TWI602795B - A method of manufacturing three dimensions printing ceramic and manufacturing silicon-based metal oxide composite material - Google Patents

Description

Method for preparing three-dimensional printing ceramic and bismuth-based metal oxide composite material

The invention relates to a method for preparing a three-dimensional printing ceramic and a cerium-based metal oxide composite material, in particular to a cerium-based metal oxide composite material which uses a liquid precursor as a raw material and mixes a ceramic or a metal material. Used in 3D printing technology to make ceramic products.

According to the three-dimensional printing technology, it has developed rapidly in recent years. It only needs to import the three-dimensional image. The three-dimensional printing machine will create an identical model according to the drawing. The application level is quite extensive, from medicine, shipbuilding, vehicle and navigation. In the fields of military, military, and construction, the three-dimensional printing machine can be used to manufacture the desired objects. Therefore, three-dimensional printing technology can be said to be an indispensable part of the development of future technology. Furthermore, there are already A considerable number of companies have commercialized 3D printers and provided them to the industry or the general public. It is known that the three-dimensional printing technology is getting closer to the people's lives.

At present, the mainstream three-dimensional printing technology can be divided into three categories: (1) fused deposition method, the material is the use of thermoplastic plastic material wire or granules, the plastic material is heated to the molten state through the nozzle, and the nozzle is under the control of the computer. According to the imported surface information for axial movement, at the same time squeezing and controlling the liquid flow, so that the molten plastic material is evenly layer by layer, and then solidified through the ambient temperature of the environment to obtain a plastic finished product; 2) Photocuring method, the raw material of which is a photopolymer, and the raw material is placed in a trough, when manufactured, The forming platform will first cure a layer of raw material as a substrate, and then the computer will control the ultraviolet light to cure according to the surface of the drawing. The forming platform will rise continuously, and the ultraviolet light will only illuminate the place where it needs to be cured by projection. The finished product can be obtained when it is fully raised. The accuracy and cost of this method are higher than that of the fused deposition method. (3) The laser laminate manufacturing method can print ceramic or metal products, and add ceramic or metal powder. The agent and solvent are used as raw materials for the laser laminate manufacturing method. After the material is deposited on the working platform, the laser is used for forming and calcining. Since the material can use ceramic or metal, the finished product will be more finished. Good mechanical properties.

For example, the Republic of China Patent Publication No. TW I526415 B "Ceramic material for three-dimensional printing and its preparation method, three-dimensional molded product" discloses a ceramic material having a two-layer structure, which can be applied to a laser laminate manufacturing method. Using the characteristics of ceramic coating to improve the accuracy after three-dimensional printing; also, the Republic of China Patent Publication No. TW I528324 "Three-dimensional molding method for ceramic parts" discloses a three-dimensional forming method in which a scanner is used to scan a target object first. According to the obtained three-dimensional coordinate data, the model is constructed, and the procedure of laser sintering forming using ceramic powder as a raw material can improve the precision of the laser laminate manufacturing method. It can be seen from the two prior patents that the current ceramic materials are mainly used as the main three-dimensional printing technology by the high cost laser laminate manufacturing method. However, the cost of the laser laminate manufacturing method is much higher than that of the fused deposition method and the photo-curing method. Therefore, the three-dimensional printing machine currently sold to the general public mainly uses the fused deposition method and the photo-curing method.

In summary, the fused deposition method has the advantages of low cost in the current three-dimensional printing technology, but the plastic material is used as a raw material, resulting in the printed product having no good mechanical properties, abrasion resistance, corrosion resistance and The mechanical strength is not good; the laser laminate manufacturing method can use ceramic materials or metal materials as raw materials to make the finished product have good mechanical properties, but the cost required is much higher than the fused deposition method; The finished product made of the polymer is between the fused deposition method and the laser laminate manufacturing method regardless of the preparation cost or mechanical properties. It can be seen that according to the current technology and materials, It is impossible to produce a defect with high mechanical strength by a three-dimensional printing method at a lower cost, and therefore, how to find a material with good mechanical properties to match a low-cost three-dimensional printing technique, so that the printed product has a high quality. Wear resistance, high corrosion resistance and better mechanical properties are the directions that the inventors intend to study.

Nowadays, the inventor is still in the spirit of tirelessness in view of the above-mentioned existing three-dimensional printing materials, and is supported by his rich professional knowledge and years of practical experience. Improvements have been made and the present invention has been developed based on this.

The main object of the present invention is to provide a method for preparing a three-dimensional printing ceramic and a cerium-based metal oxide composite material, which is prepared by using a liquid precursor as a raw material and mixing a cerium-based metal oxide composite material of a ceramic or a metal material to prepare a A composite material suitable for lower cost 3D printing technology and capable of printing ceramic products.

In order to achieve the above-mentioned object, the present invention provides a method for preparing a three-dimensional printing ceramic and a bismuth-based metal oxide composite material, wherein the method for preparing a bismuth-based metal oxide composite material comprises the steps of: taking a liquid precursor; Mixing 5 wt% to 95 wt% of the liquid precursor with 5 wt% to 95 wt% of the powder material to form a mixture; and step 3: subjecting the mixture to a heat treatment procedure to form a mercapto metal oxide composite .

In one embodiment of the present invention, the bismuth-based metal oxide composite material is suitable for three-dimensional printing technology by adding a solvent and optionally adding an adhesive to prepare a ceramic article. Among them, it can be sintered through high temperature to enhance the mechanical properties of the ceramic article.

In one embodiment of the present invention, the liquid precursor comprises a polymer material diluent, wherein the polymer material diluent is impregnated with a nano material, and the polymer material diluent is a polymer material such as decazane. , decane, decane or decane, etc. One of the nanomaterials can be, for example, one of a carbon nanotube or a nanotube.

In one embodiment of the present invention, the polymer material diluent contains about 10% by weight to 30% by weight of the polymer material, and about 70% by weight to 90% by weight of the organic solvent.

In an embodiment of the invention, the powder material is selected from the group consisting of ceramic materials, metal materials, plastic materials, semiconductor materials, and fiber materials.

In one embodiment of the invention, the ceramic material is selected from the group consisting of, for example, yttria, zirconia, alumina, tantalum nitride, and tantalum carbide.

In one embodiment of the invention, the metallic material is selected from the group consisting of, for example, cobalt, nickel, iron, aluminum, titanium, and the like.

In one embodiment of the present invention, the plastic material may be, for example, one of a thermoplastic plastic or a thermosetting plastic; the semiconductor material may be, for example, a compound composed of a group of four or six elements; the fiber material may be, for example, a glass fiber. Carbon fiber or a combination of both.

In one embodiment of the invention, the temperature of the heat treatment process is from 100 ° C to 1500 ° C.

In one embodiment of the present invention, the second step is to selectively further add a photocuring agent to impart a photocurable property to the formed bismuth-based metal oxide composite.

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First: Flow chart of the preparation steps of the bismuth-based metal oxide composite material according to the preferred embodiment of the present invention

Second: Flow chart of ceramic preparation according to preferred embodiment of the present invention

Third: ceramic surface image of a preferred embodiment of the present invention

The object of the present invention and its structural and functional advantages will be explained in conjunction with the specific embodiments according to the structure shown in the following drawings, so that the reviewing committee can have a more in-depth and specific understanding of the present invention.

Referring to the first figure, a method for preparing a three-dimensional printing ceramic and a bismuth-based metal oxide composite material, the method for preparing the bismuth-based metal oxide composite material comprises the first step (S1): taking a liquid precursor, The invention comprises a polymer material dilution solution, wherein the polymer material dilution liquid is impregnated with a nanometer material, for example, one of a carbon nanotube or a nano tube; and the second step (S2): 5 wt% to 95 wt% The liquid precursor is uniformly mixed with one of 5 wt% to 95 wt% of the powder material to form a mixture, wherein the powder material is selected from the group consisting of ceramic materials, metal materials, plastic materials, semiconductor materials, and fiber materials. And selectively adding a photocuring agent to make the formed bismuth-based metal oxide composite material have photocurable properties; and step 3 (S3): performing a heat treatment process on the mixture at a temperature of 100 ° C to 1500 ° C, Forming a bismuth-based metal oxide composite material; wherein the polymer material diluent contains about 10% by weight to 30% by weight of the polymer material, and may be, for example, a decane, a decane, a decane or a decane. First, and about 70% by weight to 90% by weight of the organic solvent, which may be, for example, methanol, ethanol or acetone; and the ceramic powder system is selected from, for example, cerium oxide, zirconium oxide, aluminum oxide, cerium nitride and cerium carbide. a group of metal powders selected from the group consisting of, for example, cobalt, nickel, iron, aluminum, and titanium; and the plastic material may be, for example, one of thermoplastic or thermosetting plastics; For example, it may be a compound composed of four or six groups of elements; the fiber material may be, for example, glass fiber, carbon fiber or a combination of both.

Furthermore, please refer to the second figure. The ruthenium-based metal oxide composite prepared by this method can be applied to the three-dimensional printing technology, and a solvent can be added during the printing process, for example, acetonitrile (Acetonitrile), and can be selected. The addition of an adhesive increases the overall adhesion, thereby producing a ceramic article in three-dimensional printing. In addition, the high-temperature sintering process can be used to increase the tightness between the grains of the material to enhance the mechanical structure of the ceramic product. nature.

In addition, the following specific embodiments can further prove that the present invention can be practically The scope of use of the invention is not intended to limit the scope of the invention in any way.

Referring to the second figure, the bismuth-based metal oxide composite material of the present invention is based on a liquid polymer material containing decazane, decane, decane or decane, and the like. After heat treatment, it will be converted into ceramic, which has high wear resistance and corrosion resistance, and the cockroach itself has biocompatibility, which is quite suitable for the preparation of biomedical materials. As an opportunity, the inventor will further It is applied to three-dimensional printing technology; however, it has been found that although the liquid polymer material after heat treatment has high wear resistance and corrosion resistance, the mechanical properties of brittleness and volume shrinkage are rather poor.

Accordingly, in order to prepare a material having a certain mechanical strength, first, a mixture of decazane and acetone is prepared as a polymer material in a ratio of 1:9, and a carbon nanotube is immersed in the diluent to complete a liquid precursor. Adding 5wt%~95wt% of ceramic powder and metal powder in 5wt%~95wt% liquid precursor, fully and uniformly mixed to form a mixture, and the mixture is directly processed by a three-dimensional printing machine by fused deposition method. Print and test if this mixture is suitable for use in 3D printing technology. After the test, it is indeed possible to form a mold by the fused deposition method and further subjected to a heat treatment process at a temperature of 400 ° C in an air or inert gas atmosphere to convert into a ceramic to provide a ceramic having a certain mechanical strength.

In order to have better mechanical properties, the mixture is also prepared by the above method. The difference is that heat treatment is performed at a temperature of 400 ° C to form a ruthenium-based metal oxide composite material having a chemical formula of SiCNO, which can be used as a raw material for ceramics. Its good wear resistance, corrosion resistance and mechanical strength can be applied to the fused deposition method of three-dimensional printing technology. In addition, in the process of adding the ceramic powder and the metal powder to the liquid precursor, the photocuring agent can be selectively added, mainly by using a compound capable of providing a photochemical reaction, for example, benzoin diethyl ether (2, 2) -Dimethoxy-2-phenylacetophenone), oxidizing the formed ruthenium-based metal The composite material has photocurable properties, so the printing process can also be carried out by a three-dimensional printing machine using a photocuring method.

The ruthenium-based metal oxide composite material is placed in a raw material tank by a three-dimensional printing machine by a fused deposition method, and the ruthenium-based metal oxide composite material is a powder, and an acetonitrile solvent is further added. Mix into a viscous liquid in the raw material tank. Since the ruthenium-based metal oxide composite material itself has adhesiveness, it is free to choose whether or not to add the adhesive together, and the adhesive can be, for example, a polyvinylidene fluoride (PVDF) resin compound; In the 3D printing machine, the host computer will recognize the input drawing information and plan a forming process. The nozzle will be layered to form the target composite ceramic model by the movement of the nozzle, and then the sintering process will be performed to make the structure of the material more Tight, as shown in the third figure, through the observation of the electron microscope, it can be seen that there are many nano particles in the structure tightly combined, indicating that the mechanical strength of the composite ceramic model has been improved, and also has good wear resistance and corrosion resistance. Sexuality makes this bismuth-based metal oxide composite more widely applicable.

It can be seen from the above description that the present invention has the following advantages compared with the prior art:

1. The method for preparing a three-dimensional printing ceramic and a ruthenium-based metal oxide composite material, which uses a liquid polymer material as a raw material, and is combined with a ceramic material or a metal material to prepare a bismuth-based metal oxide composite material by using The hardness of the ceramic material and the ductility of the metal material enable the finished product of the three-dimensional printing machine to improve the previous poor performance in terms of brittleness and volume shrinkage, in addition to good wear resistance and corrosion resistance. The mechanical strength is improved.

2. The method for preparing a three-dimensional printing ceramic and a bismuth-based metal oxide composite material, wherein the bismuth-based metal oxide composite material can prepare a composite ceramic by a fused deposition method in a three-dimensional printing technique, if in the preparation process Further adding a photocuring agent, the material can also be used to produce a composite ceramic by photocuring; it must be used higher than before. The cost of the laser laminate manufacturing method can print the finished product of metal or ceramic, and the invention can greatly reduce the cost and greatly help the use of the industry.

3. The method for preparing a three-dimensional printing ceramic and a ruthenium-based metal oxide composite material according to the present invention, since the prepared bismuth-based metal oxide composite material already has adhesiveness, it is not necessary to add adhesion when performing three-dimensional printing. The additive is required to add an adhesive to the material compared to the laser laminate manufacturing method, and the invention can reduce the complexity and cost of the process in the process of preparing the composite ceramic by using three-dimensional printing.

In summary, the method for preparing a three-dimensional printing ceramic and a ruthenium-based metal oxide composite material of the present invention can achieve the intended use efficiency by the above-disclosed embodiments, and the present invention has not been disclosed in the application. Before, Cheng has fully complied with the requirements and requirements of the Patent Law.爰Issuing an application for a patent for invention in accordance with the law, and asking for a review, and granting a patent, is truly sensible.

The illustrations and descriptions of the present invention are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; those skilled in the art, which are characterized by the scope of the present invention, Equivalent variations or modifications are considered to be within the scope of the design of the invention.

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Claims (6)

A method for preparing a three-dimensional printing ceramic and a bismuth-based metal oxide composite material, wherein the method for preparing the bismuth-based metal oxide composite material comprises the following steps: Step 1: taking a liquid precursor, comprising a polymer material diluent, The polymer material diluent contains 10% by weight to 30% by weight of the polymer material, and 70% by weight to 90% by weight of the organic solvent, and the polymer material diluent is immersed in a nanometer material, wherein the polymer material diluent polymer The material is one of decazane, decane, decane or decane, and the nano material is one of a carbon nanotube or a nano tube; step 2: 5 wt% to 95 wt% of the liquid precursor Mixing with 5 wt% to 95 wt% of a powder material to form a mixture, wherein the powder material is selected from the group consisting of ceramic materials, metal materials, plastic materials, semiconductor materials, and fiber materials; and steps Third, the mixture is subjected to a heat treatment process to form a ruthenium-based metal oxide composite material, wherein the heat treatment procedure has a temperature of 100 ° C to 1500 ° C. A method for preparing a three-dimensional printing ceramic and a ruthenium-based metal oxide composite material according to claim 1, wherein the bismuth-based metal oxide composite material is applied to three In the technical application, a solvent is added and an adhesive is selectively added to prepare a ceramic article. The method for preparing a three-dimensional printing ceramic and a cerium-based metal oxide composite material according to claim 1, wherein the ceramic material is selected from the group consisting of cerium oxide, zirconium oxide, aluminum oxide, tantalum nitride, and tantalum carbide. Group. A method of preparing a three-dimensionally-printed ceramic and a bismuth-based metal oxide composite material according to claim 1, wherein the metal material is selected from the group consisting of cobalt, nickel, iron, aluminum, and titanium. The method for preparing a three-dimensional printing ceramic and a bismuth-based metal oxide composite material according to claim 1, wherein the plastic material is one of a thermoplastic plastic or a thermosetting plastic; Or a compound composed of four or six groups; the fiber material is glass fiber, carbon fiber or a combination of the two. The method for preparing a three-dimensional printing ceramic and a ruthenium-based metal oxide composite material according to the first aspect of the invention, wherein the second step is to further selectively add a photocuring agent to form the ruthenium-based metal oxide composite. The material has photocurable properties.