CN112358299B - Ceramic substrate and 3D printing method thereof - Google Patents
Ceramic substrate and 3D printing method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature-resistant, high-heat-conductivity and electromagnetic wave-absorbing ceramic substrate product and a 3D printing method thereof, wherein the method comprises the following steps: preparing mixed ceramic powder required by 3D printing of the ceramic substrate; preparing ceramic slurry required by 3D printing of the ceramic substrate; and step three, 3D printing the ceramic substrate based on the digital model of the ceramic substrate. Compared with the traditional ceramic substrate, the ceramic substrate has the advantages of high temperature resistance, high heat conduction, electromagnetic wave absorption and the like. Compared with the traditional manufacturing method, the 3D printing method has the advantages of low cost, short period, complex shape forming and the like.
Description
Technical Field
The invention belongs to the technical field of 3D printing of ceramic materials, and particularly relates to a high-temperature-resistant, high-heat-conductivity and electromagnetic wave-absorbing ceramic substrate applied to the 5G field and a 3D printing method thereof.
Background
With the rapid development of 5G technology, more and more electronic devices supporting 5G communication are provided. However, the 5G technology has the advantages of faster data transmission speed, and the like, but correspondingly, there are some problems yet to be solved, one of which is that the power electronic device supporting the 5G technology faces a great heating problem during operation. The traditional substrate is generally printed with power electronic circuits or devices on a polymer matrix, and the polymer matrix has low melting point and poor heat dissipation, so that the problem of huge heat generation of power electronic devices caused by the rapid development of 5G technology in the future is difficult to meet.
One current solution is to use a high temperature resistant ceramic substrate, such as zirconia ceramic material, alumina ceramic material, etc. Although zirconia ceramic materials and alumina ceramic materials have good heat resistance, the thermal conductivity is low, and the heat dissipation efficiency is low, so that high thermal conductivity material systems represented by aluminum nitride (AlN) ceramic materials and composite ceramic materials thereof are gradually increased, and the high thermal conductivity materials have wide application prospects in novel ceramic substrates.
However, the AlN ceramic substrate currently under development is too simple in structure, generally flat, and has not been designed for specific directional heat conduction. A large number of researches show that if the ceramic substrate is designed to conduct heat directionally, the heat dissipation effect of the ceramic substrate can be effectively improved. However, the ceramic substrate with the heat conduction design is generally in a complex shape, and the traditional preparation technology is difficult to realize.
In addition, the development of the 5G technology in the future requires that the electromagnetic interference between internal power electronic devices is minimized, and particularly, the ceramic substrate does not generate electromagnetic interference on the power electronic devices, so that the ceramic substrate is required to have good electromagnetic wave absorption performance, does not radiate heat to the outside, reflects electromagnetic signals, and minimizes the external interference. Therefore, for the ceramic substrate with a complex shape, high temperature resistance and high heat conductivity, the design problem of the electromagnetic wave absorbing structure needs to be considered.
Disclosure of Invention
In view of the above requirements, the present invention aims to provide a high temperature resistant, high thermal conductivity, electromagnetic wave absorbing ceramic substrate product and a 3D printing method thereof, which are used to solve the problems of limited high temperature resistance, low thermal conductivity, difficult preparation of complex shapes, large electromagnetic interference on electronic devices, etc. faced by the conventional ceramic substrate.
A3D printing method of a ceramic substrate comprises the following steps:
preparing mixed ceramic powder required by 3D printing of the ceramic substrate;
preparing ceramic slurry required by 3D printing of the ceramic substrate;
and step three, 3D printing the ceramic substrate based on the digital model of the ceramic substrate.
Further, the method also comprises the following steps:
step four, carrying out glue removal and degreasing on the ceramic substrate obtained in the step three; preferably, the content of this step includes:
heating the prepared ceramic substrate green body to 500-800 ℃ at a heating rate of 2-10 ℃/min in a nitrogen atmosphere, preferably at a nitrogen pressure of 1atm, and then preserving heat for 1-5 h to carry out glue removal and degreasing treatment, so as to ensure that the cured photosensitive resin in the green body is completely cracked and carbonized.
Further, the method also comprises the following steps:
step five, performing pressureless sintering on the degreased ceramic substrate in the step four; preferably, the content of this step includes:
and heating the ceramic substrate subjected to the binder removal and degreasing to 1700-2100 ℃ at a heating rate of 1-5 ℃/min in an argon atmosphere in a vacuum sintering furnace, and carrying out pressureless sintering after heat preservation for 0.5-2 h.
Further, the mixed ceramic powder of the first step comprises the following components in percentage by volume:
the AlN ceramic powder accounts for 80-90 vol%, the graphene accounts for 5-10 vol%, and the Michael alkene (MXene) accounts for 5-10 vol%.
Further, the concrete preparation steps of the mixed ceramic powder are as follows:
selecting AlN powder, graphene powder and MXene powder according to a ratio, weighing and mixing alcohol with the same volume, and performing ball milling treatment on a planetary ball mill at a preferred rotation speed of 300-400 r/min for 6-8 hours to obtain a suspension;
the suspension is preferably subjected to rotary evaporation drying for 3 to 6 hours at the temperature of between 70 and 90 ℃ and under the conditions of between 30 and 60r/min and between-0.04 and-0.09 MPa to obtain mixed ceramic powder;
the mixed ceramic powder is sieved, for example, through a 250-400 mesh sieve, to obtain a final mixed ceramic powder.
Further, in the second step, the ceramic slurry comprises the following components in percentage by volume:
the AlN-graphene-Michael alkene (MXene) mixed ceramic powder accounts for 40-55 vol%, the photosensitive resin accounts for 35-58 vol%, the dispersing agent accounts for 1-5 vol%, and the photoinitiator accounts for 1-5 vol%.
Further, the specific preparation steps of the ceramic slurry are as follows:
weighing the mixed ceramic powder, the photosensitive resin, the photoinitiator and the dispersant according to the volume, and then carrying out ball milling treatment on a planetary ball mill, wherein the preferred rotating speed is 300-400 r/min, and the ball milling time is 6-12 h, so as to obtain ceramic slurry meeting the requirements;
preferably, the photosensitive resin is prepared from two resin monomers of 1, 6-hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA) according to the weight ratio of (3-7): (7-3) a resin system mixed in a volume ratio;
the preferable dispersing agent is two dispersing agents of a dispersing agent 17000# and a dispersing agent 20000# according to the proportion of (2-8): (8-2) a dispersant system mixed in a volume ratio;
preferably, the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO).
Further, in the third step, 3D printing of the ceramic substrate is preferably performed by a photocuring 3D printing process; the method comprises the following steps:
importing the prepared digital model of the ceramic substrate into 3D printing equipment;
the light source wavelength of the photocuring 3D printing equipment is preferably 405-450 nm, and the light source intensity is 6000-10000 mu W/cm 2 The thickness of the 3D printing slicing layer is 25-100 mu m, and the exposure time of each layer is 5-30 s;
guiding the prepared ceramic slurry into a material groove of 3D printing equipment, and starting 3D printing to obtain a ceramic substrate;
preferably, the cleaning solution is placed in alcohol and cleaned by ultrasonic oscillation for 10-30 min.
A ceramic substrate produced by the 3D printing method according to any one of claims 1 to 8.
Furthermore, the ceramic substrate meets the requirements of temperature resistance (800-1600 ℃), heat conduction (directional heat conduction, heat conductivity 50-100W/mk) and electromagnetic wave absorption (3-30 GHz, -5-10 dB).
The invention has the following beneficial effects:
the ceramic substrate can meet the requirements of high temperature resistance, high heat conduction and electromagnetic wave absorption of 5G high-power electronic devices. The photocuring 3D printing forming precision is high, the structure with a complex shape can be realized, and the advanced manufacturing of a high-temperature-resistant, high-heat-conduction and electromagnetic wave-absorbing ceramic substrate structure can be met. Provides a feasible method for the design and manufacture of the high-temperature-resistant, high-heat-conductivity and electromagnetic wave-absorbing ceramic substrate and also provides a new idea for the application of 5G related ceramic materials and devices thereof in the manufacture.
The invention provides certain reference experience for 3D printing of the high-temperature-resistant, high-heat-conduction and electromagnetic wave-absorbing ceramic substrate applied to the 5G field.
Compared with the traditional ceramic substrate, the ceramic substrate has the advantages of high temperature resistance, high heat conduction, electromagnetic wave absorption and the like. Compared with the traditional manufacturing method, the 3D printing method has the advantages of low cost, short period, complex shape forming and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the embodiments will be described below with reference to the accompanying drawings. It is to be understood that the drawings in the following description are merely exemplary embodiments of the invention.
FIG. 1 is a flow chart of a 3D printing method of the present invention;
FIG. 2 is a three-dimensional model of a ceramic substrate according to the present invention.
Detailed Description
The invention is further described below with reference to the following figures and examples.
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
Example 1:
a high temperature resistant, high thermal conductivity, electromagnetic wave absorbing ceramic substrate product and a 3D printing method thereof, the process flow is shown in figure 1, and the method specifically comprises the following steps:
and (5) designing a substrate structure. The next generation of ceramic substrate is faced with the requirements of temperature resistance (1600 ℃), heat conduction (directional heat conduction, heat conductivity 80W/mk) and electromagnetic wave absorption (20-30 GHz and-5 dB), and based on the system parameters of silicon nitride, graphene and Macene (MXene) composite ceramic materials, the design of a high-temperature-resistant, high-heat-conduction and electromagnetic wave absorption structure is completed.
And establishing a three-dimensional model of the substrate structure. And (3) establishing a three-dimensional model of the substrate structure by using three-dimensional drawing software, as shown in figure 2, and exporting the STL format file for later use. In fig. 2, a ceramic substrate is provided with a heat conduction channel therein, and an electromagnetic unit is provided on the ceramic substrate.
The ceramic substrate is designed in a structure that: comprehensively considering the requirements of the next generation of ceramic substrates on temperature resistance, heat conduction and electromagnetic wave absorption, and completing the structural design of the substrate with a complex shape;
the three-dimensional model is established: drawing a three-dimensional model diagram by adopting three-dimensional drawing software for the designed ceramic substrate structure with the complex shape, and exporting the three-dimensional model diagram into an STL file format;
and preparing mixed ceramic powder. First, 100g of AlN ceramic powder was weighed with 10g of graphene and 5g of michael (MXene). Weighing and mixing alcohol with the volume of 100ml, and then carrying out ball milling treatment on a planetary ball mill at the rotating speed of 400r/min for 8 hours to obtain a suspension; carrying out rotary evaporation drying on the suspension for 4 hours at 80 ℃, 60r/min and-0.05 MPa to obtain mixed ceramic powder; sieving the mixed ceramic powder by a 300-mesh sieve to obtain final mixed ceramic powder;
and preparing the 3D printing ceramic slurry. Weighing 80g of AlN-graphene-Michael alkene (MXene) mixed ceramic powder, 26.3g of photosensitive resin, 0.53g of dispersing agent and 0.26g of photoinitiator, and then carrying out ball milling treatment on a planetary ball mill at the rotating speed of 400r/min for 6 hours to obtain the 3D printing ceramic slurry meeting the requirements. Wherein the photosensitive resin is prepared from two resin monomers of 1, 6-hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA) according to the weight ratio of 5: 5 by volume; the dispersant is two dispersants of 17000# dispersant and 20000# dispersant, wherein the weight ratio of the dispersant is 5: 5 volume ratio of the dispersant system; the photoinitiator was 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO).
3D printing of ceramic substrate green bodies. Firstly, a prepared three-dimensional model of the ceramic substrate structure is led into a 3D printing device, the light source wavelength of the 3D printing device is 405nm, and the light source intensity is 8000 mu W/cm 2 The 3D printing slice layer is 25 μm thick, and the exposure time of each layer is 10 s. And guiding the prepared 3D printing ceramic slurry into a material groove of 3D printing equipment, and starting 3D printing. And (4) obtaining a ceramic substrate green body by stacking layer by layer. And placing the ceramic substrate in alcohol, and washing the ceramic substrate in the alcohol for 10min by ultrasonic oscillation to obtain a final ceramic substrate green body.
And (4) removing glue and degreasing of the ceramic substrate green body. Heating the prepared ceramic substrate green body to 800 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere and the nitrogen pressure of 1atm, and then preserving heat for 1h for glue removal and degreasing treatment. Ensuring that the cured photosensitive resin in the green body is completely cracked and carbonized.
Pressureless sintering of ceramic substrates. And heating the ceramic substrate subjected to binder removal and degreasing to 2000 ℃ at a heating rate of 2 ℃/min in an argon atmosphere in a vacuum sintering furnace, and carrying out pressureless sintering after heat preservation for 1h to finally obtain a ceramic substrate product with high temperature resistance, high heat conductivity and electromagnetic wave absorption.
Example 2:
a high temperature resistant, high heat conduction, electromagnetic wave absorption ceramic substrate product and a 3D printing method thereof are disclosed, the process flow is shown in figure 1, and the specific steps are as follows:
and (5) designing a substrate structure. The next generation of ceramic substrate is faced with the requirements of temperature resistance (1200 ℃), heat conduction (directional heat conduction, heat conductivity 60W/mk) and electromagnetic wave absorption (5-20 GHz to-10 dB), and based on the system parameters of silicon nitride, graphene and Macene (MXene) composite ceramic materials, the design of a high-temperature-resistant, high-heat-conduction and electromagnetic wave absorption structure is completed.
And establishing a three-dimensional model of the substrate structure. And (3) establishing a three-dimensional model of the substrate structure by using three-dimensional drawing software, as shown in figure 2, and exporting the STL format file for later use.
The ceramic substrate is designed in a structure that: comprehensively considering the requirements of the next generation of ceramic substrates on temperature resistance, heat conduction and electromagnetic wave absorption, and completing the structural design of the substrate with a complex shape;
the three-dimensional model is established: drawing a three-dimensional model diagram by adopting three-dimensional drawing software on the designed ceramic substrate structure with the complex shape, and exporting the three-dimensional model diagram into an STL file format;
and preparing mixed ceramic powder. First, 82g of AlN ceramic powder, 6g of graphene, and 6g of Michael alkene (MXene) were weighed. Weighing and mixing 80ml of alcohol, and then carrying out ball milling treatment on a planetary ball mill at the rotating speed of 300r/min for 10 hours to obtain a suspension; the suspension is subjected to rotary evaporation drying for 4 hours at 60 ℃ and 30r/min and under-0.05 MPa to obtain mixed ceramic powder; sieving the mixed ceramic powder by a 250-mesh sieve to obtain final mixed ceramic powder;
and preparing the 3D printing ceramic slurry. Weighing 50g of AlN-graphene-Michael alkene (MXene) mixed ceramic powder, 25g of photosensitive resin, 0.4g of dispersing agent and 0.4g of photoinitiator, and then carrying out ball milling treatment on a planetary ball mill at the rotating speed of 300r/min for 10h to obtain the 3D printing ceramic slurry meeting the requirements. Wherein the photosensitive resin is prepared from two resin monomers of 1, 6-hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA) according to the weight ratio of 6: 4 by volume; the dispersant is two dispersants of 17000# dispersant and 20000# dispersant, and the weight ratio of the dispersant is 7: 3 volume ratio of the dispersant system; the photoinitiator was 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO).
3D printing of ceramic substrate green bodies. Firstly, guiding a prepared three-dimensional model of the ceramic substrate structure into a 3D printing device, wherein the light source wavelength of the 3D printing device is 450nm, and the light source intensity is 7500 mu W/cm 2 3D printing slice layerThe thickness was 50 μm and the exposure time for each layer was 15 s. And guiding the prepared 3D printing ceramic slurry into a material groove of 3D printing equipment, and starting 3D printing. And (4) obtaining a ceramic substrate green body by stacking layer by layer. And placing the ceramic substrate in alcohol, and washing the ceramic substrate in the alcohol for 10min by ultrasonic oscillation to obtain a final ceramic substrate green body.
And (4) removing glue and degreasing of the ceramic substrate green body. Heating the prepared ceramic substrate green body to 800 ℃ at a heating rate of 6 ℃/min under the nitrogen atmosphere and the nitrogen pressure of 1atm, and then preserving heat for 1h for glue removal and degreasing treatment. Ensuring that the cured photosensitive resin in the green body is completely cracked and carbonized.
Pressureless sintering of ceramic substrates. And heating the ceramic substrate subjected to binder removal and degreasing to 2000 ℃ at a heating rate of 3 ℃/min in an argon atmosphere in a vacuum sintering furnace, and carrying out pressureless sintering after heat preservation for 1h to finally obtain a ceramic substrate product with high temperature resistance, high heat conductivity and electromagnetic wave absorption.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (6)
1. The high-temperature-resistant, high-heat-conduction and electromagnetic wave-absorbing ceramic substrate applied to the 5G field is characterized in that the high-temperature-resistant, high-heat-conduction and electromagnetic wave-absorbing ceramic substrate applied to the 5G field meets the temperature resistance requirement of 800-1600 ℃, the heat conduction requirement of directional heat conduction and 50-100W/mk heat conductivity, and the electromagnetic wave-absorbing requirement of 3-30 GHz, -5-10 dB, a heat conduction channel is arranged in the ceramic substrate, and the ceramic substrate is manufactured by adopting the following 3D printing method:
preparing mixed ceramic powder required by 3D printing of the ceramic substrate, wherein the mixed ceramic powder comprises the following components in percentage by volume:
the volume fraction of the AlN ceramic powder is 80-90 vol%, the volume fraction of the graphene is 5-10 vol%, and the volume fraction of the Mackene is 5-10 vol%;
step two, preparing ceramic slurry required by 3D printing of the ceramic substrate, wherein the ceramic slurry comprises the following components in percentage by volume:
the AlN-graphene-mikene mixed ceramic powder accounts for 40-55 vol%, the photosensitive resin accounts for 35-58 vol%, the dispersant accounts for 1-5 vol%, and the photoinitiator accounts for 1-5 vol%;
step three, 3D printing the ceramic substrate based on the digital model of the ceramic substrate,
the digital model for establishing the ceramic substrate comprises a substrate structure design, and the high temperature resistance requirement, the heat conduction requirement and the electromagnetic wave absorption requirement are considered in the substrate structure design.
2. The ceramic substrate of claim 1, wherein the 3D printing method further comprises the steps of:
step four, carrying out glue removal and degreasing on the ceramic substrate obtained in the step three; the content of the step comprises the following steps:
heating the prepared ceramic substrate green body to 500-800 ℃ at a heating rate of 2-10 ℃/min under the nitrogen atmosphere and a nitrogen pressure of 1atm, and then preserving heat for 1-5 h to carry out glue removal and degreasing treatment, so as to ensure that the cured photosensitive resin in the green body is completely cracked and carbonized.
3. The ceramic substrate of claim 2, wherein the 3D printing method further comprises the steps of:
step five, carrying out pressureless sintering on the degreased ceramic substrate in the step four; the content of the step comprises the following steps:
and heating the ceramic substrate subjected to the binder removal and degreasing to 1700-2100 ℃ at a heating rate of 1-5 ℃/min in an argon atmosphere in a vacuum sintering furnace, and carrying out pressureless sintering after heat preservation for 0.5-2 h.
4. The ceramic substrate according to claim 1,
the specific preparation steps of the mixed ceramic powder are as follows:
selecting AlN powder, graphene powder and MXene powder according to a proportion, weighing and mixing alcohol with the same volume, and performing ball milling treatment on a planetary ball mill at the rotating speed of 300-400 r/min for 6-8 h to obtain suspension;
the suspension is subjected to rotary evaporation drying for 3-6 hours at the temperature of 70-90 ℃ and under the pressure of-0.04-0.09 MPa to obtain mixed ceramic powder;
the mixed ceramic powder is sieved by 250-400 meshes to obtain the final mixed ceramic powder.
5. The ceramic substrate according to claim 1, wherein the ceramic slurry is prepared by the following steps:
weighing the mixed ceramic powder, photosensitive resin, photoinitiator and dispersant according to the volume, and then carrying out ball milling treatment on a planetary ball mill at the rotating speed of 300-400 r/min for 6-12 h to obtain ceramic slurry meeting the requirements;
the photosensitive resin is prepared from two resin monomers of 1, 6-hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA) according to the weight ratio of (3-7): (7-3) a resin system mixed in a volume ratio;
the dispersing agent is 17000# and 20000# according to (2-8): (8-2) a dispersant system mixed in a volume ratio;
the photoinitiator was 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO).
6. The ceramic substrate according to any one of claims 1-3, wherein the 3D printing of the ceramic substrate in step three employs a photo-curing 3D printing process; the method comprises the following steps:
importing the prepared digital model of the ceramic substrate into 3D printing equipment;
the light source wavelength of the photocuring 3D printing equipment is 405-450 nm, and the light source intensity is 6000-10000 mu W/cm 2 The thickness of the 3D printing slice layer is 25-100 μm, and the exposure time of each layer is 5-E30s；
Guiding the prepared ceramic slurry into a material groove of 3D printing equipment, and starting 3D printing to obtain a ceramic substrate;
and (3) placing the mixture in alcohol and washing the mixture for 10-30 min by ultrasonic oscillation.
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