon material-metal composite material. The polymer compound is cross-linked between the nano-carbon material and the metal composite material to increase its elongation at break. After carbonization, its benzene ring structure further improves the thermal conductivity, hardness, and thermal expansion performance of the nano-carbon material and metal composite material.

[0040] Beneficial effects:

[0041] The present invention provides a polymer reinforced nano-carbon material-metal composite material. The polymer reinforced nano-carbon material-metal composite material has high thermal conductivity, hardness and good thermal expansion performance, and has good application prospects. DETAILED DESCRIPTION

[0042] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are illustrative of the present invention and are intended only to illustrate the present invention and are not intended to limit the present invention. Other combinations and various modifications within the scope of the present invention may be made without departing from the spirit or scope of the present invention.

[0043] Unless otherwise specified, the chemical reagents used in the present invention were all commercially available analytical grade; the phenolic resin model was BMJ-92, purchased from Ruibo Chemical Co., Ltd.

[0044] Preparation of metal composite materials:

[0045] S1: 1 kg nickel powder, 0.5 kg chromium powder, and 0.5 kg titanium powder were added to a ball mill, and 5 L ethanol was added for ball milling. The mixture was ball milled for 0.5 h to obtain a uniformly mixed metal composite powder. The metal composite powder was dried in a vacuum drying oven at 50°C, and the ethanol was removed for later use.

[0046] S2: adding 0.4 kg of phenolic resin to the metal composite powder dried in step S1 according to a certain ratio, and kneading the mixture in a mixer to obtain a kneaded mixture;

[0047] S3: placing the kneaded mixture prepared in step S2 into a mold and performing hot pressing on a hot press at a temperature of 180°C, a pressure of 25 MPa, and a holding time of 2 hours;

[0048] S4: Sintering the sample formed by hot pressing in step S3 under a nitrogen atmosphere at a sintering temperature of 1800° C. for a holding time of 2 hours to obtain a metal composite material.

[0049] Preparation of polymer compound A:

[0050] S1: Add 1 kg of 2-hydroxybenzaldehyde and 1 L of dimethylformamide to a three-necked flask, then add 1 kg of aspartic acid and 0.04 kg of tetrabutyl titanate and stir evenly;

[0051] S2: Heat the reaction in step S1 to 120°C for 12 hours;

[0052] S3: After the reaction in step S2 is completed, the reaction solution is cooled to room temperature and then poured into cold water to precipitate the polymer. The obtained polymer precipitate is filtered, washed with deionized water, and then dried in a vacuum drying oven to constant weight at a drying temperature of 50° C. and a drying time of 24 hours to obtain a polymer compound.

[0053] Preparation of polymer compound B:

[0054] The difference between the present preparation and the polymer compound A is that 1 kg of 2-hydroxybenzaldehyde and 1 kg of aspartic acid in step S1 are replaced by 0.8 kg of 2-hydroxybenzaldehyde and 1 kg of aspartic acid.

[0055] Preparation of polymer compound C:

[0056] The difference between the present preparation and polymer compound A is that 1 kg of 2-hydroxybenzaldehyde and 1 kg of aspartic acid in step S1 are replaced by 1.2 kg of 2-hydroxybenzaldehyde and 0.8 kg of aspartic acid.

[0057] Preparation of polymer reinforced nanocarbon-metal composites:

[0058] (1) Adding nanocarbon materials into a reactor, and then adding an acidic mixed solution (the mass ratio of concentrated sulfuric acid to concentrated nitric acid is 1:1) with a mass of 5 times that of the nanocarbon materials to pretreat the nanocarbon materials;

[0059] (2) adding the nano-carbon material, the metal composite material and the strengthening agent pretreated in step (1) to chlorosulfonic acid 10 times the mass of the nano-carbon material and the metal composite material, controlling the temperature at 0° C. and stirring for 2 hours to form a uniform composite carbon nanotube dispersion;

[0060] (3) adding the polymer compound to the composite carbon nanotube dispersion prepared in step (2), stirring and mixing to form a uniform spinning solution, the stirring speed is 1000 rpm, and the stirring time is 5 hours;

[0061] (4) Pour the prepared spinning solution into the liquid storage tank of the spinning equipment and extrude it into the coagulation bath through the spinneret for wet spinning. The coagulation bath is an aqueous solution of water and calcium chloride (the mass ratio of water to calcium chloride is 10:1), the temperature is 20°C, the extrusion pressure is 0.25 MPa, and the drawing speed is 2 m / min;

[0062] (5) subjecting the fiber obtained by wet spinning in step (4) to high-temperature carbonization treatment under nitrogen protection, with a heating rate of 10°C / min, a carbonization temperature of 1000°C, and a holding time of 2 hours;

[0063] (6) After the high-temperature carbonization treatment in step (5), the temperature is raised to 2500° C. and kept at this temperature for 1 hour to obtain the polymer-reinforced nano-carbon material-metal composite material.

[0064] Examples 1-4

[0065] According to the above-mentioned preparation method of the polymer reinforced nano-carbon material-metal composite material, Table 1 is the ingredient list of the polymer reinforced nano-carbon material-metal composite material of Examples 1-4 in parts.

[0066] Table 1:

[0067]

[0068]

[0069] Comparative Example 1-2

[0070] Comparative Examples 1-2 were prepared according to the above-mentioned method for preparing polymer-reinforced nano-carbon material-metal composite materials. Table 2 is a list of ingredients of the polymer-reinforced nano-carbon material-metal composite materials of Comparative Examples 1-2, calculated in parts.

[0071] Table 2:

[0072]

[0073] The polymer reinforced nano-carbon material-metal composite material prepared in Examples 1-4 and Comparative Examples 1-2 was prepared into The carbon tubes were tested for the following properties:

[0074] 1. Thermal conductivity test:

[0075] According to the standard GB / T 8722-2019 "Determination of thermal conductivity of carbon materials", the polymer reinforced nano-carbon material-metal composite materials prepared in Examples 1-4 and Comparative Examples 1-2 were prepared. The carbon tube samples were tested for thermal conductivity.

[0076] 2. Hardness test:

[0077] According to the standard GB / T 39535-2020 "High-temperature stress relaxation test method for high-temperature alloys", the polymer reinforced nano-carbon material-metal composite materials prepared in Examples 1-4 and Comparative Examples 1-2 were prepared. The carbon tube samples were tested for hardness.

[0078] 3. Thermal expansion coefficient test:

[0079] According to the standard JB / T 8133.18-2017 "Test methods for physical and chemical properties of electric carbon products Part 18: Linear expansion coefficient", the polymer reinforced nano-carbon material-metal composite materials prepared in Examples 1-4 and Comparative Examples 1-2 were prepared. The carbon tube samples were tested for thermal expansion coefficient.

[0080] Table 3: Test results

[0081]

[0082] From the above data, it can be seen that the carbon tubes prepared from the polymer reinforced nano-carbon material-metal composite material prepared in Examples 1-3 have high thermal conductivity, high hardness, small linear expansion coefficient, high stability, and will not produce excessive deformation due to thermal expansion and contraction; from the comparison between Example 4 and Example 2, it can be seen that adjusting the mass ratio of 2-hydroxybenzaldehyde and aspartic acid for preparing the polymer compound will cause the thermal conductivity of the carbon tubes of the prepared polymer reinforced nano-carbon material-metal composite material to deteriorate, the hardness to decrease, and the linear expansion coefficient to decrease; from the comparison between Comparative Example 1 and Example 2, it can be seen that without adding the polymer compound, the thermal conductivity of the carbon tubes prepared from the polymer reinforced nano-carbon material-metal composite material will deteriorate, the hardness will decrease, and the linear expansion coefficient will decrease; from the comparison between Comparative Example 2 and Example 2, it can be seen that without adding the metal composite material, the thermal conductivity of the carbon tubes prepared from the polymer reinforced nano-carbon material-metal composite material will deteriorate, the hardness will decrease, and the linear expansion coefficient will decrease, and the expected effect will not be achieved.

[0083] The present invention can also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to the present invention.

Claims

1. A polymer reinforced nano-carbon material-metal composite material, characterized in that: The raw materials of the polymer reinforced nano-carbon material-metal composite material include, by weight, 40-70 parts of nano-carbon material, 20-50 parts of metal composite material, 5-10 parts of polymer compound, and 1-3 parts of reinforcing agent; The preparation of the metal composite material comprises the following steps: S1: Add metal powders in a certain proportion to a ball mill, add an appropriate amount of ethanol and mix by ball milling for 0.5-1 hour to obtain a uniformly mixed metal composite powder, dry the metal composite powder in a vacuum drying oven at a drying temperature of 40-60°C, remove the ethanol and set aside; S2: mixing the metal composite powder dried in step S1 with phenolic resin in a certain proportion, and kneading the mixture in a mixer to obtain a kneaded mixture; S3: placing the mixed mixture prepared in step S2 into a mold and performing hot pressing on a hot press at a temperature of 180-200°C, a pressure of 20-30 MPa, and a holding time of 1-2 hours; S4: Sintering the sample formed by hot pressing in step S3 under a nitrogen atmosphere at a sintering temperature of 1600-1800° C. for 2-3 hours to obtain a metal composite material; the metal powder in step S1 is a mixture of one or more of nickel, chromium, titanium, silver, tungsten, molybdenum, and manganese; In step S2, the mass ratio of the metal composite powder to the phenolic resin is 3-5:1; The preparation of the polymer compound comprises the following steps: S1: Add 2-hydroxybenzaldehyde and dimethylformamide into a three-necked flask, then add aspartic acid and tetrabutyl titanate, and stir evenly; S2: Heat the reaction mixture in step S1 to 100-120°C for 10-16 hours; S3: After the reaction in step S2 is completed, the reaction solution is cooled to room temperature and then poured into cold water to precipitate the polymer. The obtained polymer precipitate is filtered, washed with deionized water, and then dried in a vacuum drying oven to constant weight at a drying temperature of 50-60° C. for a drying time of 12-24 hours to obtain a polymer compound; The mass ratio of the 2-hydroxybenzaldehyde to aspartic acid is 0.8-1:1; the added amount of the tetrabutyl titanate is 2-5% of the total mass of the 2-hydroxybenzaldehyde and aspartic acid.

2. The polymer reinforced nano-carbon material-metal composite material according to claim 1, characterized in that: The nano-carbon material is a mixture of one or more of nano-carbon tubes, nano-carbon balls and graphite.

3. The polymer reinforced nano-carbon material-metal composite material according to claim 1, characterized in that: The strengthening auxiliary agent is a mixture of one or more of silicon dioxide, calcium oxide and calcium sulfate.

4. The method for preparing the polymer reinforced nano-carbon material-metal composite material according to any one of claims 1 to 3, characterized in that: The following steps are involved: (1) Adding nanocarbon materials into a reactor, and then adding an acidic mixed solution to pretreat the nanocarbon materials; (2) adding the nano-carbon material, metal composite material and strengthening agent pretreated in step (1) into chlorosulfonic acid, controlling the temperature at 0-10°C and stirring for 1-3 hours to form a uniform composite carbon nanotube dispersion; (3) adding the polymer compound to the composite carbon nanotube dispersion prepared in step (2), stirring and mixing to form a uniform spinning solution; (4) Pour the prepared spinning solution into the liquid storage tank of the spinning equipment and extrude it into the coagulation bath through the spinneret for wet spinning; (5) subjecting the fibers obtained by wet spinning in step (4) to high-temperature carbonization treatment under the protection of an inert atmosphere; (6) After the high-temperature carbonization treatment in step (5), the temperature is raised again and then kept warm for a period of time to obtain the polymer-reinforced nano-carbon material-metal composite material.

5. The method for preparing a polymer reinforced nano-carbon material-metal composite material according to claim 4, characterized in that: The acidic mixed solution in step (1) is a mixture of concentrated sulfuric acid and concentrated nitric acid; the mass ratio of the acidic mixed solution to the nano-carbon material is 5-10:1; In step (3), the stirring speed is 500-1500 rpm and the stirring time is 3-6 hours; In step (4), the coagulation bath is an aqueous solution of water and inorganic salts, the temperature is 20-40°C, the extrusion pressure is 0.1-0.5 MPa, and the drawing speed is 1-5 m / min; The inorganic salt in step (4) is one or more of calcium chloride and sodium sulfate; In step (5), the heating rate is 5-10°C / min, the carbonization temperature is 800-1500°C, and the holding time is 1-3 hours; In step (6), the temperature is raised again to 2000-3000° C. and the holding time is 0.5-2 hours.

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