Silicon carbide-diamond composite powder for 3D printing and preparation method and application thereof

Abstract

The application discloses a kind of 3D printing with silicon carbide-diamond composite powder and its preparation method and application, belong to advanced ceramic material technical field.The application first mixes diamond with phenolic resin solution, stirs uniformly under low-speed condition for a long time, is heated into paste, further vacuum heating is obtained, and diamond coated with phenolic resin is obtained;Then, according to the proportion, silicon carbide is mixed with diamond coated with phenolic resin, the obtained mixture is further homogenized, and the 3D printing with silicon carbide-diamond composite powder is obtained.The silicon carbide-diamond composite powder prepared by the application can meet the requirements of binder jet printing, and the complex shape, densified silicon carbide-diamond composite material parts are obtained by using liquid silicon infiltration at low temperature.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of advanced ceramic materials, and particularly relates to a silicon carbide-diamond composite powder for 3D printing and a preparation method and application thereof. BACKGROUND

[0002] SiC (silicon carbide) ceramics still maintain excellent thermal stability, corrosion resistance, thermal conductivity and wear resistance in harsh environments, and can be used as heat exchangers, sealing rings and the like, and are widely used in metallurgical, electric power, mechanical and other industrial fields. The large band gap, high breakdown voltage, excellent thermal conductivity and thermal expansion performance of silicon carbide can greatly improve the power and use efficiency of devices, and are also very suitable for use as electronic packaging heat dissipation materials. The density and thermal expansion coefficient of diamond and silicon carbide are close, and the semiconductor performance is excellent, and both have cubic crystal type. The diamond / silicon carbide composite material obtained by combining silicon carbide and diamond has ultra-high hardness and specific stiffness, and at the same time has excellent thermal conductivity, wear resistance and the like, and is expected to be used as electronic packaging materials in the thermal management field, as semiconductor wafer chucks, high-stability optical substrates and high-speed laser scanning mirrors for high-power lasers in the optical component field, and is considered to be one of the new generation of high-performance special ceramic matrix composites with great development potential.

[0003] At present, most of the researches on the preparation of silicon carbide-diamond composite materials adopt diamond as raw material, add binders, carbon sources (graphite) and the like, and generate silicon carbide through the reaction between carbon and silicon by gas phase or liquid phase silicon infiltration method, and combine with diamond to generate diamond-silicon carbide composite material: How new wave (CN 110698202B) adopts diamond particles as raw material, mixes graphite, silicon powder and binder to obtain a mixture; then performs laser selective sintering treatment on the obtained mixture to obtain a green body; and then performs infiltration treatment on the green body in a vacuum environment to obtain a dense diamond / silicon carbide composite material. Although the material prepared by this method has the characteristics of high thermal conductivity, the raw material mainly adopts diamond, and the content of the binder is high (20-60wt%), which causes a long degumming time (15h-25h); Huang Yihua (CN 116143542A) adopts diamond micro powder coated with a silicon carbide layer, silicon carbide powder, carbon black, silicon powder and binder to perform die pressing to obtain a diamond combined silicon carbide composite ceramic after silicon infiltration treatment. However, the diamond surface needs to be pre-coated with silicon carbide, the preparation cost is high, and die pressing cannot be used to prepare parts with complex shapes.

[0004] Based on the above reasons, the present application is proposed. SUMMARY

[0005] Based on the above reasons, in view of the problems or defects in the prior art, the purpose of the present application is to provide a silicon carbide-diamond composite powder for 3D printing and a preparation method and application thereof, to solve or at least partially solve the above technical defects in the prior art: the silicon carbide-diamond composite powder prepared by the present application can meet the requirements of binder jet printing, and the complex-shaped, densified silicon carbide-diamond composite material parts are obtained by using liquid silicon infiltration at low temperature.

[0006] In order to achieve one of the above purposes of the present application, the technical solution adopted by the present application is as follows:

[0007] A preparation method of a silicon carbide-diamond composite powder for 3D printing, the method specifically comprises the following steps:

[0008] (1) mixing diamond with phenolic resin solution, then stirring uniformly under low speed for a long time, heating to paste, and further vacuum heating to obtain phenolic resin coated diamond;

[0009] (2) mixing silicon carbide with the phenolic resin coated diamond of step (1) according to the proportion, then further homogenizing the obtained mixture to obtain the silicon carbide-diamond composite powder for 3D printing.

[0010] Further, in step (1) of the above technical solution, the particle size of the diamond ranges from 10 to 100 microns.

[0011] Further, in step (1) of the above technical solution, the amount of phenolic resin added is 10-30% of the mass of diamond. In the preferred embodiment of the present application, the phenolic resin is added in the form of a phenolic resin solution.

[0012] Preferably, in the above technical solution, the phenolic resin solution is composed of phenolic resin and organic alcohol solvent, and the organic alcohol solvent can be any one of anhydrous methanol, anhydrous ethanol or anhydrous isopropyl alcohol, etc. In the preferred embodiment of the present application, the organic alcohol solvent is anhydrous ethanol.

[0013] Specifically, in the above technical solution, the amount ratio of phenolic resin and organic alcohol solvent can not be specifically limited, as long as it can achieve complete and uniform dissolution of phenolic resin, for example, the volume ratio of phenolic resin and organic alcohol solvent can be 1:(1-5). In the preferred embodiment of the present application, the volume ratio of phenolic resin and organic alcohol solvent is 1:1.

[0014] Further, in the step (1) of the above technical solution, the low speed refers to a stirring speed of 100-1000 revolutions per minute; in the preferred embodiment of the present application, the stirring speed is lower than 600 revolutions per minute, for example, it can be 550 revolutions per minute, 500 revolutions per minute, 400 revolutions per minute, 200 revolutions per minute, 50 revolutions per minute, etc.

[0015] Further, in the step (1) of the above technical solution, the long-time stirring refers to a stirring time of 6-12 hours, and in the preferred embodiment of the present application, the stirring time is 6 hours.

[0016] Further, in the step (1) of the above technical solution, the temperature of the first heating is 40-70℃. The purpose of the heating is to concentrate the mixed system into a paste. The temperature of the second heating under vacuum condition is 40-70℃, and the purpose of this heating is to completely volatilize the organic alcohol solvent in the mixed system.

[0017] Further, in the step (2) of the above technical solution, the particle size of the silicon carbide is 5-100 microns, and a single particle size can be used or several particle sizes can be mixed.

[0018] Further, in the step (2) of the above technical solution, the use amount of the silicon carbide and the phenolic resin coated diamond is as follows:

[0019] Silicon carbide 80-20wt%

[0020] Phenolic resin coated diamond 80-20wt%.

[0021] Preferably, in the above technical solution, the sum of the use amount of the diamond in the silicon carbide and the phenolic resin coated diamond is 100wt%.

[0022] Further, in the step (2) of the above technical solution, in the preferred embodiment of the present application, the mixing method of the silicon carbide and the phenolic resin coated diamond is carried out in a jar mill, and the mixing time is not less than 6 hours, for example, the mixing time can be 6 hours, 8 hours, 10 hours, 12 hours, etc., so as to realize the complete and uniform mixing of the silicon carbide and the phenolic resin coated diamond.

[0023] The second object of the present application is to provide a 3D printing silicon carbide-diamond composite powder prepared by the above method.

[0024] The third object of the present application is to provide the application of the 3D printing silicon carbide-diamond composite powder prepared by the above method in the preparation of a densified silicon carbide-diamond composite material part by jet printing, in particular, in the preparation of a complex-shaped and densified silicon carbide-diamond composite material part.

[0025] A kind of densification silicon carbide-diamond composite material parts, using the above-mentioned silicon carbide-diamond composite powder is prepared by jet printing, the specific preparation method is as follows:

[0026] The silicon carbide-diamond composite powder is obtained by binder jet printing, then the green body is heated and degreased under vacuum conditions to obtain a degreased green body;The degreased green body is placed in a vacuum sintering furnace, silicon powder is added, and silicon is infiltrated under constant temperature conditions of 1480-1560 ℃ to obtain a densified silicon carbide-diamond composite material part.

[0027] Specifically, the above technical solution, silicon is infiltrated under constant temperature conditions of 1480-1560 ℃, because the melting point of silicon is 1430 ℃, in the temperature range of 1480-1560 ℃, silicon becomes liquid phase, reacts with carbon in the system to generate silicon carbide, the newly generated silicon carbide is combined with the original carbon in the green body, and the liquid silicon fills the remaining pores between the silicon carbide and diamond particles, thereby obtaining a dense sintered body. Too high temperature will make silicon gasify a lot.

[0028] Further, in the above technical solution, the binder uses thermosetting phenolic resin or furan resin.

[0029] Further, in the above technical solution, the amount of binder jetting is 5-15% of the mass of silicon carbide-diamond composite powder.

[0030] Further, in the above technical solution, when the binder uses thermosetting phenolic resin, the degreasing temperature is 900-1100 ℃;When the binder uses furan resin, the degreasing temperature is 1000-1100 ℃. In the preferred embodiment of the present application, the degreasing temperature is 1050 ℃, so that the phenolic resin or furan resin can be completely cracked.

[0031] Further, in the above technical solution, the degreasing time is 1-3 hours. In the preferred embodiment of the present application, the degreasing time is 2 hours.

[0032] Further, in the above technical solution, the mass ratio of silicon powder to silicon carbide-diamond composite powder is 1.2-1.5:1.

[0033] Further, in the above technical solution, the vacuum degree in the vacuum sintering furnace is less than or equal to 10 Pa.

[0034] The role of each raw material used in the above preparation method of the present application is as follows:

[0035] Phenolic resin: Phenolic resin in the present application is used as part of carbon source, and the phenolic resin can reduce the graphitization of diamond in the silicon infiltration process.

[0036] Thermosetting phenolic resin or furan resin for spraying: as a binder in the spraying process, it plays a role in bonding silicon carbide and diamond particles.

[0037] Silicon powder: two functions

[0038] 1) Provide silicon source for reaction with carbon source, and the following reaction occurs: Si (liquid) + C = SiC;

[0039] 2) At the silicon infiltration temperature, the silicon liquid phase enters the remaining pores between the silicon carbide and diamond particles to fill them, promoting densification.

[0040] Compared with the prior art, the present application has the following beneficial effects:

[0041] 1) The present application uses silicon carbide as the matrix and adds diamond, which greatly reduces the cost compared with using pure diamond to prepare silicon carbide-diamond materials.

[0042] 2) The organic phenolic resin content in the present application does not exceed 30wt% of the entire system material, which can greatly reduce the degumming time and reduce the preparation cost.

[0043] 3) The present application uses 3DP printing technology, which can realize the preparation of complex-shaped parts. BRIEF DESCRIPTION OF DRAWINGS

[0044] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiment or prior art description. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0045] Figure 1 Fig. 1 (a), (b) are the real photos of the green body prepared in application example 1 and the green body prepared in application example 2, respectively;

[0046] Figure 2 Fig. 2 (a), (b) are scanning electron microscope (SEM) pictures of the densified silicon carbide-diamond composite material parts prepared in application example 1 under different magnifications;

[0047] Figure 3 Fig. 3 (a), (b) are scanning electron microscope (SEM) pictures of the densified silicon carbide-diamond composite material parts prepared in application example 2 under different magnifications. DETAILED DESCRIPTION

[0048] To solve the problems in the prior art, the present application provides a silicon carbide composite diamond powder for 3D binder jet printing, which uses diamond coated with phenolic resin as raw material, then a green body with complex shape is prepared by 3D printing, and densification of the material is realized through liquid silicon infiltration process.

[0049] The application will be further described in detail through the following examples.

[0050] In order to better understand the present application without limiting the scope of the present application, all the numbers and other numerical values used in this application to express amount, percentage, and other values should be understood as being modified by the word "about" in all cases. Therefore, unless specifically stated otherwise, the numerical parameters set forth in the specification are approximations that can vary depending on different desired properties sought to be obtained. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0051] The phenolic resin used for coating diamond in the following examples of the present application is purchased from Henan Pluton Foundry Material Co., Ltd., with the product number of 2123#.

[0052] The binder thermosetting phenolic resin used in the following application examples of the present application is purchased from Gexing New Material (Shandong) Co., Ltd., with the product number of KPR-P-01.

[0053] The binder furan resin used in the following application examples of the present application is purchased from Gexing New Material (Shandong) Co., Ltd., with the product number of KPR-F-02.

[0054] The equipment and raw materials used in the present application can be purchased from the market or are commonly used in the art. The methods in the following examples are conventional methods in the art, unless otherwise specified.

[0055] Example 1

[0056] The method for preparing a silicon carbide-diamond composite powder for 3D printing of the present embodiment specifically comprises the following steps:

[0057] (1) 50 grams of diamond (particle size of 50 microns) is mixed with 10 grams of phenolic resin solution under low speed (less than 600 revolutions per minute) in a magnetic stirrer for 6 hours; then the obtained mixture is heated and stirred at 50 DEG C until it becomes paste; the obtained paste slurry is placed in a vacuum oven, heated at 60 DEG C under 0.7 Mpa vacuum until the ethanol is completely volatilized, to obtain diamond particles coated with phenolic resin; wherein the phenolic resin solution is prepared by mixing phenolic resin and anhydrous ethanol in a volume ratio of 1:1.

[0058] (2) 50 grams of silicon carbide (particle size of 74 microns) is mixed with all the phenolic resin coated diamond particles prepared in step (1) and transferred to a jar mill for further mixing for 12 hours to obtain a mixed system; the mixed system is further homogenized by a homogenizer to obtain the silicon carbide-diamond composite powder for 3D printing.

[0059] Example 2

[0060] The preparation method of a silicon carbide-diamond composite powder for 3D printing in this example specifically comprises the following steps:

[0061] (1) 35 grams of diamond (particle size of 100 microns) is mixed with 10 grams of phenolic resin solution under a magnetic stirrer (less than 600 rpm), stirred for 6 hours, and then the obtained mixture is stirred and heated at 50°C until it becomes paste. The obtained paste slurry is placed in a vacuum oven, heated at 60°C under 0.7 Mpa vacuum until the ethanol is completely volatilized to obtain phenolic resin coated diamond particles; wherein: the phenolic resin solution is prepared by phenolic resin and anhydrous ethanol in a volume ratio of 1:1.

[0062] (2) 65 grams of silicon carbide (particle size of 74 microns) is mixed with all the phenolic resin coated diamond particles prepared in step (1) and transferred to a jar mill for further mixing for 12 hours to obtain a mixed system; the mixed system is further homogenized by a homogenizer to obtain the silicon carbide-diamond composite powder for 3D printing.

[0063] Example 3

[0064] The preparation method of a silicon carbide-diamond composite powder for 3D printing in this example specifically comprises the following steps:

[0065] (1) 25 grams of diamond (particle size of 50 microns) is mixed with 10 grams of phenolic resin solution under a magnetic stirrer (less than 600 rpm), stirred for 6 hours, and then the obtained mixture is stirred and heated at 50°C until it becomes paste. The obtained paste slurry is placed in a vacuum oven, heated at 60°C under 0.7 Mpa vacuum until the ethanol is completely volatilized to obtain phenolic resin coated diamond particles; wherein: the phenolic resin solution is prepared by phenolic resin and anhydrous ethanol in a volume ratio of 1:1.

[0066] (2) 75 grams of silicon carbide (particle size of 74 microns) is mixed with all the phenolic resin coated diamond particles prepared in step (1) and transferred to a jar mill for further mixing for 12 hours to obtain a mixed system; the mixed system is further homogenized by a homogenizer to obtain the silicon carbide-diamond composite powder for 3D printing.

[0067] Example 4

[0068] The preparation method of the silicon carbide-diamond composite powder for 3D printing in the embodiment specifically comprises the following steps:

[0069] (1) 50 grams of diamond (particle size 50 microns) is mixed with 10 grams of phenolic resin solution, stirred for 6 hours under a magnetic stirrer (less than 600 rpm), and then the obtained mixture is heated and stirred at 50°C until it becomes paste. Then the obtained paste slurry is placed in a vacuum oven, heated at 60°C under 0.7 Mpa vacuum until the ethanol is completely volatilized, to obtain diamond particles coated with phenolic resin; wherein the phenolic resin solution is prepared by mixing phenolic resin and anhydrous ethanol at a volume ratio of 1:1.

[0070] (2) 50 grams of silicon carbide (mixed with silicon carbide of particle size 74 microns and silicon carbide of particle size 50 microns at a mass ratio of 6:4) is mixed with all the diamond particles coated with phenolic resin prepared in step (1), and then transferred to a jar mill for further mixing for 12 hours to obtain a mixed system; the mixed system is further homogenized by a homogenizer to obtain the silicon carbide-diamond composite powder for 3D printing.

[0071] Comparative Example 1

[0072] The preparation method of the silicon carbide powder in the present comparative example specifically comprises the following steps:

[0073] 100 grams of silicon carbide (particle size 74 microns) is mixed with 10 grams of phenolic resin solution, stirred for 6 hours under a magnetic stirrer, and then the obtained mixture is heated and stirred at 50°C until it becomes paste. Then the obtained paste slurry is placed in a vacuum oven, heated at 60°C under 0.7 Mpa vacuum until the ethanol is completely volatilized, to obtain the silicon carbide powder; wherein the phenolic resin solution is prepared by mixing phenolic resin and anhydrous ethanol at a volume ratio of 1:1.

[0074] Application Example 1

[0075] The dense silicon carbide-diamond composite material part in the present application example is prepared by jet printing using the silicon carbide-diamond composite powder described in the above Example 1, and the specific preparation method is as follows:

[0076] The silicon carbide-diamond composite powder prepared in Example 1 is jet printed using a binder thermosetting phenolic resin to obtain a green body; the obtained green body is degreased at 1050°C for 2 hours under vacuum, and then the degreased green body is placed in a vacuum sintering furnace, 1.2 times of silicon powder is added, and silicon infiltration is carried out at 10 Pa and 1560°C for 1 hour to obtain the dense silicon carbide-diamond composite material part.

[0077] Application Example 2

[0078] A densified silicon carbide-diamond composite material part of the application example is prepared by spray printing the silicon carbide-diamond composite powder of the above-mentioned example 2, and the specific preparation method is as follows:

[0079] The silicon carbide-diamond composite powder prepared in example 2 is spray printed to obtain a green body by using a binder of thermosetting phenolic resin; the obtained green body is vacuum degreased at 1050℃ for 2 hours, and the degreased green body is placed into a vacuum sintering furnace, 1.2 times of silicon powder is added, silicon infiltration is carried out at 10Pa and 1560℃ for 1 hour, and a densified silicon carbide-diamond composite material part is obtained.

[0080] Application example 3

[0081] A densified silicon carbide-diamond composite material part of the application example is prepared by spray printing the silicon carbide-diamond composite powder of the above-mentioned example 3, and the specific preparation method is as follows:

[0082] The silicon carbide-diamond composite powder prepared in example 3 is spray printed to obtain a green body by using a binder of furan resin; the obtained green body is vacuum degreased at 1050℃ for 2 hours, and the degreased green body is placed into a vacuum sintering furnace, 1.2 times of silicon powder is added, silicon infiltration is carried out at 10Pa and 1560℃ for 1 hour, and a densified silicon carbide-diamond composite material part is obtained.

[0083] Application example 4

[0084] A densified silicon carbide-diamond composite material part of the application example is prepared by spray printing the silicon carbide-diamond composite powder of the above-mentioned example 4, and the specific preparation method is as follows:

[0085] The silicon carbide-diamond composite powder prepared in example 4 is spray printed to obtain a green body by using a binder of thermosetting phenolic resin; the green body is vacuum degreased at 1050℃ for 2 hours, and the degreased green body is placed into a vacuum sintering furnace, 1.5 times of silicon powder is added, silicon infiltration is carried out at 10Pa and 1560℃ for 1 hour, and a densified silicon carbide-diamond composite material part is obtained.

[0086] Comparative application example 1

[0087] A silicon carbide ceramic part of the comparative application example is prepared by spray printing the silicon carbide powder of the above-mentioned comparative example 1, and the specific preparation method is as follows:

[0088] The green body was prepared by using the silicon carbide powder prepared in the Comparative Example 1 and a binder jet printing; the green body was vacuum degreased at 1050℃ for 2 hours, and then was put into a vacuum sintering furnace, 1.2 times of silicon powder was added, and silicon infiltration was carried out at 10 Pa and 1560℃ for 1 hour to obtain a silicon carbide ceramic part.

[0089] Structure and performance test

[0090] Table 1 Performance comparison table of the parts prepared in the application examples 1-4 and the reaction silicon infiltration silicon carbide ceramic part prepared in the comparative application example 1

[0091]

[0092]

[0093] The test results in Table 1 show that the silicon carbide-diamond composite material part prepared in the application has high density and thermal conductivity, and has similar mechanical properties to the reaction silicon infiltration silicon carbide ceramic part (comparative application example 1), and can be used as a thermal management material.

[0094] The above shows and describes the basic principles and main features of the application and the advantages of the application. It should be understood by those skilled in the art that the application is not limited by the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the application. Without departing from the spirit and scope of the application, various changes and improvements can be made to the application, and these changes and improvements all fall within the scope of the claimed application. The scope of protection of the application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a densified silicon carbide-diamond composite material component, characterized in that: Silicon carbide-diamond composite powder for 3D printing is printed using a binder jet to obtain a green blank, which is then heated and debonded under vacuum conditions to obtain a debonded green blank; the debonded green blank is then placed in a vacuum sintering furnace, silicon powder is added, and siliconization is performed at a constant temperature of 1480-1560°C to obtain a densified silicon carbide-diamond composite component; the mass ratio of the silicon powder to the silicon carbide-diamond composite powder for 3D printing is 1.2-1.5:1; the binder is a thermosetting phenolic resin or furan resin; the amount of the binder jetted is 5-15% of the mass of the silicon carbide-diamond composite powder for 3D printing; and the debonding time is 1-3 hours; The silicon carbide-diamond composite powder for 3D printing is prepared by the following method: (1) diamonds are mixed with a phenolic resin solution, and then stirred for a long time at a low speed to mix, heated to a paste, and further heated in a vacuum to obtain phenolic resin-coated diamonds; the diamond particle size range is 10-100 microns; the amount of phenolic resin added is 10-30% of the mass of the diamond; (2) Silicon carbide and the phenolic resin-coated diamonds of step (1) are mixed in a proportion, and the resulting mixture is further homogenized to obtain the silicon carbide-diamond composite powder for 3D printing; the particle size of the silicon carbide is 5-100 μm.

2. The method for preparing a densified silicon carbide-diamond composite material component according to claim 1, characterized in that: In step (1), the low speed refers to a stirring speed of 100-1000 rpm; the long stirring refers to a stirring time of 6-12 hours.

3. The method for preparing a densified silicon carbide-diamond composite material component according to claim 1, characterized in that: In step (2), the amounts of silicon carbide and phenolic resin-coated diamond are as follows: Silicon carbide 80-20wt% Phenolic resin coated diamond 80-20wt%.

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