A high heat dissipation nickel-based composite material and its preparation method

Abstract

The application discloses a high-heat-dissipation nickel-based composite material and a preparation method thereof, and relates to the technical field of composite materials. In the application, chromium is added to the nickel-based material to reduce the expansion coefficient of the composite material and match the semiconductor chip, and the thermal expansion coefficient is reduced without affecting the corrosion resistance. However, the overall mechanical properties and the heat conductivity coefficient of the nickel-based material are relatively low, and therefore, a boron nitride high-heat-conducting layer and a high-strength heat-dissipation coating layer are arranged on the surface of the nickel-based material to improve the heat-dissipation performance and the mechanical properties of the nickel-based material. The high-strength heat-dissipation coating layer comprises mercapto-terminated polyurethane and double-bond modified graphene, and the two are combined through a mercapto-ene click reaction, so that the graphene is uniformly dispersed in the coating system. The sheet structure of the graphene and the tubular structure of the carbon nanotube form a continuous and uniform heat-conducting network, the coating layer is more uniform and denser, and the heat-dissipation performance and the mechanical properties of the coating layer are further improved.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, specifically to a high heat dissipation nickel-based composite material and its preparation method. Background Technology

[0002] With the rapid development of modern electronic information, the electronics industry is also improving human production methods. Electronic components, as the cornerstone of the rapid development of the electronics industry, are the key to ensuring the stability of the electronics industry. Semiconductor materials are an important carrier of electronic components, and the semiconductor manufacturing process requires properties such as high temperature resistance and corrosion resistance.

[0003] In semiconductor manufacturing, nickel-based materials have emerged in several key stages. Nickel-based materials possess excellent high-temperature resistance, oxidation resistance, and corrosion resistance. Some high-temperature components in semiconductors are often made of nickel-based alloys to ensure stable operation of equipment for extended periods in harsh environments. In the field of chip packaging, the good conductivity of nickel-based composite materials ensures efficient transmission of electrical signals between the chip and external circuits. However, although nickel-based materials have good heat resistance, their thermal conductivity is not high enough to quickly dissipate heat, leading to excessively high local temperatures on the chip, which affects heat dissipation and device reliability.

[0004] Therefore, we propose a high heat dissipation nickel-based composite material and its preparation method, which gives the composite material good heat dissipation and high temperature stability. Summary of the Invention

[0005] The purpose of this invention is to provide a high heat dissipation nickel-based composite material and its preparation method, so as to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a high heat dissipation nickel-based composite material, comprising a nickel-based material, a boron nitride high thermal conductivity layer, and a high-strength heat dissipation coating;

[0007] Nickel-based materials comprise the following components by mass percentage: 0.03-0.05% Mg (magnesium), 10-20% Cr (chromium), 0.06-0.10% Y (yttrium), 0.6-1.2% Cu (copper), with the remainder being Ni (nickel).

[0008] Furthermore, the nickel-based material undergoes heat treatment, with the specific process conditions being: temperature 700~750℃, holding for 100~120 min, and temperature 600~700℃, holding for 100~140 min.

[0009] In the above technical solutions, pure nickel has a low thermal conductivity, while copper has a significantly higher thermal conductivity than nickel. Adding copper can improve the thermal conductivity of nickel-based materials. Magnesium and yttrium in nickel-based materials can refine the grain structure of the alloy, thereby improving the strength and toughness of the nickel-based materials. Chromium has a high melting point, which can increase the recrystallization temperature of nickel. Chromium can also form a continuous passivation film, reducing the oxidation rate of nickel-based materials. Chromium can also significantly reduce the thermal expansion coefficient of nickel, so that the thermal expansion coefficient of the obtained nickel-based material (high heat dissipation nickel-based composite material) matches that of the semiconductor chip (silicon material), reducing the risk of device failure caused by cracking or delamination due to the different shrinkage degrees of the chip and nickel-based material caused by temperature changes.

[0010] Heat treatment can promote recrystallization of nickel-based materials, further refine the grains, and obtain a uniform fine-grained structure.

[0011] A method for preparing a high heat dissipation nickel-based composite material includes the following processes:

[0012] Step 1: Take mercapto-terminated polyurethane, double bond modified graphene, and initiator, mix them, and stir evenly to obtain a high-strength heat dissipation coating.

[0013] Step 2: Heat the nickel-based material to 300~500℃, pass hydrogen and argon gas at a flow ratio of 1:1, perform vapor deposition using solid borane ammonia to form a high thermal conductivity boron nitride layer, then uniformly coat it with a high-strength heat dissipation coating, and irradiate it with ultraviolet light to form a high-strength heat dissipation coating, thus obtaining a high heat dissipation nickel-based composite material.

[0014] Furthermore, in step 1, the mass ratio of mercapto-terminated polyurethane, double-bond modified graphene, and initiator is 10:(1.5~2.5):(0.2~0.6).

[0015] The initiator is 2-hydroxy-2-methyl-1-phenylpropanone.

[0016] Furthermore, in step 2, the deposition thickness of the boron nitride high thermal conductivity layer is 40~60μm;

[0017] In step 2, the thickness of the high-strength heat dissipation coating is 10~20μm;

[0018] In step 2, the process conditions for vapor deposition are: temperature 100~110℃, time 25~35min, power 25~30W;

[0019] In step 2, the process conditions for ultraviolet irradiation are: irradiation power 100~200mW / cm². 2 Irradiation time: 20-30 minutes.

[0020] Furthermore, the mercapto-terminated polyurethane is prepared by the following process:

[0021] S1: Carboxylated carbon nanotubes, branched polyethyleneimine and deionized water are mixed and heated under reflux. After the reaction is completed, the mixture is filtered, washed and freeze-dried to obtain aminoated carbon nanotubes.

[0022] S2: Mix amino-modified carbon nanotubes, m-phenylenedimethyl isocyanate and N-methylpyrrolidone, stir evenly, and heat to react to obtain functionalized carbon nanotubes.

[0023] S3: Mix 4-fluorophenyl isocyanate, functionalized carbon nanotubes, polyethylene glycol, and dibutyltin dilaurate, and heat to react to obtain a polyurethane prepolymer. Then add trimethylolpropane tris(3-mercaptopropionic acid) ester, heat to react, and after the reaction is complete, cool to 50~60℃ and adjust the pH to 7.0~8.0 to obtain mercapto-terminated polyurethane.

[0024] Furthermore, in S1, the mass ratio of carboxylated carbon nanotubes, branched polyethyleneimine, and deionized water is 1:(1~5):(10~15).

[0025] Furthermore, in S1, the process conditions for the heating reflux reaction are: temperature 110~120℃, time 10~12h.

[0026] Furthermore, in S2, the mass ratio of aminated carbon nanotubes, isophthalic dimethyl isocyanate, and N-methylpyrrolidone is 1:(4~6):1.

[0027] Furthermore, in S2, the process conditions for the heating reaction are: temperature 35~45℃, time 1.6~2.0h.

[0028] Furthermore, in S3, the mass ratio of 4-fluorophenyl isocyanate, functionalized carbon nanotubes, polyethylene glycol, dibutyltin dilaurate, and trimethylolpropane tris(3-mercaptopropionic acid) ester is 2: (0.6~1.0): (1.6~2.0): (0.003~0.005): (2.4~2.6).

[0029] Furthermore, in S3, the process conditions for the heating reaction are: temperature 70~80℃, time 3.5~4.5h;

[0030] The process conditions for the heating reaction are: temperature 85~95℃, time 2~3h.

[0031] In the above technical solution, carboxyl groups of carboxylated carbon nanotubes undergo an amidation reaction with amino groups of branched polyethyleneimine to obtain aminated carbon nanotubes. Then, amino groups on the surface of the aminated carbon nanotubes undergo an addition reaction with one isocyanate group of m-phenylenedimethyl isocyanate to form a urea group, while retaining the other isocyanate group, forming carbon nanotubes containing isocyanate groups, referred to as functionalized carbon nanotubes. Finally, a polyurethane prepolymer is generated by reacting functionalized carbon nanotubes, 4-fluorophenyl isocyanate, and polyethylene glycol. During the reaction, the isocyanate group is controlled to be in excess, and then trimethylolpropane tris(3-mercaptopropionic acid) ester is added to end-cap the polyurethane prepolymer with mercapto groups to obtain mercapto-terminated polyurethane.

[0032] Branched polyethyleneimine has high functionality, with numerous primary, secondary, and tertiary amine groups on its molecular chain, resulting in multiple active reaction sites. This allows it to form a high crosslinking density with polyurethane systems, enhancing the mechanical properties of polyurethane. The high crosslinking density also makes it difficult for polyurethane to penetrate, thus improving its corrosion resistance. Functionalized carbon nanotubes possess both urea and isocyanate groups. The amino and carbonyl groups in the urea group form strong hydrogen bonds with high bond energy. Introducing these into polyurethane improves its hardness and wear resistance. The introduced isocyanate groups allow carbon nanotubes to directly participate in the polyurethane synthesis system, increasing the bonding strength between carbon nanotubes and the polyurethane system compared to modification followed by blending, and reducing the likelihood of precipitation. Furthermore, carbon nanotubes exhibit good thermal conductivity and corrosion resistance; introducing them into polyurethane systems significantly enhances their thermal conductivity and corrosion resistance.

[0033] Furthermore, double-bond modified graphene is prepared by the following process:

[0034] Step A: Triethoxysilane, xylene, catalyst, and tetraethylenesilane are mixed and heated to react, yielding a siloxane containing double bonds;

[0035] Step B: Mix graphene oxide, double-bonded siloxane, ethanol aqueous solution, and citric acid, disperse by ultrasonication, heat to react, filter, and wash to obtain double-bonded modified graphene.

[0036] Furthermore, in step A, the mass ratio of triethoxysilane, xylene, catalyst, and tetraethylenesilane is 6:(8~10):(0.006~0.008):(6~8).

[0037] In step A, the catalyst is a cassiterite catalyst.

[0038] Furthermore, in step A, the process conditions for the heating reaction are: temperature 90~100℃, time 8~10h.

[0039] Furthermore, in step B, the mass ratio of graphene oxide, double-bonded siloxane, ethanol aqueous solution, and citric acid is 1:(0.5~1.5):(4~6):(0.05~0.1).

[0040] The mass fraction of the ethanol aqueous solution is 50%.

[0041] Furthermore, in step B, the ultrasonic dispersion process conditions are: frequency 60~80kHz, time 20~30min;

[0042] In step B, the process conditions for the heating reaction are: temperature 65~75℃, time 5~7h.

[0043] In the above technical solution, tetraethylenesilane has four vinyl groups, which can react with triethoxysilane to form a three-dimensional cross-linked network. By controlling the excess of tetraethylenesilane, a siloxane containing double bonds is obtained, which has a more stable structure and better heat resistance compared to ordinary silane coupling agents. Then, by hydrolyzing the siloxane and reacting it with the hydroxyl groups of graphene oxide, double-bond modified graphene is obtained. This not only improves the dispersibility of graphene, but the high degree of cross-linking of the siloxane and polyurethane can also improve the interfacial strength of the polyurethane-graphene bond, thereby improving the mechanical strength of the coating to a certain extent. Then, it is mixed with mercapto-terminated polyurethane, and under the action of an initiator, a mercapto-olefin click reaction occurs, thereby uniformly dispersing the graphene in the coating system and enhancing the bonding force between the graphene and the coating. In addition, both graphene and carbon nanotubes have good corrosion resistance and thermal conductivity. The sheet structure of graphene and the tubular structure of carbon nanotubes form a continuous and uniform thermally conductive network, making the coating more uniform and dense, further improving the heat dissipation and corrosion resistance of the coating.

[0044] Compared with the prior art, the beneficial effects of the present invention are:

[0045] 1. To improve the matching of thermal expansion coefficients between nickel-based materials and semiconductor chips (silicon materials), chromium is added to nickel-based materials to reduce the thermal expansion coefficient of nickel-based materials. This reduces the risk of device failure caused by cracking or delamination due to the shrinkage of the chip and nickel-based materials caused by temperature changes. The resulting high heat dissipation nickel-based composite material can be applied in fields such as semiconductor substrate fabrication.

[0046] 2. A high-strength heat-dissipating coating is applied to the surface of the nickel-based material. The coating system includes mercapto-terminated polyurethane and double-bond modified graphene. In the mercapto-terminated polyurethane, carbon nanotubes with isocyanate groups on their surface are prepared and participate in the polyurethane synthesis process. Mercapto compounds are used for end-capping, and double bonds are grafted onto the graphene surface. Finally, through a mercapto-olefin click reaction, the graphene is uniformly dispersed in the coating system. The sheet structure of graphene and the tubular structure of carbon nanotubes form a continuous and uniform heat-conducting network, making the coating more uniform and dense, and further improving the heat dissipation and corrosion resistance of the coating.

[0047] 3. By using a vapor deposition method with solid boron and nitrogen as the reaction source, a high thermal conductivity boron nitride layer is formed between nickel-based materials and high-strength heat-dissipating coatings. This high thermal conductivity layer has a high surface roughness and the thermal conductivity of boron nitride is significantly higher than that of nickel-based materials. On the one hand, it can improve the bonding strength between high-strength heat-dissipating coatings and nickel-based materials, and on the other hand, it enhances the thermal conductivity of nickel-based materials, further improving heat dissipation performance. Detailed Implementation

[0048] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0049] In the following specific implementation,

[0050] The raw material was melted at 1450℃, poured into a mold, water-quenched and solution-treated at 830℃ for 1.0 h, hot-rolled at 930℃ with a deformation of 75%, cold-rolled with a deformation of 70%, held at 750℃ for 110 min, and held at 650℃ for 120 min to obtain the nickel-based material.

[0051] In Examples 1-3, the nickel-based material comprises the following components by mass percentage: 0.04% Mg, 15% Cr, 0.08% Y, 1.0% Cu, with the remainder being Ni;

[0052] Carboxylated carbon nanotubes, with an inner diameter of 10-20 nm, a tube length of 5-15 μm, and a purity >99.5%;

[0053] Branched polyethyleneimine, with a molecular weight of 25,000, was sourced from Wuhan Kemic Biomedical Technology Co., Ltd.

[0054] The initiator is 2-hydroxy-2-methyl-1-phenylpropanone;

[0055] Polyethylene glycol, average molecular weight 2000;

[0056] Graphene oxide, with a diameter of 0.5~3μm, a thickness of 0.55~1.2nm, and a purity of >99%.

[0057] Example 1: A method for preparing a high heat dissipation nickel-based composite material, comprising the following processes:

[0058] (1) Preparation of mercapto-terminated polyurethane:

[0059] S1: Carboxylated carbon nanotubes, branched polyethyleneimine, and deionized water are mixed and heated under reflux. After the reaction, the mixture is filtered, washed, and freeze-dried to obtain aminated carbon nanotubes. S2: Aminated carbon nanotubes, m-phenylenedimethyl isocyanate, and N-methylpyrrolidone are mixed, stirred evenly, and heated to react, yielding functionalized carbon nanotubes. S3: 4-fluorophenyl isocyanate, functionalized carbon nanotubes, polyethylene glycol, and dibutyltin dilaurate are mixed and heated to react, yielding a polyurethane prepolymer. Trimethylolpropane tris(3-mercaptopropionic acid) ester is then added, and the mixture is heated to react. After the reaction, the temperature is lowered to 60°C, and the pH is adjusted to 8.0 to obtain mercapto-terminated polyurethane. In S1, carboxylated carbon nanotubes, branched polyethyleneimine, and... The mass ratio of deionized water is 1:5:15; in S1, the process conditions for the reflux reaction are: temperature 120℃, time 12h; in S2, the mass ratio of aminated carbon nanotubes, m-phenylenedimethyl isocyanate, and N-methylpyrrolidone is 1:6:1; in S2, the process conditions for the heating reaction are: temperature 45℃, time 2.0h; in S3, the mass ratio of 4-fluorophenyl isocyanate, functionalized carbon nanotubes, polyethylene glycol, dibutyltin dilaurate, and trimethylolpropane tris(3-mercaptopropionic acid) ester is 2:1.0:2.0:0.005:2.6; in S3, the process conditions for the heating reaction are: temperature 80℃, time 4.5h; the process conditions for the temperature-increasing reaction are: temperature 95℃, time 3h.

[0060] (2) Preparation of double bond modified graphene:

[0061] Step A: Triethoxysilane, xylene, catalyst, and tetraethylenesilane are mixed and heated to obtain a double-bonded siloxane. Step B: Graphene oxide, the double-bonded siloxane, an aqueous ethanol solution, and citric acid are mixed, ultrasonically dispersed, heated, filtered, and washed to obtain double-bonded modified graphene. In Step A, the mass ratio of triethoxysilane, xylene, catalyst, and tetraethylenesilane is 6:10:0.008:8; the catalyst is a Castrol catalyst. In Step A, the heating reaction conditions are: temperature 100℃, time 10h. In Step B, the mass ratio of graphene oxide, the double-bonded siloxane, the aqueous ethanol solution, and citric acid is 1:1.5:6:0.1; the aqueous ethanol solution has a mass fraction of 50%. In Step B, the ultrasonic dispersion conditions are: frequency 80kHz, time 30min. In Step B, the heating reaction conditions are: temperature 75℃, time 7h.

[0062] (3) Preparation of high heat dissipation nickel-based composite materials:

[0063] Step 1: Mix mercapto-terminated polyurethane, double-bond modified graphene, and 2-hydroxy-2-methyl-1-phenylpropanone, and stir until homogeneous to obtain a high-strength heat-dissipating coating; Step 2: Heat nickel-based material to 500℃, pass hydrogen and argon gas at a flow ratio of 1:1, and perform vapor deposition using solid borane ammonia to form a boron nitride high thermal conductivity layer. Then, uniformly coat the layer with the high-strength heat-dissipating coating and subject it to ultraviolet irradiation to form a high-strength heat-dissipating coating, thus obtaining a high-heat-dissipating nickel-based composite material; In Step 1... The mass ratio of mercapto-terminated polyurethane, double-bond modified graphene, and 2-hydroxy-2-methyl-1-phenylpropanone is 10:2.5:0.6; in step 2, the deposition thickness of the boron nitride high thermal conductivity layer is 60 μm; in step 2, the thickness of the high-strength heat dissipation coating is 20 μm; in step 2, the vapor phase deposition process conditions are: temperature 110℃, time 35 min, power 30 W; in step 2, the ultraviolet irradiation process conditions are: irradiation power 200 mW / cm². 2 Irradiation time: 30 minutes.

[0064] Example 2: A method for preparing a high heat dissipation nickel-based composite material, comprising the following processes:

[0065] (1) Preparation of mercapto-terminated polyurethane:

[0066] S1: Carboxylated carbon nanotubes, branched polyethyleneimine, and deionized water are mixed and heated under reflux. After the reaction, the mixture is filtered, washed, and freeze-dried to obtain aminated carbon nanotubes. S2: Aminated carbon nanotubes, m-phenylenediamine isocyanate, and N-methylpyrrolidone are mixed, stirred evenly, and heated to react, yielding functionalized carbon nanotubes. S3: 4-fluorophenyl isocyanate, functionalized carbon nanotubes, polyethylene glycol, and dibutyltin dilaurate are mixed and heated to react, yielding a polyurethane prepolymer. Trimethylolpropane tris(3-mercaptopropionic acid) ester is then added, and the mixture is heated to react. After the reaction, the temperature is lowered to 55°C, and the pH is adjusted to 7.5 to obtain mercapto-terminated polyurethane. In S1, carboxylated carbon nanotubes, branched polyethyleneimine, and deionized water are mixed and heated under reflux. After the reaction, the mixture is filtered, washed, and freeze-dried to obtain aminated carbon nanotubes. The mass ratio of deionized water is 1:3:12; in S1, the process conditions for the reflux reaction are: temperature 115℃, time 11h; in S2, the mass ratio of aminated carbon nanotubes, m-phenylenedimethyl isocyanate, and N-methylpyrrolidone is 1:5:1; in S2, the process conditions for the heating reaction are: temperature 40℃, time 1.8h; in S3, the mass ratio of 4-fluorophenyl isocyanate, functionalized carbon nanotubes, polyethylene glycol, dibutyltin dilaurate, and trimethylolpropane tris(3-mercaptopropionic acid) is 2:0.8:1.8:0.004:2.5; in S3, the process conditions for the heating reaction are: temperature 75℃, time 4.0h; the process conditions for the temperature-increasing reaction are: temperature 90℃, time 2.5h.

[0067] (2) Preparation of double bond modified graphene:

[0068] Step A: Triethoxysilane, xylene, catalyst, and tetraethylenesilane are mixed and heated to obtain a double-bonded siloxane. Step B: Graphene oxide, the double-bonded siloxane, an aqueous ethanol solution, and citric acid are mixed, ultrasonically dispersed, heated, filtered, and washed to obtain double-bonded modified graphene. In Step A, the mass ratio of triethoxysilane, xylene, catalyst, and tetraethylenesilane is 6:9:0.007:7; the catalyst is a Castrol catalyst. In Step A, the heating reaction conditions are: temperature 95℃, time 9h. In Step B, the mass ratio of graphene oxide, the double-bonded siloxane, the aqueous ethanol solution, and citric acid is 1:1.0:5:0.08; the aqueous ethanol solution has a mass fraction of 50%. In Step B, the ultrasonic dispersion conditions are: frequency 70kHz, time 25min. In Step B, the heating reaction conditions are: temperature 70℃, time 6h.

[0069] (3) Preparation of high heat dissipation nickel-based composite materials:

[0070] Step 1: Mix mercapto-terminated polyurethane, double-bond modified graphene, and 2-hydroxy-2-methyl-1-phenylpropanone, and stir until homogeneous to obtain a high-strength heat-dissipating coating; Step 2: Heat nickel-based material to 400℃, pass hydrogen and argon gas at a flow ratio of 1:1, and perform vapor deposition using solid borane ammonia to form a boron nitride high thermal conductivity layer. Then, uniformly coat the layer with the high-strength heat-dissipating coating and subject it to ultraviolet irradiation to form a high-strength heat-dissipating coating, thus obtaining a high-heat-dissipating nickel-based composite material; In Step 1... The mass ratio of mercapto-terminated polyurethane, double-bond modified graphene, and 2-hydroxy-2-methyl-1-phenylpropanone is 10:2.0:0.4; in step 2, the deposition thickness of the boron nitride high thermal conductivity layer is 50 μm; in step 2, the thickness of the high-strength heat dissipation coating is 15 μm; in step 2, the vapor deposition process conditions are: temperature 105℃, time 30 min, power 28 W; in step 2, the ultraviolet irradiation process conditions are: irradiation power 150 mW / cm². 2 Irradiation time: 25 minutes.

[0071] Example 3: A method for preparing a high heat dissipation nickel-based composite material, comprising the following processes:

[0072] (1) Preparation of mercapto-terminated polyurethane:

[0073] S1: Carboxylated carbon nanotubes, branched polyethyleneimine, and deionized water are mixed and heated under reflux. After the reaction, the mixture is filtered, washed, and freeze-dried to obtain aminated carbon nanotubes. S2: Aminated carbon nanotubes, m-phenylenedimethyl isocyanate, and N-methylpyrrolidone are mixed, stirred evenly, and heated to react, yielding functionalized carbon nanotubes. S3: 4-fluorophenyl isocyanate, functionalized carbon nanotubes, polyethylene glycol, and dibutyltin dilaurate are mixed and heated to react, yielding a polyurethane prepolymer. Trimethylolpropane tris(3-mercaptopropionic acid) ester is then added, and the mixture is heated to react. After the reaction, the temperature is lowered to 50°C, and the pH is adjusted to 7.0 to obtain mercapto-terminated polyurethane. In S1, carboxylated carbon nanotubes, branched polyethyleneimine, and... The mass ratio of deionized water is 1:1:10; in S1, the process conditions for the reflux reaction are: temperature 110℃, time 10h; in S2, the mass ratio of aminated carbon nanotubes, m-phenylenedimethyl isocyanate, and N-methylpyrrolidone is 1:4:1; in S2, the process conditions for the heating reaction are: temperature 35℃, time 1.6h; in S3, the mass ratio of 4-fluorophenyl isocyanate, functionalized carbon nanotubes, polyethylene glycol, dibutyltin dilaurate, and trimethylolpropane tris(3-mercaptopropionic acid) is 2:0.6:1.6:0.003:2.4; in S3, the process conditions for the heating reaction are: temperature 70℃, time 3.5h; the process conditions for the temperature-increasing reaction are: temperature 85℃, time 2h.

[0074] (2) Preparation of double bond modified graphene:

[0075] Step A: Triethoxysilane, xylene, catalyst, and tetraethylenesilane are mixed and heated to obtain a double-bonded siloxane. Step B: Graphene oxide, the double-bonded siloxane, an aqueous ethanol solution, and citric acid are mixed, ultrasonically dispersed, heated, filtered, and washed to obtain double-bonded modified graphene. In Step A, the mass ratio of triethoxysilane, xylene, catalyst, and tetraethylenesilane is 6:8:0.006:6; the catalyst is a Castrol catalyst. In Step A, the heating reaction conditions are: temperature 90℃, time 8h. In Step B, the mass ratio of graphene oxide, the double-bonded siloxane, the aqueous ethanol solution, and citric acid is 1:0.5:4:0.05; the aqueous ethanol solution has a mass fraction of 50%. In Step B, the ultrasonic dispersion conditions are: frequency 60kHz, time 20min. In Step B, the heating reaction conditions are: temperature 65℃, time 5h.

[0076] (3) Preparation of high heat dissipation nickel-based composite materials:

[0077] Step 1: Mix mercapto-terminated polyurethane, double-bond modified graphene, and 2-hydroxy-2-methyl-1-phenylpropanone, and stir until homogeneous to obtain a high-strength heat-dissipating coating; Step 2: Heat nickel-based material to 300℃, pass hydrogen and argon gas at a flow ratio of 1:1, and perform vapor deposition using solid borane ammonia to form a boron nitride high thermal conductivity layer. Then, uniformly coat the layer with the high-strength heat-dissipating coating and subject it to ultraviolet irradiation to form a high-strength heat-dissipating coating, thus obtaining a high-heat-dissipating nickel-based composite material; In Step 1... The mass ratio of mercapto-terminated polyurethane, double-bond modified graphene, and 2-hydroxy-2-methyl-1-phenylpropanone is 10:1.5:0.2; in step 2, the deposition thickness of the boron nitride high thermal conductivity layer is 40 μm; in step 2, the thickness of the high-strength heat dissipation coating is 10 μm; in step 2, the vapor phase deposition process conditions are: temperature 100℃, time 25 min, power 25; in step 2, the ultraviolet irradiation process conditions are: irradiation power 100 mW / cm². 2 Irradiation time: 20 minutes.

[0078] Comparative Example 1: Compared with Example 1, the functionalized carbon nanotubes were replaced with carbon nanotubes, while the other conditions remained unchanged.

[0079] Comparative Example 2: Compared with Example 1, the double-bonded siloxane was replaced with vinyltrimethoxysilane, while the other conditions remained unchanged.

[0080] Comparative Example 3: Compared with Example 1, no iron was added to the nickel-based material, and all other conditions remained the same.

[0081] Comparative Example 4: Compared with Example 1, no high thermal conductivity boron nitride layer was deposited on the nickel-based material, while all other conditions remained the same.

[0082] Comparative Example 5: Compared with Example 1, no high thermal conductivity boron nitride layer was deposited on the nickel-based material, and no high-strength heat dissipation coating was applied, while other conditions remained unchanged.

[0083] Experiment: The high heat dissipation nickel-based composite materials obtained in the examples and comparative examples were subjected to various performance tests.

[0084] Mechanical property testing: The tensile rate was 2 mm / min, tested using an electronic universal testing machine.

[0085] Thermal conductivity: The thermal conductivity of high heat dissipation nickel-based composite materials was tested according to ASTM D5470.

[0086] Corrosion resistance test: Three-electrode electrochemical corrosion detection was adopted, with high heat dissipation nickel-based composite material as the test electrode, graphite as the auxiliary electrode, saturated calomel as the reference electrode, and neutral 3.5wt% sodium chloride aqueous solution as the medium. The scanning range was -2~2V and the rate was 100mV / s.

[0087] Thermal expansion coefficient test: The thermal expansion coefficient of nickel-based composite materials was tested using a NETZSCHDIL420C thermal expansion coefficient tester.

[0088] The table below shows the test results of the mechanical properties and thermal conductivity of high heat dissipation nickel-based composite materials;

[0089]

[0090] The table below shows the test results of corrosion resistance and thermal expansion coefficient of high heat dissipation nickel-based composite materials;

[0091]

[0092] Based on the data in the table above, the following conclusions can be drawn:

[0093] Compared with Comparative Examples 1-4, the high heat dissipation nickel-based composite materials in Examples 1-3 have superior mechanical properties, thermal conductivity, corrosion resistance, and low coefficient of thermal expansion. Comparative Example 1 replaced functionalized carbon nanotubes with carbon nanotubes, and Comparative Example 2 replaced double-bonded siloxanes with vinyltrimethoxysilanes. Comparative Example 3 did not add iron to the nickel-based material. Comparative Example 4 did not deposit a high thermal conductivity boron nitride layer on the nickel-based material. The mechanical properties, thermal conductivity, corrosion resistance, and coefficient of thermal expansion all deteriorated to varying degrees. According to Comparative Example 5, in this application, the selection of nickel-based materials and the setting of high-strength heat dissipation coating components can promote the improvement of various properties of the prepared high heat dissipation nickel-based composite material.

[0094] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A preparation method of high heat dissipation nickel-based composite material, comprising the following processes: Step 1, taking mercapto-terminated polyurethane, double bond modified graphene and initiator, stirring uniformly to obtain high-strength heat dissipation coating; Step 2, taking nickel-based material, heating to 300-500℃, passing hydrogen and argon at a flow ratio of 1:1, using solid borane ammonia for vapor deposition to form boron nitride high-thermal-conductivity layer, then uniformly coating high-strength heat dissipation coating, and performing ultraviolet irradiation to form high-strength heat dissipation coating layer, thereby obtaining high heat dissipation nickel-based composite material; the nickel-based material comprises the following components: 0.03-0.05% Mg, 10-20% Cr, 0.06-0.10% Y, 0.6-1.2% Cu, and the balance of Ni; in Step 1, the initiator is 2-hydroxy-2-methyl-1-phenylpropanone; in Step 1, the double bond modified graphene is prepared by the following process: Step A, mixing triethoxysilane, dimethylbenzene, catalyst and tetraethylenesilane, heating to react to obtain double bond containing siloxane; Step B, mixing graphene oxide, double bond containing siloxane, ethanol aqueous solution and citric acid, ultrasonic dispersion, heating to react, and then filtering, washing and freeze-drying to obtain double bond modified graphene; in Step 1, the mercapto-terminated polyurethane is prepared by the following process: S1, mixing carboxylated carbon nanotube, branched polyethyleneimine and deionized water, heating to reflux to react, filtering, washing and freeze-drying after the reaction to obtain aminated carbon nanotube; S2, mixing aminated carbon nanotube, m-xylylene isocyanate and N-methylpyrrolidone, stirring uniformly, heating to react to obtain functionalized carbon nanotube; S3, mixing 4-fluorophenyl isocyanate, functionalized carbon nanotube, polyethylene glycol, dibutyltin dilaurate, heating to react to obtain polyurethane prepolymer, then adding trimethylolpropane tris(3-mercaptopropionate), heating to react, cooling to 50-60℃ after the reaction, adjusting pH to 7.0-8.0 to obtain mercapto-terminated polyurethane; in Step 1, the mass ratio of mercapto-terminated polyurethane, double bond modified graphene and initiator is 10:(1.5-2.5):(0.2-0.6); in S1, the mass ratio of carboxylated carbon nanotube, branched polyethyleneimine and deionized water is 1:(1-5):(10-15); in S2, the mass ratio of aminated carbon nanotube, m-xylylene isocyanate and N-methylpyrrolidone is 1:(4-6):1; in S3, the mass ratio of 4-fluorophenyl isocyanate, functionalized carbon nanotube, polyethylene glycol, dibutyltin dilaurate and trimethylolpropane tris(3-mercaptopropionate) is 2:(0.6-1.0):(1.6-2.0):(0.003-0.005):(2.4-2.6); in Step A, the mass ratio of triethoxysilane, dimethylbenzene, catalyst and tetraethylenesilane is 6:(8-10):(0.006-0.008):(6-8); in Step A, the catalyst is Kast catalyst. ​ ​ ​ ​ ​ ​ ​ 2. The method of claim 1, wherein the high heat dissipation nickel-based composite material is prepared by the following steps. ​ ​ ​ ​ 3. The method for preparing a high heat dissipation nickel-based composite material according to claim 1, characterized in that: ​ 4. The method of claim 2, wherein the high heat dissipation nickel-based composite material is prepared by the following steps of: ​ ​ 5. A method for preparing a high heat dissipation nickel-based composite material according to claim 2, characterized in that: ​ 6. The method of claim 2, wherein the high heat dissipation nickel-based composite material is prepared by the following steps of: ​ ​ 7. The method of claim 1 wherein the high heat dissipation nickel-based composite material is prepared by the steps of: ​ ​ ​ 8. The method of claim 1 wherein the high heat dissipation nickel-based composite material is prepared by the steps of: The mass ratio of graphene oxide, double bond-containing siloxane, aqueous ethanol solution, and citric acid in step B is 1:(0.5-1.5):(4-6):(0.05-0.1). ​ 9. A high heat dissipation nickel-based composite material, characterized in that: The preparation method according to any one of claims 1-8.

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