CN108929113B - Manufacturing method of three-dimensional additive forming material - Google Patents
Manufacturing method of three-dimensional additive forming material Download PDFInfo
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- CN108929113B CN108929113B CN201710370827.5A CN201710370827A CN108929113B CN 108929113 B CN108929113 B CN 108929113B CN 201710370827 A CN201710370827 A CN 201710370827A CN 108929113 B CN108929113 B CN 108929113B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
- C04B35/62635—Mixing details
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63472—Condensation polymers of aldehydes or ketones
- C04B35/63476—Phenol-formaldehyde condensation polymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
Abstract
The invention provides a formula, a manufacturing method and a forming process of a ceramic-like material, which introduces the thermosetting effect of phenolic resin into the field of 3D ceramic printing and greatly reduces the forming difficulty and the sintering requirement.
Description
Technical Field
The invention relates to a formula, a manufacturing method and a forming process of an additive forming material. In particular to a formula, a manufacturing method and a forming process of a ceramic-like material.
Background
In recent years, with scientific progress, "additive forming technology" has been rapidly developed, and ceramic materials are no exception. However, the curing of the ceramic material after forming is difficult and requires specialized equipment for sintering, and the defect limits the development of the field of manufacturing the additive forming artwork.
Disclosure of Invention
The invention provides a formula, a manufacturing method and a forming process of a ceramic-like material, which introduces the thermosetting effect of phenolic resin into the field of 3D ceramic printing and greatly reduces the forming difficulty and the sintering requirement.
The material of the invention consists of four components, including ceramic powder, resin, solvent and additive, and the material is prepared into paste or mud and can be stored for a short time.
The ceramic powder can be oxide ceramic, carbide ceramic and nitride ceramic.
The resin is a thermosetting resin, in particular a water-soluble or alcohol-soluble phenolic resin.
The solvent can be water or an organic solvent such as methanol, ethanol or acetone. In the case of using a water-soluble phenol resin, water is used as a solvent, and in the case of using an alcohol-soluble phenol resin, an organic solvent such as methanol, ethanol, acetone, carbon tetrachloride, or tetrahydrofuran may be used as a solvent.
Wherein the additive is urotropin and dye, and the urotropin is curing agent. In the case of using a phenol resin which already contains urotropin, it may not be added. The dye may not be added if not required.
The material manufacturing method related by the invention comprises the following steps: firstly, mixing the resin and the additive according to a certain proportion (the concrete mixing proportion is that the phenolic resin is increased or decreased by 3-30% according to different forming temperatures, the urotropine is 0.1-2.5% and the rest is ceramic powder), and then doping the solvent for dissolving. Preparing the phenolic resin solution. And pouring the solution into ceramic powder, and stirring and mixing the solution in a closed container to form the ceramic mud. The mixing proportion of the solution and the ceramic powder is proportioned according to the field requirement. The above blending step is required to be carried out at normal temperature.
The method 2 comprises the following steps: and mixing the resin powder containing the additive and the ceramic powder together, and uniformly stirring and storing for later use. When in use, a certain amount of solvent is added to prepare ceramic mud with proper viscosity.
The material of the invention comprises the following four steps: primary forming: and (3) performing additive forming under the driving of a numerical control motion system by using a pneumatic dispensing valve, a screw dispensing valve or a professional 3D ceramic printing extruder.
And (3) drying: and a blowing and heating device is arranged in the forming chamber, so that the solvent in the ceramic mud is quickly evaporated, and only blowing is carried out without heating when the solvent with particularly strong volatility is used.
Primary curing: after drying, the formed product is heated to 150-250 ℃ for primary curing, and the heating time is determined according to the wall thickness or the size of the formed product.
Carbonizing: after drying and primary curing, the formed product is put into a sintering furnace to be sintered at high temperature in an oxygen-free environment, the sintering temperature is above 650 ℃, so that the phenolic resin is decomposed and carbonized to finally form a material with a C-C network structure, and the material is a permanent bonding phase and has extremely high bonding strength.
Advantageous effects
The invention describes components, a preparation method and a forming step of a ceramic-like material suitable for additive forming, the material can be suitable for the field of additive forming manufacturing, the forming and curing temperature is reduced to a relatively low temperature, the manufacturing process is simplified, and carbonization and sintering can be carried out under other requirements so that a formed product can be used under the special working condition of relatively high ambient temperature.
Drawings
Fig. 1 is a flow chart of a material manufacturing method 1 of the present invention.
Fig. 2 is a flow chart of a material manufacturing method 2 of the present invention.
Fig. 3 is a schematic flow chart of a machine for 3D printing of ceramics according to the present invention.
FIG. 4 is a schematic view of the extrusion molding process of the ceramic paste according to the present invention.
Fig. 5 is a schematic diagram of the drying process of the present invention.
In the figure: 1 ceramic 3D printer, 2 ceramic extrusion heads, 3 hot air drying devices, 4 forming tables and 5 ceramic formed objects.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below by combining the specific drawings.
The material manufacturing method according to the present invention is, as shown in fig. 1, method 1: firstly, mixing resin and additive according to a certain proportion (the concrete mixing proportion is that the resin is increased or decreased by 3-30% according to different forming temperatures and the urotropine is added by 0-2.5%) and then adding solvent to dissolve. Preparing the phenolic resin solution. And pouring the solution into ceramic powder, and stirring and mixing the solution in a closed container to form the ceramic mud. The mixing proportion of the solution and the ceramic powder is proportioned according to the field requirement. The above blending step is required to be carried out at normal temperature.
The material forming steps of the invention are shown in the figure: as shown in fig. 3 and 4: the 1 ceramic 3D printer drives the 2 ceramic extrusion head to move according to a programmed knife path of a program under the control of the program and extrudes ceramic mud on the surface of the 4 forming table, and the ceramic mud is accumulated layer by layer to form a ceramic forming object.
Drying as shown in fig. 5: 1 the 3 hot air drying device installed in the ceramic 3D printer is started to quickly evaporate the solvent in the ceramic mud to complete drying when the 5 ceramic forming object is formed to a certain degree. When using particularly volatile solvents, it is possible to use only blowing air without heating.
Primary curing: after the drying is completed, the 5-degree ceramic formed object is heated to 150-250 degrees to complete the primary curing. The heating time is determined according to the wall thickness or the size of the molded article. In general, the primary curing can be carried out.
Carbonizing: after drying or primary curing, the 5 ceramic forming object is put into a sintering furnace to be sintered at high temperature under oxygen-free environment, the sintering temperature is above 650 ℃, so that the phenolic resin starts to generate decomposition and carbonization reactions, and finally a C-C network structure is formed, so that the permanent binding phase is formed and has extremely high binding strength.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The manufacturing method of the three-dimensional additive forming material is characterized in that the formula of the material comprises four components, namely 30-40% of ceramic powder, 1.5-20% of thermosetting resin, 30-40% of solvent and 0.1-2.5% of additive; the manufacturing method comprises the steps of preparing ceramic mud, and then forming the ceramic mud;
the manufacturing method is divided into two methods;
the method comprises the following steps: firstly, mixing resin and additive according to a certain proportion, dissolving the mixture by using a solvent, and then mixing and stirring the solution and ceramic powder to form ceramic mud;
the second method comprises the following steps: uniformly stirring resin powder, an additive and ceramic powder to prepare mixed powder, and uniformly mixing and stirring the mixed powder and a solvent to prepare ceramic mud when the ceramic mud is used;
the forming process comprises the following four steps;
1) and primary forming: performing additive forming by using a pneumatic dispensing valve, a screw dispensing valve or a professional 3D ceramic printing extruder under the driving of a numerical control motion system;
2) and (3) drying: a blowing and heating device is arranged in the forming chamber, so that the solvent in the ceramic mud is quickly evaporated, and only blowing is carried out without heating when the solvent with particularly strong volatility is used;
3) and (3) primary curing: after drying, heating the formed product to 150-250 ℃ to complete primary curing, wherein the heating time is determined according to the wall thickness or the size of the formed product;
4) and carbonizing: after drying and primary curing, placing the formed product into a sintering furnace for high-temperature sintering in an oxygen-free environment, wherein the sintering temperature is above 650 ℃, so that phenolic resin is subjected to decomposition and carbonization reactions, and finally a material with a C-C network structure is formed;
the method is characterized in that the thermal curing effect and the low-oxygen environment carbonization phenomenon of the phenolic resin are introduced into the 3D ceramic mud printing field, so that the forming difficulty and the sintering requirement are greatly reduced.
2. The method of claim 1, wherein the ceramic powder is a powder material of oxide ceramic, carbide ceramic or nitride ceramic; the resin comprises water-soluble phenolic resin or alcohol-soluble phenolic resin; the solvent, water is used as the solvent in the case of using a water-soluble phenol resin, and methanol, ethanol, acetone, carbon tetrachloride or tetrahydrofuran is used as the solvent in the case of using an alcohol-soluble phenol resin; the additive comprises urotropine and dye.
3. The method of claim 2, wherein the phenolic resin is pre-mixed with a predetermined amount of urotropin.
4. The method of claim 2, wherein the ceramic 3D printer is internally installed with blowing and heating devices for drying the ceramic formed article, and the blowing and heating devices are integrated to cooperate or separate and independent work.
5. The manufacturing method of the three-dimensional additive forming material according to claim 2, wherein the ceramic 3D printer is configured to extrude ceramic mud for stacking forming, wherein the number of the extrusion heads for extruding the ceramic mud is one or more.
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| CN201710370827.5A CN108929113B (en) | 2017-05-24 | 2017-05-24 | Manufacturing method of three-dimensional additive forming material |
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| CN201710370827.5A CN108929113B (en) | 2017-05-24 | 2017-05-24 | Manufacturing method of three-dimensional additive forming material |
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| CN108929113A CN108929113A (en) | 2018-12-04 |
| CN108929113B true CN108929113B (en) | 2021-11-12 |
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| CN110441023B (en) * | 2019-07-30 | 2022-07-29 | 中国商用飞机有限责任公司北京民用飞机技术研究中心 | Miniature measurement rake for wind tunnel test and 3D printing method thereof |
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| DE3768887D1 (en) * | 1986-09-10 | 1991-05-02 | United Technologies Corp | MOLDING PROCESS FOR COAL-CARBON COMPOSITE. |
| CN1253410C (en) * | 2004-10-22 | 2006-04-26 | 西安交通大学 | Technological process of forming composite silicon carbide ceramic material based on pyrolysis of photocured prototype |
| DE102013018182A1 (en) * | 2013-10-30 | 2015-04-30 | Voxeljet Ag | Method and device for producing three-dimensional models with binder system |
| CN103554841B (en) * | 2013-11-08 | 2015-07-08 | 沈阳工业大学 | Resin composite material applicable to fast prototyping technology |
| CN105313332B (en) * | 2014-06-09 | 2020-05-05 | 联合工艺公司 | Two-part thermosetting resin additive manufacturing system |
| CN104163634A (en) * | 2014-07-02 | 2014-11-26 | 中国电子科技集团公司第五十五研究所 | A thermoplastic material used for three-dimensional printing and an application method thereof |
| CN104526838B (en) * | 2014-12-30 | 2017-01-11 | 宁波伏尔肯陶瓷科技有限公司 | Method for 3D ceramic printing forming |
| US10112873B2 (en) * | 2015-05-29 | 2018-10-30 | Raytheon Company | Ceramics with engineered microstructures via 3D printing and templated grain growth |
| CN105172142B (en) * | 2015-09-17 | 2018-06-08 | 中南大学 | A kind of 3D printing prepares carbon/carbon compound material method |
| CN105399428B (en) * | 2015-12-09 | 2019-02-12 | 中国建筑材料科学研究总院 | A kind of ceramic slurry and ceramic material 3D printing forming method |
| CN105669208A (en) * | 2016-03-07 | 2016-06-15 | 武汉理工大学 | Phenolic resin coated ceramic powder for laser 3D printing and preparation method thereof |
| CN106042408A (en) * | 2016-06-22 | 2016-10-26 | 武汉易制科技有限公司 | Powder material used for 3D printing and powder 3D printing forming method |
| CN106431357A (en) * | 2016-08-31 | 2017-02-22 | 淄博高新技术产业开发区先进陶瓷研究院 | Ceramic paste for 3D printing and molding, preparation method of paste and application thereof |
| CN106312069A (en) * | 2016-11-22 | 2017-01-11 | 赵晴堂 | Melt pool control method for additive manufacturing |
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Non-Patent Citations (1)
| Title |
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| 直写成型技术：一种新型微纳尺度三维结构的制备方法;孙月花 等;《中国有色金属学报》;20150731;第25卷(第6期);第1525-1537页 * |
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