CN116041067B - Photo-curing 3D printing magnetic composite wave-absorbing ceramic and preparation method and application thereof - Google Patents
Photo-curing 3D printing magnetic composite wave-absorbing ceramic and preparation method and application thereof Download PDFInfo
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- 238000000016 photochemical curing Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000010146 3D printing Methods 0.000 title claims abstract description 32
- 238000000197 pyrolysis Methods 0.000 claims abstract description 45
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001723 curing Methods 0.000 claims description 6
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- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 4
- VGBAECKRTWHKHC-UHFFFAOYSA-N cyclopenta-1,3-diene;1-ethenylcyclopenta-1,3-diene;iron(2+) Chemical group [Fe+2].C=1C=C[CH-]C=1.[CH2-]C=C1C=CC=C1 VGBAECKRTWHKHC-UHFFFAOYSA-N 0.000 claims description 3
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- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- B33Y10/00—Processes of additive manufacturing
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Abstract
The invention relates to the technical field of additive manufacturing of wave-absorbing ceramic materials, in particular to a magnetic composite wave-absorbing ceramic for photo-curing 3D printing and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding polysiloxane and a magnetic additive into an organic solvent for stirring and ultrasonic dispersion, and sequentially carrying out vacuum spin-steaming treatment and pre-crosslinking treatment on the obtained ceramic slurry to obtain a premix; adding an active diluent and a photoinitiator into the premix, mixing and stirring to obtain photosensitive resin, and performing photocuring 3D printing to obtain a magnetic composite wave-absorbing ceramic blank; and (3) carrying out pyrolysis treatment on the blank body to obtain the magnetic composite wave-absorbing ceramic. The invention not only adopts a novel photocuring 3D printing forming technology, but also adopts an ultrasonic dispersion and pre-crosslinking treatment process used in the preparation of slurry, so that the content of magnetic particles in the wave-absorbing ceramic can be effectively improved, and meanwhile, the pyrolysis treatment temperature of the ceramic is lower, so that the material is ensured to have certain magnetic loss capacity and wave-absorbing performance.
Description
Technical Field
The invention relates to the technical field of additive manufacturing of wave-absorbing ceramic materials, in particular to a magnetic composite wave-absorbing ceramic for photo-curing 3D printing, and a preparation method and application thereof.
Background
The wave absorbing material is an electromagnetic functional material which can effectively absorb the incident electromagnetic wave and convert the electromagnetic energy into heat energy or other forms of energy to be consumed, so that the echo intensity is weakened. Chinese patent CN113735590a discloses a preparation method and product of high temperature resistant electromagnetic wave-absorbing ceramic matrix composite, the preparation steps of which include: first, preparing SiC/C/TiO 2 And (3) carrying out photocuring 3D printing on the ceramic matrix composite photosensitive slurry to obtain a green body, then sintering the green body, immersing the green body in a mixed solution with the volume ratio of Polycarbosilane (PCS) to Divinylbenzene (DVB) of 1:1, and repeating the immersing-curing-sintering steps for 6 times to finally obtain the high-temperature-resistant electromagnetic wave-absorbing ceramic matrix composite. The density of the high-temperature-resistant electromagnetic wave-absorbing ceramic matrix composite material prepared by the method is 94%, the three-point bending strength measured by a mechanical testing machine is 217MPa, and the effective wave-absorbing bandwidth (EAB) measured by a vector network analyzer is 6-40 GHz. However, the preparation method is complex in preparation process and complex in flow, and is not suitable for industrial production.
Bin Du et al prepared Fe-SiOC ceramic with wave-absorbing properties by combining freeze-drying and precursor pyrolysis, first adding ferric nitrate solution to SiOC precursor to form a mixed solution, then freeze-drying in liquid nitrogen to form SiFeOC hydrogel, and finally pyrolyzing at a high temperature of 1450 ℃ to form Fe-SiOC wave-absorbing ceramic. In the frequency band of 2-18 GHz, when the thickness of the wave-absorbing ceramic is 4.55mm, the effective absorption bandwidth is 2GHz, and the reflection coefficient is minimum-59.6 dB at 5.4 GHz. The Fe-SiOC wave-absorbing ceramic has higher wave-absorbing strength, but has narrower effective wave-absorbing bandwidth; the content of Fe in the sample is small (the maximum addition amount is 0.6 mol/L), so that the effect of magnetic loss is difficult to be exerted when electromagnetic waves are absorbed; and the pyrolysis temperature of the ceramic is higher, so that Fe ions are easy to lose magnetism due to exceeding the Curie temperature. ( See: bin Du, junjie Qian, ping Hu, et al enhanced electromagnetic wave absorption of Fe-doped silicon oxycarbide nanocomposites [ J ]. Journal of the American Ceramic Society,2019,103 (3): 1732-1743. )
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a photo-curing 3D printed magnetic composite wave-absorbing ceramic, and a preparation method and application thereof, and aims to solve the problems of complex preparation process, low magnetic particle content, poor wave-absorbing capacity and the like of a magnetic composite wave-absorbing material at the present stage.
The technical scheme of the invention is as follows:
a preparation method of photo-curing 3D printed magnetic composite wave-absorbing ceramic comprises the following steps:
adding polysiloxane and a magnetic additive into an organic solvent, stirring and performing ultrasonic dispersion to obtain ceramic slurry;
the ceramic slurry sequentially undergoes vacuum spin steaming treatment and pre-crosslinking treatment to obtain a premix;
adding an active diluent and a photoinitiator into the premix, and mixing and stirring to obtain photosensitive resin;
performing photocuring 3D printing on the photosensitive resin to obtain a magnetic composite wave-absorbing ceramic blank;
and carrying out pyrolysis treatment on the magnetic composite wave-absorbing ceramic blank to obtain the magnetic composite wave-absorbing ceramic.
The preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic comprises the steps that the magnetic additive is one or more selected from ferromagnetic compounds, cobalt-containing magnetic compounds and nickel-containing magnetic compounds; the organic solvent is selected from one or two of tetrahydrofuran and tripropylene glycol monomethyl ether.
The preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic comprises the steps of selecting the magnetic additive from vinylferrocene and Fe 2 O 3 、Co 2 O 3 One or more of NiO。
The preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic comprises the following steps of, wherein the mass of polysiloxane is 30-40% of the total mass of the organic solvent; the addition amount of the magnetic additive is 5-15% of the ceramic slurry.
The preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic comprises the steps of carrying out vacuum rotary evaporation treatment for 30-45min, wherein the temperature of the vacuum rotary evaporation treatment is 40-50 ℃, and the rotating speed of the vacuum rotary evaporation treatment is 30-50r/min.
The preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic comprises the following steps of pre-crosslinking treatment under inert atmosphere; the temperature of the pre-crosslinking treatment is 100-150 ℃, the heating rate of the pre-crosslinking treatment is 3-5 ℃/min, and the heat preservation time of the pre-crosslinking treatment is 50-70min.
The preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic comprises the following steps that the reactive diluent is one or two of hexanediol diacrylate and trimethylolpropane triacrylate; the photoinitiator is diacylphosphine oxide 819; the mass of the reactive diluent is 30-40% of the total mass of the premix; the mass of the photoinitiator is 3-8% of the total mass of the premix.
The preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic comprises the following steps of performing pyrolysis treatment in an inert atmosphere; the temperature of the pyrolysis treatment is 800-1200 ℃, the heating rate of the pyrolysis treatment is 3-5 ℃/min, and the heat preservation time of the pyrolysis treatment is 2-3h.
The photo-curing 3D printed magnetic composite wave-absorbing ceramic is prepared by the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic.
The application of the photo-cured 3D printed magnetic composite wave-absorbing ceramic in stealth materials and radar detection.
The beneficial effects are that: the invention provides a photo-curing 3D printed magnetic composite wave-absorbing ceramic, and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding polysiloxane and a magnetic additive into an organic solvent, stirring and performing ultrasonic dispersion to obtain ceramic slurry; the ceramic slurry sequentially passes through vacuum spin steaming treatment and pre-crosslinking treatment to obtain a premix; adding an active diluent and a photoinitiator into the premix, and mixing and stirring to obtain photosensitive resin; performing photocuring 3D printing on the photosensitive resin to obtain a magnetic composite wave-absorbing ceramic blank; and carrying out pyrolysis treatment on the magnetic composite wave-absorbing ceramic blank to obtain the magnetic composite wave-absorbing ceramic. The invention prepares the magnetic composite wave-absorbing ceramic material by combining photocuring 3D printing forming and precursor pyrolysis, not only adopts a novel photocuring 3D printing forming technology, but also uses ultrasonic dispersion and pre-crosslinking treatment technology in the process of preparing slurry, can effectively improve the content of magnetic particles in the wave-absorbing ceramic, and simultaneously ensures that the material has certain magnetic loss capacity and wave-absorbing performance due to lower pyrolysis treatment temperature of the ceramic.
Drawings
FIG. 1 is a schematic process flow diagram of a preparation method of a photo-cured 3D printed magnetic composite wave-absorbing ceramic;
FIG. 2 is a graph of SiOC (Fe) ceramic added with various mass percentages VcFe in example 1 of the present invention: (a) XRD pattern, (b) partial magnified pattern;
FIG. 3 is a graph of SiOC (Fe) ceramic added with 10wt.% VcFe in accordance with example 1 of the present invention: (a) a cross-sectional SEM image, (b) an EDS analysis image;
FIG. 4 shows SiOC (Fe) ceramics of different structures obtained in example 1 of the present invention: (a) (c) printing a physical image of the part, (b) and (d) SEM micro-topography;
FIG. 5 is a graph showing changes in the wave-absorbing reflectivity of SiOC (Fe) ceramics added with different mass fractions VcFe obtained in example 1 of the present invention.
Detailed Description
The invention provides a photo-curing 3D printing magnetic composite wave-absorbing ceramic, a preparation method and application thereof, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood by those skilled in the art that all terms (including 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 unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The wave absorbing material is an electromagnetic functional material which can effectively absorb incident electromagnetic waves, convert the electromagnetic waves into heat energy or other forms of energy to be consumed, and further weaken echo intensity. The excellent wave-absorbing material has the characteristics of thin thickness, light weight, wide absorption frequency band, high wave-absorbing strength and the like, and has the advantages of high temperature resistance, oxidation resistance, good mechanical property and the like in order to meet the use under certain special conditions.
At present, more wave-absorbing materials such as ferrite, carbonyl iron, magnetic metal oxide and the like are applied, and the wave-absorbing strength is high when the wave-absorbing material is used at normal temperature, but the wave-absorbing material has the advantages of narrower absorption frequency band, larger weight, intolerance to high temperature and poor oxidation resistance, so that the development of the wave-absorbing material in the field of high-temperature wave-absorbing materials is limited; the emerging wave-absorbing ceramic material has potential application value in the field of high-temperature wave-absorbing materials due to the excellent performances of low density, high temperature resistance, absorption frequency band and the like.
The polymer precursor converted ceramics (PDCs) have the advantages of uniform components, lower preparation temperature, better thermal shock resistance and high-temperature oxidation resistance, and can design the electromagnetic performance of the precursor ceramics from a microscopic angle by adjusting the types and the quantity of functional groups, so that the polymer precursor converted ceramics has a certain application prospect in the field of wave-absorbing materials. The traditional ceramic forming process such as isostatic pressing, slip casting, gel casting, casting and the like is suitable for mass production, but has low processing precision and is difficult to prepare parts with complex shapes.
The 3D printing forming technology is used as a novel ceramic forming process, has the characteristics of high processing precision, strong designability and the like, and can prepare devices with complex shapes, and the 3D printing forming technology is used for laminating processing and one-step forming in the processing process, so that the production steps are greatly simplified, and the production efficiency is improved. The polymer precursor converted wave-absorbing ceramic material prepared by adopting the 3D printing forming technology can fully exert and utilize the processing advantages and excellent electromagnetic performances of the PDCs ceramic material to prepare the electromagnetic functional ceramic material with integrated structure and function, thereby developing a new thought for researching the structure complicacy, refinement and functionalization of the ceramic material.
However, the preparation method disclosed in the prior patent CN113735590A is complex in process and complex in flow, and is not suitable for industrial production. The Fe-SiOC ceramic with wave absorbing performance prepared by Bin Du et al in a way of combining freeze drying and precursor pyrolysis has narrower effective wave absorbing bandwidth, less Fe content in a sample and difficult magnetic loss effect in electromagnetic wave absorption; and the pyrolysis temperature of the ceramic is higher, so that Fe ions are easy to lose magnetism due to exceeding the Curie temperature.
Based on the above, as shown in fig. 1, the invention provides a preparation method of a photo-curing 3D printed magnetic composite wave-absorbing ceramic, comprising the following steps:
step S10: adding polysiloxane and a magnetic additive into an organic solvent, stirring and performing ultrasonic dispersion to obtain ceramic slurry;
step S20: the ceramic slurry sequentially undergoes vacuum spin steaming treatment and pre-crosslinking treatment to obtain a premix;
step S30: adding an active diluent and a photoinitiator into the premix, and mixing and stirring to obtain photosensitive resin;
step S40: performing photocuring 3D printing on the photosensitive resin to obtain a magnetic composite wave-absorbing ceramic blank;
step S50: and carrying out pyrolysis treatment on the magnetic composite wave-absorbing ceramic blank to obtain the magnetic composite wave-absorbing ceramic.
In the embodiment, polysiloxane (PSO), an organic solvent and a magnetic additive are taken as main raw materials, ceramic slurry is obtained through stirring and ultrasonic dispersion, and then a pre-mixed liquid is obtained through combining vacuum rotary evaporation treatment and pre-crosslinking treatment; and finally adding an active diluent and a photoinitiator, mixing, and performing photo-curing 3D printing and pyrolysis treatment to finally obtain the magnetic composite wave-absorbing ceramic. The magnetic composite wave-absorbing ceramic material is prepared by combining photocuring 3D printing forming and precursor pyrolysis, not only is a novel photocuring 3D printing forming technology adopted, but also the ultrasonic dispersion and pre-crosslinking technology adopted in the process of preparing slurry can effectively improve the content of magnetic particles in the wave-absorbing ceramic, and meanwhile, the pyrolysis treatment temperature of the ceramic is lower, so that the magnetic composite wave-absorbing ceramic material is ensured to have certain magnetic loss capacity and wave-absorbing performance.
In some embodiments, the magnetic additive is selected from one or more of a ferromagnetic containing compound, a cobalt containing magnetic compound, a nickel containing magnetic compound; the organic solvent is selected from one or two of Tetrahydrofuran (THF) and tripropylene glycol monomethyl ether (TPM).
In a preferred embodiment, the organic solvent is a mixture of tetrahydrofuran and tripropylene glycol monomethyl ether.
In some embodiments, the magnetic additive is selected from vinylferrocene, fe 2 O 3 、Co 2 O 3 One or more of NiO.
In some embodiments, the polysiloxane is 30-40% of the total mass of the organic solvent; the addition amount of the magnetic additive is 5-15% of the ceramic slurry.
Specifically, the wave-absorbing ceramic absorbs and attenuates the incident electromagnetic wave mainly through two modes of dielectric loss and magnetic loss, and the polysiloxane can separate out carbon simple substance at high temperature, so that the dielectric loss can be carried out in the material, and the magnetic loss of the wave-absorbing ceramic can be increased by adding the magnetic additive, so that the wave-absorbing performance of the wave-absorbing ceramic is improved; and the solubility of the magnetic additive in polysiloxane can be improved by adding a proper amount of organic solvent, and the two organic solvents can be removed by evaporation in the vacuum spin evaporation and pre-crosslinking treatment processes at a lower temperature, so that the strength of a subsequent ceramic blank is not influenced.
In some embodiments, in the step S10, the stirring speed is 200-400r/min, and the stirring time is 10-20min; the ultrasonic dispersion time is 15-30min; the polysiloxane, the magnetic additive and the organic solvent are fully stirred and then subjected to ultrasonic dispersion, so that the polysiloxane, the organic solvent and the magnetic additive can be uniformly mixed, magnetic particles are uniformly dispersed and distributed in the polysiloxane, and the performance of each part of the wave-absorbing ceramic is uniform.
In some embodiments, the time of the vacuum spin-steaming treatment is 30-45min, the temperature of the vacuum spin-steaming treatment is 40-50 ℃, and the rotating speed of the vacuum spin-steaming treatment is 30-50r/min.
In some embodiments, the pre-crosslinking treatment is performed under an inert atmosphere; the temperature of the pre-crosslinking treatment is 100-150 ℃, the heating rate of the pre-crosslinking treatment is 3-5 ℃/min, and the heat preservation time of the pre-crosslinking treatment is 50-70min.
In the embodiment, the vacuum spin steaming treatment and the pre-crosslinking treatment can be adopted to effectively remove the organic solvent, and the magnetic particles and polysiloxane molecules can be mutually bonded and crosslinked to form a network structure through the pre-crosslinking treatment, so that the magnetic particles are stably kept in the ceramic slurry.
In a preferred embodiment, the time of the vacuum rotary steaming treatment is 45min, the temperature of the vacuum rotary steaming treatment is 40 ℃, and the rotating speed of the vacuum rotary steaming treatment is 30r/min; the equipment for the pre-crosslinking treatment is a tube furnace, nitrogen atmosphere is adopted, the temperature of the pre-crosslinking treatment is 100 ℃, the heating rate of the pre-crosslinking treatment is 3 ℃/min, and the heat preservation time of the pre-crosslinking treatment is 60min.
In some embodiments, the reactive diluent is selected from one or both of hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA); the photoinitiator is diacylphosphine oxide 819 (TPO); the mass of the reactive diluent is 30-40% of the total mass of the premix; the mass of the photoinitiator is 3-8% of the total mass of the premix.
In some embodiments, the stirring in step S30 is performed at a speed of 300-400r/min for a period of 10-20min.
The viscosity of the pre-crosslinked resin premix is high, and the viscosity of the resin can be effectively reduced by adding the reactive diluent, so that the viscosity is adjusted to be suitable for photocuring 3D printing; and the photoinitiator can be added to increase the sensitivity of the resin to laser, thereby facilitating the photo-curing molding of the resin.
In some embodiments, in the step S40, the apparatus for photo-curing 3D printing is a digital photo-processing molding machine, and the molding parameters include: the laser power density is 2-100mW/cm 2 The single layer curing thickness is 25-100 mu m, and the single layer exposure time is 25-200s; the principle of parameter selection in the step is to shorten the total time length of 3D printing as much as possible on the premise of ensuring smooth molding of the photosensitive resin, thereby improving the production efficiency.
In some embodiments, the pyrolysis treatment is performed under an inert atmosphere; the temperature of the pyrolysis treatment is 800-1200 ℃, the heating rate of the pyrolysis treatment is 3-5 ℃/min, and the heat preservation time of the pyrolysis treatment is 2-3h.
Specifically, the pyrolysis treatment equipment is a tube furnace, and the pyrolysis treatment equipment is characterized in that N is as follows 2 Under the protection of atmosphere, the temperature of the pyrolysis treatment is 1000 ℃, the heating rate of the pyrolysis treatment is 3 ℃/min, and the heat preservation time of the pyrolysis treatment is 2h. The slower heating rate is selected when the magnetic composite wave-absorbing ceramic is prepared, so that cracking of a ceramic blank body can be avoided; the pyrolysis treatment temperature is in the range, so that carbon precipitation can be ensured, the magnetic property of the magnetic particles cannot disappear due to overhigh temperature, dielectric loss and magnetic loss wave absorption mechanisms in the ceramic are ensured, and the wave absorption performance of the material is improved.
In addition, the invention also provides the photo-curing 3D printed magnetic composite wave-absorbing ceramic, which is prepared by the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic.
In the embodiment, the photo-curing 3D printed magnetic composite wave-absorbing ceramic prepared by the preparation method has complete structure, has crystal precipitation with magnetic loss and dielectric loss inside, and has good wave-absorbing performance in the frequency range of 7-18 GHz.
The invention also provides application of the photo-cured 3D printed magnetic composite wave-absorbing ceramic in stealth materials and radar detection.
The following examples are further illustrative of the invention. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation method of the magnetic composite wave-absorbing ceramic for photo-curing 3D printing comprises the following steps:
(1) Preparing ceramic slurry: PSO, THF, TPM is prepared by the following steps of: 55:15, respectively adding VcFe accounting for 5%, 7.5%, 10%, 12.5% and 15% of the total mass of the ceramic slurry into a beaker, stirring the ceramic slurry at the rotating speed of 300r/min for 15min, and then performing ultrasonic dispersion for 20min to obtain mixed ceramic slurry added with VcFe with different mass percentages;
(2) Preparing a resin premix: performing vacuum rotary steaming on the mixed ceramic slurry obtained in the step (1), wherein the temperature is 45 ℃, the rotating speed is 30r/min, and the rotary steaming time is 40min; then, carrying out pre-crosslinking treatment on the ceramic slurry subjected to rotary steaming treatment, wherein pre-crosslinking equipment is a tube furnace, nitrogen atmosphere is adopted, the crosslinking temperature is 100 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 60min, so as to obtain resin premix;
(3) Preparing photosensitive resin: adding HDDA, TMPTA and TPO into the premix according to a certain proportion, wherein the addition amount of the HDDA and the TMPTA is 36% of the total mass of the premix, the addition amount of the TPO is 5% of the total mass of the premix, and mixing and stirring are carried out after the addition, the stirring speed is 300r/min, and the time is 20min, so as to obtain photosensitive resin;
(4) Printing and forming: photo-curing 3D printing forming is carried out on the photosensitive resin, and forming is carried out on the photosensitive resin by a digital light processing forming machineThe parameters are laser power density 4mW/cm 2 The single-layer curing thickness is 50 mu m, and the SiOC (Fe) composite wave-absorbing ceramic blank is obtained;
(5) Preparing a ceramic material: pyrolysis treatment is carried out on SiOC (Fe) composite wave-absorbing ceramic blank, pyrolysis equipment is a tube furnace, and the SiOC (Fe) composite wave-absorbing ceramic blank is prepared by the steps of 2 Under the protection of atmosphere, the heat treatment temperature is 1000 ℃, the heating rate is 3 ℃/min, the heat is preserved for 2 hours after the temperature is raised to the heat treatment temperature, and the SiOC (Fe) composite wave-absorbing ceramic material added with different mass percentages of VcFe is obtained.
As shown in FIG. 2, the SiOC (Fe) composite wave-absorbing ceramic material contains amorphous carbon and Fe after pyrolysis 3 C and crystallization C are separated out, which means that the ceramic not only separates out simple substance C with dielectric loss in the pyrolysis process, but also combines Fe atoms with C in SiOC to react to generate Fe with magnetic loss 3 And C, amorphous phase still exists in the ceramic at high temperature, which also shows that the material has good high temperature resistance. The spectral scan in fig. 3 shows that the ceramic contains Fe element inside and exists in a crystal form inside the ceramic. Fig. 4 shows a photo-cured 3D printing formed SiOC (Fe) ceramic body and a pyrolyzed SiOC (Fe) wave-absorbing ceramic body, which can be seen that the ceramic body has a complete structure after printing forming, no collapse and deformation occur, and the pyrolyzed ceramic body basically maintains the structure after printing forming, and no large cracking phenomenon occurs. FIG. 5 is a graph showing the change of the wave-absorbing reflectivity of SiOC (Fe) ceramic added with 5%, 7.5%, 10%, 12.5% and 15% VcFe with frequency, and it can be seen that the sample added with 7.5wt.% VcFe has the best wave-absorbing performance, and is, -10dB in the frequency range of 7 GHz-18 GHz<R<-5dB, indicating an electromagnetic wave absorption rate between 70% and 90%.
Example 2:
the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic is different from the embodiment 1 in that:
the mass ratio of PSO, THF, TPM in the step (1) is 40:50:10; in the step (3), the addition amount of the HDDA and the TMPTA is 40% of the total mass of the premix, and the rotation speed of mixing and stirring after the addition is 400r/min for 20min.
Compared with the example 1, the mass ratio of the PSO raw material is increased, the consumption of the reactive diluent is also increased, so that the light transmittance of the photosensitive resin is reduced, the time required for single-layer printing forming is prolonged when the same printing laser power and curing thickness are selected, the shrinkage rate of the SiOC (Fe) composite wave-absorbing ceramic material obtained after pyrolysis is increased from 51.3% to 57.4%, and the number of cracks in the ceramic is increased.
Example 3:
the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic is different from the embodiment 1 in that:
the pre-crosslinking temperature in the step (2) is 150 ℃; the single-layer curing thickness of the photosensitive resin in the step (4) when the photosensitive resin is subjected to photo-curing 3D printing forming is 25 mu m.
Compared with the embodiment 1, the temperature of the pre-crosslinking of the ceramic slurry is increased, the viscosity of the resin premix obtained after the pre-crosslinking is increased, the color is deepened, the total time required for printing and molding is prolonged after the single-layer curing thickness during printing and molding is reduced, but the stepped effect of the finally prepared Fe/SiOC composite wave-absorbing ceramic material is improved.
Example 4:
the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic is different from the embodiment 1 in that:
the laser power density in the molding parameters of the photo-curing 3D printing molding of the photosensitive resin in the step (4) is 10mW/cm 2 The monolayer cured thickness was 50 μm.
Compared with the embodiment 1, the laser power density during printing and molding is improved, the time required by printing and molding is reduced, the density of the finally prepared Fe/SiOC composite wave-absorbing ceramic material is higher, and the ceramic shrinkage is reduced from 51.3% to 46.7%.
Example 5:
the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic is different from the embodiment 1 in that:
the heat treatment temperature at the time of pyrolysis in step (5) was 1200 ℃.
The ceramic pyrolysis temperature was increased as compared with example 1, and the precipitation amount of C in the finally produced SiOC (Fe) composite wave-absorbing ceramic material was increased, contributing to the improvement of the wave-absorbing performance, but the shrinkage rate of the ceramic became large, cracks were easily generated, and the mechanical properties were deteriorated.
Comparative example 1:
the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic is different from the embodiment 1 in that:
the pre-crosslinking temperature in step (2) was 200 ℃.
The pre-crosslinking temperature of the ceramic slurry was increased as compared with example 1, and the resin obtained after the pre-crosslinking was gel-like and was difficult to dissolve in the reactive diluent in step (3), so that the subsequent step was not performed to prepare SiOC (Fe) composite wave-absorbing ceramic material.
Comparative example 2:
the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic is different from the embodiment 1 in that:
and (3) improving the quality of the photoinitiator in the step (3) to 10% of the quality of the premix, and stirring for 30min.
Compared with the embodiment 1, the addition amount of the photoinitiator is increased, so that the photoinitiator cannot be completely dissolved in the resin, and is deposited on a platform during subsequent printing and forming, the process of photo-curing and forming is hindered, the shape of a printed green body is incomplete, and subsequent experimental steps cannot be completed.
Comparative example 3:
the preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic is different from the embodiment 1 in that:
the heat treatment temperature at the time of pyrolysis in step (5) was 600 ℃.
Compared with the embodiment 1, the pyrolysis temperature of the ceramic is reduced, a large amount of amorphous phase structures exist in the finally prepared SiOC (Fe) composite wave-absorbing ceramic material, C is not precipitated basically, the wave-absorbing performance is poor, and the electromagnetic wave absorption rate of the ceramic is lower than 70% in the frequency range of 2-18 GHz.
In summary, the invention provides a photo-curing 3D printed magnetic composite wave-absorbing ceramic, and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding polysiloxane and a magnetic additive into an organic solvent, stirring and performing ultrasonic dispersion to obtain ceramic slurry; the ceramic slurry sequentially passes through vacuum spin steaming treatment and pre-crosslinking treatment to obtain a premix; adding an active diluent and a photoinitiator into the premix, and mixing and stirring to obtain photosensitive resin; performing photocuring 3D printing on the photosensitive resin to obtain a magnetic composite wave-absorbing ceramic blank; and carrying out pyrolysis treatment on the magnetic composite wave-absorbing ceramic blank to obtain the magnetic composite wave-absorbing ceramic. The invention prepares the magnetic composite wave-absorbing ceramic material by combining photocuring 3D printing forming and precursor pyrolysis, not only adopts a novel photocuring 3D printing forming technology, but also uses ultrasonic dispersion and pre-crosslinking treatment technology in the process of preparing slurry, can effectively improve the content of magnetic particles in the wave-absorbing ceramic, and simultaneously ensures that the material has certain magnetic loss capacity and wave-absorbing performance due to lower pyrolysis treatment temperature of the ceramic.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (5)
1. The preparation method of the photo-curing 3D printed magnetic composite wave-absorbing ceramic is characterized by comprising the following steps:
adding polysiloxane and a magnetic additive into an organic solvent, stirring for 10-20min at the rotating speed of 200-400r/min, and then performing ultrasonic dispersion for 15-30min to obtain ceramic slurry;
the ceramic slurry sequentially undergoes vacuum spin steaming treatment and pre-crosslinking treatment to obtain a premix;
adding an active diluent and a photoinitiator into the premix, and mixing and stirring for 10-20min at the rotating speed of 300-400r/min to obtain photosensitive resin;
performing photocuring 3D printing on the photosensitive resin to obtain a magnetic composite wave-absorbing ceramic blank;
performing pyrolysis treatment on the magnetic composite wave-absorbing ceramic blank to obtain magnetic composite wave-absorbing ceramic;
the organic solvent is a mixture of tetrahydrofuran and tripropylene glycol monomethyl ether;
the magnetic additive is selected from vinylferrocene and Fe 2 O 3 、Co 2 O 3 One or more of NiO;
the mass of the polysiloxane is 30-40% of the total mass of the organic solvent; the addition amount of the magnetic additive is 5-15% of the ceramic slurry; the mass of the photoinitiator is 3-8% of the total mass of the premix;
the pre-crosslinking treatment is carried out under inert atmosphere; the temperature of the pre-crosslinking treatment is 100-150 ℃, the heating rate of the pre-crosslinking treatment is 3-5 ℃/min, and the heat preservation time of the pre-crosslinking treatment is 50-70min; the pyrolysis treatment is carried out under an inert atmosphere; the temperature of the pyrolysis treatment is 800-1200 ℃, the heating rate of the pyrolysis treatment is 3-5 ℃/min, and the heat preservation time of the pyrolysis treatment is 2-3h;
the light curing 3D printing device is a digital light processing forming machine.
2. The method for preparing the photo-cured 3D printed magnetic composite wave-absorbing ceramic according to claim 1, wherein the time of the vacuum spin-steaming treatment is 30-45min, the temperature of the vacuum spin-steaming treatment is 40-50 ℃, and the rotating speed of the vacuum spin-steaming treatment is 30-50r/min.
3. The method for preparing the photo-curing 3D printed magnetic composite wave-absorbing ceramic according to claim 1, wherein the reactive diluent is one or two selected from hexanediol diacrylate and trimethylolpropane triacrylate; the photoinitiator is diacylphosphine oxide 819; the mass of the reactive diluent is 30-40% of the total mass of the premix.
4. A photo-cured 3D printed magnetic composite wave-absorbing ceramic, characterized in that it is produced by the method for producing a photo-cured 3D printed magnetic composite wave-absorbing ceramic according to any one of claims 1 to 3.
5. Use of the photo-cured 3D printed magnetic composite wave-absorbing ceramic according to claim 4 in stealth material, radar detection.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001358493A (en) * | 2000-04-10 | 2001-12-26 | Hitachi Ltd | Electromagnetic-wave absorber, its manufacturing method and various applications using the same |
| CN104528725A (en) * | 2015-01-08 | 2015-04-22 | 厦门大学 | Preparation method of magnetic silicon carbide ceramic nano particles |
| CN108975916A (en) * | 2018-08-01 | 2018-12-11 | 渤海大学 | A kind of preparation method of high conductivity ceramic material |
| KR102117829B1 (en) * | 2018-11-21 | 2020-06-02 | 포항공과대학교 산학협력단 | Method of manufacturing 3d ceramic structure using silica nanoparticle and ceramic microreactor for high temeprature chemical process using the same |
| CN111362702A (en) * | 2020-03-17 | 2020-07-03 | 中国工程物理研究院激光聚变研究中心 | Preparation method of SiOC radar type wave-absorbing material |
| CN112321318A (en) * | 2020-10-20 | 2021-02-05 | 上海航翼高新技术发展研究院有限公司 | Polymer precursor porous magnetic ceramic system based on 3D printing technology and preparation method thereof |
| CN112960972A (en) * | 2021-03-19 | 2021-06-15 | 西北工业大学 | Broadband adjustable light and thin structure type ceramic-based wave-absorbing material and cross-scale design and preparation method |
| CN213680424U (en) * | 2020-10-20 | 2021-07-13 | 上海航翼高新技术发展研究院有限公司 | Polymer precursor porous magnetic ceramic system based on 3D printing technology |
| CN114956827A (en) * | 2022-05-09 | 2022-08-30 | 深圳市宁鹏时代科技有限公司 | Preparation method of ceramic printing material, 3D printing method and ceramic product |
-
2022
- 2022-11-28 CN CN202211499606.5A patent/CN116041067B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001358493A (en) * | 2000-04-10 | 2001-12-26 | Hitachi Ltd | Electromagnetic-wave absorber, its manufacturing method and various applications using the same |
| CN104528725A (en) * | 2015-01-08 | 2015-04-22 | 厦门大学 | Preparation method of magnetic silicon carbide ceramic nano particles |
| CN108975916A (en) * | 2018-08-01 | 2018-12-11 | 渤海大学 | A kind of preparation method of high conductivity ceramic material |
| KR102117829B1 (en) * | 2018-11-21 | 2020-06-02 | 포항공과대학교 산학협력단 | Method of manufacturing 3d ceramic structure using silica nanoparticle and ceramic microreactor for high temeprature chemical process using the same |
| CN111362702A (en) * | 2020-03-17 | 2020-07-03 | 中国工程物理研究院激光聚变研究中心 | Preparation method of SiOC radar type wave-absorbing material |
| CN112321318A (en) * | 2020-10-20 | 2021-02-05 | 上海航翼高新技术发展研究院有限公司 | Polymer precursor porous magnetic ceramic system based on 3D printing technology and preparation method thereof |
| CN213680424U (en) * | 2020-10-20 | 2021-07-13 | 上海航翼高新技术发展研究院有限公司 | Polymer precursor porous magnetic ceramic system based on 3D printing technology |
| CN112960972A (en) * | 2021-03-19 | 2021-06-15 | 西北工业大学 | Broadband adjustable light and thin structure type ceramic-based wave-absorbing material and cross-scale design and preparation method |
| CN114956827A (en) * | 2022-05-09 | 2022-08-30 | 深圳市宁鹏时代科技有限公司 | Preparation method of ceramic printing material, 3D printing method and ceramic product |
Non-Patent Citations (3)
| Title |
|---|
| 基于DLP技术的前驱体转化SiOC（Fe）陶瓷研究;杨赞德;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第2期);第18-20页、第23-28页和第34-36页 * |
| 热解硅氧烷合成低碳硅氧碳陶瓷和金属复合;梁田;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第8期);第1页、第14页和第53-54页 * |
| 聚合物转化SiOC陶瓷的微结构设计及电磁性能优化;段文艳;《中国博士学位论文全文数据库 工程科技Ⅰ辑》(第1期);第89-90页和第100页 * |
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