CN110734273A - 3D printing-based cultural relic copying composite material and preparation method thereof - Google Patents
3D printing-based cultural relic copying composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses composite materials for 3D printing-based cultural relic replication and a preparation method thereof, wherein the composite materials comprise, by weight, 25-30 parts of aluminum oxide, 22-26 parts of zirconium oxide, 8-12 parts of hexagonal boron nitride, 12-16 parts of epoxy acrylate, 3-5 parts of glass fiber, 4-6 parts of nano-montmorillonite, 2-3 parts of nano-titanium dioxide, 0.6-0.8 part of water-based organic silicon resin, 2-4 parts of absolute ethyl alcohol, 0.1-0.5 part of dispersing agent, 0.4-0.6 part of photoinitiator and 1-2 parts of silane coupling agent.
Description
Technical Field
The invention relates to the technical field of 3D printing of cultural relics, in particular to composite materials for cultural relic replication based on 3D printing and a preparation method thereof.
Background
The cultural relics are used as the intelligent crystals left by ancestors, and the intelligent crystals have great historical and cultural values, wherein the ceramic cultural relics play an important role in 5000-year brilliant culture in China, but many precious cultural heritages face the danger of being destroyed due to historical, natural or artificial reasons, the cultural relic replication is effective protections for the cultural relics, and the research on the ceramic cultural relic replication method and the replication material has important practical significance and application value.
The principle of the 3D printer is that a three-dimensional digital model of a printing piece is firstly subjected to layering processing to generate a scanning path required by printing each layers, then the powder material is selectively melted by laser, the wire material is melted and extruded by an electrothermal nozzle, an image is printed by ultraviolet light projection in a layer-by-layer mode, and the printing platform is lowered by layer thickness, and in some 3D printing methods, a new layers of unprocessed materials are required to be arranged on the formed surface by powder laying procedures, then the layer-by-layer forming process is carried out in a circulating reciprocating mode, and finally the three-dimensional digital model can be printed into a three-dimensional object.
The application of 3D printing technology to ceramic cultural relic replication is mainly limited by replication materials, the existing ceramic cultural relic replication materials can be applied to 3D printing, are few and cannot meet the requirement of ceramic cultural relic replication, and therefore how to design cultural relic replication composite materials based on 3D printing and a preparation method thereof are the technical problems to be solved by the invention.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides composite materials for cultural relic replication based on 3D printing and a preparation method thereof.
The invention solves the technical problems through the following technical means:
cultural relic replication composite material based on 3D printing comprises, by weight, 25-30 parts of alumina, 22-26 parts of zirconia, 8-12 parts of hexagonal boron nitride, 12-16 parts of epoxy acrylate, 3-5 parts of glass fiber, 4-6 parts of nano montmorillonite, 2-3 parts of nano titanium dioxide, 0.6-0.8 part of water-based organic silicon resin, 2-4 parts of absolute ethyl alcohol, 0.1-0.5 part of dispersing agent, 0.4-0.6 part of photoinitiator and 1-2 parts of silane coupling agent.
Preferably, the hexagonal boron nitride is nano hexagonal boron nitride.
Preferably, the dispersing agent is or more of polyamide, polypropoxy ammonium salt, quaternary ammonium acetate and phosphate.
Preferably, the photoinitiator is or more of benzoin dimethyl ether, 2, 4, 6 (trimethylbenzoyl) diphenyl phosphine oxide and benzophenone.
A preparation method of 3D printing-based cultural relic replication composite material, comprising the following steps:
mixing alumina and hexagonal boron nitride, adding absolute ethyl alcohol, ball-milling for 8-10h, vacuum-drying at 60-70 ℃, sieving with a 250-mesh sieve, then placing in a vacuum pressure furnace, and carrying out heat treatment for 1-2h at 850-;
b, adding the raw materials subjected to the heat treatment in the step a into an SPS mold, sintering for 10min at the temperature of 1500-;
c, mixing the epoxy acrylate, the water-based organic silicon resin and the dispersing agent, and stirring at the normal temperature for 20-30min at the stirring speed of 350-450 r/min;
and d, mixing the raw materials obtained in the step b and the step c, adding zirconium oxide, glass fiber, nano montmorillonite and nano titanium dioxide, carrying out ball milling for 4-6h at the temperature of 45-55 ℃, then adding a dispersing agent, a photoinitiator and a silane coupling agent, and carrying out ball milling for 3-5h continuously to obtain the nano titanium dioxide.
The invention has the advantages that: the 3D printing-based composite material for cultural relic replication has a compact structure, excellent weather resistance and crack resistance, and good self-cleaning and sterilization capabilities; the sintering process time is short, and a sintering aid is not required to be added, so that the material cost is reduced.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention are described below, and it is obvious that the described embodiments are some embodiments of of the present invention, but not all embodiments.
Example 1, cultural relic replication-based composite materials for 3D printing comprise the following raw materials, by weight (kg), of alumina 25, zirconia 22, hexagonal boron nitride 8, epoxy acrylate 12, glass fiber 3, nano montmorillonite 4, nano titanium dioxide 2, water-based organic silicon resin 0.6, absolute ethyl alcohol 2, dispersing agent 0.1, photoinitiator 0.4 and silane coupling agent 1.
Example 2, cultural relic replication-based composite materials for 3D printing comprise the following raw materials, by weight (kg), of alumina 28, zirconia 24, hexagonal boron nitride 10, epoxy acrylate 14, glass fiber 4, nano montmorillonite 5, nano titanium dioxide 3, water-based organic silicon resin 0.7, anhydrous ethanol 3, dispersant 0.3, photoinitiator 0.5 and silane coupling agent 1.
Example 3, cultural relic replication-based composite materials for 3D printing, which comprise the following raw materials, by weight (kg), of alumina 30, zirconia 26, hexagonal boron nitride 12, epoxy acrylate 16, glass fiber 5, nano montmorillonite 6, nano titanium dioxide 3, water-based organic silicon resin 0.8, absolute ethyl alcohol 4, dispersing agent 0.5, photoinitiator 0.6 and silane coupling agent 2.
In each of the above embodiments, the hexagonal boron nitride is nano hexagonal boron nitride, the dispersant is or more selected from polyamide, polypropoxy ammonium salt, quaternary ammonium acetate and phosphate, and the photoinitiator is or more selected from benzoin dimethyl ether, 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide and benzophenone.
A preparation method of 3D printing-based cultural relic replication composite material, comprising the following steps:
mixing alumina and hexagonal boron nitride, adding absolute ethyl alcohol, ball-milling for 9 hours, carrying out vacuum drying at 65 ℃, sieving with a 250-mesh sieve, then placing in a vacuum air pressure furnace, and carrying out heat treatment for 1.5 hours at 950 ℃;
b, adding the raw materials subjected to heat treatment in the step a into an SPS (semi-solid phase sintering) mould, sintering for 10min at 1600 ℃ under the axial pressure of 30MPa, and then cooling along with a furnace;
c, mixing the epoxy acrylate, the water-based organic silicon resin and the dispersing agent, and stirring at the normal temperature for 25min at the stirring speed of 400 r/min;
and d, mixing the raw materials obtained in the step b and the step c, adding zirconium oxide, glass fiber, nano montmorillonite and nano titanium dioxide, carrying out ball milling for 5 hours at the temperature of 50 ℃, then adding a dispersing agent, a photoinitiator and a silane coupling agent, and carrying out ball milling for 4 hours continuously to obtain the nano titanium dioxide.
The composite material for cultural relic replication of the invention comprises the following raw materials: through adding nanometer titanium dioxide, improve combined material's ultraviolet resistance ability greatly, and then improve the weatherability of duplicating the historical relic, simultaneously, nanometer titanium dioxide still has bactericidal effect, cooperates raw materials nanometer montmorillonite, can effectively kill the bacterium, and the two complex effect principle is: the nano montmorillonite has an adsorption effect on bacteria, can adsorb the bacteria to the nano titanium dioxide, and then kills the bacteria by the nano titanium dioxide, and the sterilization effect can be greatly improved by matching the nano titanium dioxide and the nano titanium dioxide, and rutile type is preferably selected as the nano titanium dioxide;
the hexagonal boron nitride and the alumina are compounded to form a compact oxide layer, so that the oxidation resistance of the composite material is greatly improved.
The composite material for cultural relic replication of the invention is prepared by the following steps: in the step a, hexagonal boron nitride is coated on the surface of alumina by using an in-situ chemical reaction, and when the composite material is oxidized, a compact boric acid aluminum oxygen diffusion barrier layer can be generated on the surface of the composite material, so that oxygen is prevented from rapidly diffusing into the composite material, and the composite material has good crack resistance and oxidation resistance;
and (b) adopting an SPS (spark plasma sintering) technology in the step (b), wherein the sintering time is short, a sintering aid is not required to be added in the sintering process, the raw material cost is saved, a spark plasma effect exists in the sintering process, an activated plasma is generated, the plasma generated in aspect can clean the surface of the powder body formed by compounding the hexagonal boron nitride and the alumina, and in addition, in aspect, the diffusion and mass transfer in the sintering process are promoted, so that the produced composite material has a compact structure and excellent performance.
It should be noted that, in this document, relational terms such as , second and the like are only used to distinguish entities or operations from another entities or operations without necessarily requiring or implying any actual such relationship or order between such entities or operations, furthermore, the terms "comprise", "comprise" or any other variation thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises the family of elements does not include only those elements but also other elements not explicitly listed or inherent to such process, method, article, or apparatus.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
- The 3D printing-based cultural relic replication composite material is characterized by comprising the following raw materials, by weight, 25-30 parts of aluminum oxide, 22-26 parts of zirconium oxide, 8-12 parts of hexagonal boron nitride, 12-16 parts of epoxy acrylate, 3-5 parts of glass fiber, 4-6 parts of nano montmorillonite, 2-3 parts of nano titanium dioxide, 0.6-0.8 part of water-based organic silicon resin, 2-4 parts of absolute ethyl alcohol, 0.1-0.5 part of a dispersing agent, 0.4-0.6 part of a photoinitiator and 1-2 parts of a silane coupling agent.
- 2. The composite material for cultural relic replication based on 3D printing according to claim 1, wherein the hexagonal boron nitride is nano hexagonal boron nitride.
- 3. The composite material for cultural relic replication based on 3D printing according to claim 1, wherein the dispersant is or more of polyamide, polypropoxy ammonium salt, quaternary ammonium acetate and phosphate.
- 4. The composite material for cultural relic replication based on 3D printing according to claim 1, wherein the photoinitiator is or more of benzoin dimethyl ether, 2, 4, 6 (trimethylbenzoyl) diphenylphosphine oxide and benzophenone.
- 5, A preparation method of 3D printing-based cultural relic replication composite material, which is characterized by comprising the following steps:mixing alumina and hexagonal boron nitride, adding absolute ethyl alcohol, ball-milling for 8-10h, vacuum-drying at 60-70 ℃, sieving with a 250-mesh sieve, then placing in a vacuum pressure furnace, and carrying out heat treatment for 1-2h at 850-;b, adding the raw materials subjected to the heat treatment in the step a into an SPS mold, sintering for 10min at the temperature of 1500-;c, mixing the epoxy acrylate, the water-based organic silicon resin and the dispersing agent, and stirring at the normal temperature for 20-30min at the stirring speed of 350-450 r/min;and d, mixing the raw materials obtained in the step b and the step c, adding zirconium oxide, glass fiber, nano montmorillonite and nano titanium dioxide, carrying out ball milling for 4-6h at the temperature of 45-55 ℃, then adding a dispersing agent, a photoinitiator and a silane coupling agent, and carrying out ball milling for 3-5h continuously to obtain the nano titanium dioxide.
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