WO2019200733A1 - 一种3d打印用料、其制备方法和用途 - Google Patents

一种3d打印用料、其制备方法和用途 Download PDF

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WO2019200733A1
WO2019200733A1 PCT/CN2018/095004 CN2018095004W WO2019200733A1 WO 2019200733 A1 WO2019200733 A1 WO 2019200733A1 CN 2018095004 W CN2018095004 W CN 2018095004W WO 2019200733 A1 WO2019200733 A1 WO 2019200733A1
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printing
binder
printing material
degreasing
mixing
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PCT/CN2018/095004
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English (en)
French (fr)
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侯春树
周龙金
侯文洁
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昆山卡德姆新材料科技有限公司
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Priority to US17/047,999 priority Critical patent/US20210163364A1/en
Publication of WO2019200733A1 publication Critical patent/WO2019200733A1/zh

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Definitions

  • the present application belongs to the technical field of 3D printing, and relates to a material for 3D printing, a preparation method thereof and use thereof.
  • 3D printing technology also known as 3D printing technology, is a technique for constructing objects by layer-by-layer printing based on digital model files using adhesive materials such as powder or plastic. It eliminates the need for machining or any mold to create parts of any shape directly from computer graphics data, dramatically reducing product development cycles, increasing productivity and reducing production costs. Products such as lampshades, body organs, jewelry, football boots tailored to the player's foot, racing parts, solid-state batteries, and custom-made cell phones, violins, etc. can be manufactured using this technology.
  • 3D printing technology is actually a collective term for a series of rapid prototyping technologies.
  • the basic principle is lamination manufacturing.
  • the rapid prototyping machine forms the cross-sectional shape of the workpiece by scanning in the XY plane, and intermittently makes the layer thickness in the Z coordinate. The displacement eventually forms a three-dimensional piece.
  • the rapid prototyping technology on the market is divided into 3DP technology, SLA (full name Service-Level Agreement) stereo light curing technology, SLS (full name Selective Laser Sintering) selective laser sintering technology, DMLS (full name Direct Metal Laser-Sintering) direct metal laser Sintering technology and FDM (Fused Deposition Modeling) fusion layer forming technology.
  • FDM fusion layer forming technology is the main method at present. It is to melt and melt the hot melt material, and the three-dimensional nozzle is selectively coated on the worktable according to the sectional profile information under the control of the computer. After rapid cooling. Form a section. After the formation of one layer, the machine table is lowered to a height (ie layer thickness) and continues to form until the entire solid shape is formed. It has many kinds of molding materials, high precision of molded parts and low price, and is mainly suitable for molding small plastic parts. However, the plastic products produced in this way have low strength and cannot meet the requirements of customers.
  • the DMLS technology uses the alloy powder material as a raw material, and the metal is melted by the focused energy laser to perform 3D printing lamination. It has the characteristics of high precision, high strength, fast speed, smooth surface of the finished product, etc. It is generally used in the aerospace and industrial parts manufacturing industry, and can be used in high-end mold design. However, the laser sintering equipment is complicated, and the energy consumption in the preparation process is high. Considering factors such as product resolution, equipment cost, product appearance requirements and mass production capacity, it is still not widely applicable and is not suitable for non-metallic materials with high melting point.
  • the current 3D printing method of non-metallic materials generally uses the SLA (full service-level agreement) stereo light curing technology to meet the needs of the current industry, this process needs to undergo molding, degreasing, sintering and other processes. Moreover, the state of the slurry is used, so that the product has a large sintering shrinkage ratio and a large thermal deformation.
  • SLA full service-level agreement
  • CN106270510A discloses a method for manufacturing metal/alloy parts by using a plastic 3D printer, which comprises the steps of sintering raw material pretreatment, raw material coating, powder reduction, 3D printing, degreasing, sintering, and the like.
  • CN106426916A discloses a 3D printing method comprising: mixing powdery material to be processed and powdered nylon material; melting the nylon material by selective laser sintering technology to bond the material to be processed to form a green body; heating the The green body is thermally degreased to volatilize the nylon material; the green body is heated to a sintering temperature of the material to be processed to sinter the green body; and the ambient temperature of the green body is lowered to room temperature to obtain a dense Components.
  • the feeding modes are powder or granular, which mainly has the following disadvantages: when using powdery or granular raw materials for 3D printing, it is necessary to The raw materials are spread and spread from the bottom to the top in the whole area, which greatly increases the feeding amount and causes waste of materials.
  • the hot zone since the hot zone is too large, the materials are easily melted and crosslinked.
  • the laser is used to melt and melt, the melting point of the polymer material is low, and the surrounding materials are also heated and melted, thereby affecting the accuracy and appearance of the product.
  • the shape of the powdery or granular feed is irregular, so that effective and uniform coating cannot be performed, which tends to cause uneven thickness of the surface of the product.
  • CN104669407A discloses that ceramic printing is performed by adding ceramic powder to each layer of paraffin wax, which is easy to form layer analysis and product joint strength problems. Subsequent patterns of slurry ceramic powder were proposed and evolved into a photocured slurry mode.
  • the photocurable slurry maintains its high fluidity to achieve a fast and stable laying work surface, and its ceramic powder has a low solid content, resulting in a high post-process sintering shrinkage rate, which makes the product easy to deform.
  • CN105728729A discloses a metal/ceramic powder forming method comprising the steps of: mixing a thermoplastic binder with a metal powder or a ceramic powder, and extruding a printing material for a fused deposition type 3D printer.
  • the powder solid content of the printing material obtained by the molding method cannot be improved, and can only reach 14% to 15%, and the high temperature sintering shrinkage rate of the product printed by using the printing material is as high as 47% to 48%, while the normal CIM
  • the high-temperature sintering shrinkage rate in the medium is 20% to 30%, and the product is easily deformed and distorted at high temperature sintering with the increase of the binder, which is disadvantageous for mass production.
  • CN106984805A discloses a feed for 3D printing and a preparation method and application thereof, wherein the feed is a metal powder wrapped with a polymer binder and has a linear shape. After the linear feeding prints the green body of the preset shape through the 3D printer, it is sequentially degreased and sintered, and a metal product with complicated structure and high precision can be obtained.
  • the preparation method cannot be applied to a non-metal material because the metal powder has a particle size distribution D90 of 20 to 25 ⁇ m (refer to particles having a particle diameter of 20 to 25 ⁇ m or less and 90% by weight of the total material), and the non-metal powder particle size distribution D90.
  • the non-metallic powder In the case of 0.5 to 1.0 ⁇ m (the 3D printing material obtained by the non-metallic powder having a coarse particle size causes the product to have a problem of sintering compactness, the density is low, and the mechanical properties are also lowered), so the non-metallic powder per unit weight
  • the overall surface area is much larger than the total surface area of the metal powder, and the fluidity of the non-metal material is much lower than that of the metal material at the same polymer binder content.
  • the non-metallic material cannot be prepared into a high solid content wire for use in 3D printing. Therefore, it is the direction of the industry to make non-metallic materials use this process technology to achieve the same effect as metal materials.
  • the purpose of the present application is to provide a 3D printing material, a preparation method thereof and a use thereof, wherein the solid content of the non-metal material in the 3D printing material is remarkably improved, and the obtained 3D printing product has small shrinkage and low variation in high-temperature sintering.
  • the product yield is improved.
  • the existing powder injection molding technology is combined with the 3D printing technology photosensitive resin, the raw material waste, complicated equipment and insufficient precision due to the curing form of the feed are avoided, and the preparation method is simple. Widely used in 3D printing.
  • vol% means volume percentage
  • wt% means mass percentage
  • One of the purposes of the present application is to provide a 3D printing material which is linear and contains the following components in volume percent:
  • the second binder is 0.1 to 1%.
  • the volume percentage of the non-metal material in the 3D printing material is 16-82%, such as 16%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%. %, 65%, 70%, 75% or 82%, etc.; the first binder has a volume percentage of 17.9 to 83%, such as 17.9%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 82%, etc.; the second binder has a volume percentage of 0.1 to 1%, such as 0.2%, 0.3%, 0.5%, 0.8% Or 0.9%, etc.
  • the solid content of the non-metal material in the 3D printing material is remarkably improved, and the obtained 3D printing product has small shrinkage and less variation in high-temperature sintering, and the product yield is improved; and the existing powder injection molding technology and 3D printing technology are avoided.
  • the photosensitive resin is combined, the raw material is wasted due to the solidification form of the feed, the equipment is complicated and expensive, and the precision is insufficient.
  • first binder and the second binder can be removed during degreasing and high temperature sintering after the preparation of the print.
  • the material can be supplied according to the required amount of materials for each layer of the printing piece, thereby saving raw materials; and the product can be controlled by selecting different wire diameters and controlling heating temperature.
  • the accuracy of the surface; and the 3D printing material can be melted by ordinary thermocouple heating, and does not require expensive photocuring printer equipment.
  • the linear 3D printing material has a diameter of 0.1 to 5 mm, such as 0.1 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, 3.5 mm, 4 mm, 4.5 mm or 5 mm, etc., preferably 1 to 3 mm. More preferably, it is 1.75 mm.
  • the non-metallic material has a particle size distribution D90 of 0.5 to 1.0 ⁇ m (refer to particles having a particle diameter of 0.5 to 1.0 ⁇ m or less, accounting for 90% by weight of the total material), such as 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m or 0.9 ⁇ m.
  • the smaller the particle size the larger the surface area per unit weight.
  • the frictional heat causes the polymer to be cracked to produce a pungent and spicy taste. Therefore, the use of the second binder can maintain the sintering characteristics of the fine powder and can achieve low OSF high fluidity.
  • the non-metallic material is selected from any one or a combination of at least two of an oxide ceramic material, a carbide ceramic material, a nitride ceramic material or a graphite material, a typical but non-limiting combination such as an oxide ceramic.
  • an oxide ceramic material a carbide ceramic material, a nitride ceramic material or a graphite material, a typical but non-limiting combination such as an oxide ceramic.
  • the oxide ceramic material is preferably any one or a combination of at least two of alumina ceramics, zirconia ceramics or piezoelectric ceramics, typical but non-limiting combinations such as alumina ceramics and zirconia ceramics, alumina ceramics , zirconia ceramics and piezoelectric ceramics.
  • the carbide ceramic material is preferably any one or a combination of at least two of a silicon carbide ceramic, a tungsten carbide ceramic, a vanadium carbide ceramic, a titanium carbide ceramic, a tantalum carbide ceramic or a boron carbide ceramic, a typical but non-limiting combination.
  • the nitride ceramic material is preferably any one or a combination of at least two of an aluminum nitride ceramic, a silicon nitride ceramic, a boron nitride ceramic, a titanium nitride ceramic or a chromium nitride ceramic, typically but not limited. Combinations such as aluminum nitride ceramics and silicon nitride ceramics, boron nitride ceramics, titanium nitride ceramics and chromium nitride ceramics.
  • the piezoelectric ceramics such as lead zirconate titanate (PZT) ceramic series, barium titanate (SBT) ceramic series.
  • the first binder is selected from a plastic based binder and/or a wax based binder.
  • the primary filler of the plastic-based binder is preferably polyoxymethylene (POM), and the primary filler of the wax-based binder is preferably paraffin (PW).
  • POM polyoxymethylene
  • PW paraffin
  • the second binder is selected from the group consisting of a thermosetting polymer material and/or a thermoplastic polymer material, preferably a thermosetting polymer material.
  • the thermosetting polymer material is selected from any one or a combination of at least two of a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, an epoxy resin, a silicone resin or a polyurethane.
  • a phenol resin a urea resin
  • a melamine resin an unsaturated polyester resin
  • an epoxy resin a silicone resin or a polyurethane.
  • Typical but non-limiting combinations are phenolic resins, urea-formaldehyde resins and melamine resins, unsaturated polyester resins and epoxy resins, silicone resins and polyurethanes.
  • the main design point is that after the thermosetting polymer is agglomerated, it will not be pulverized in the subsequent curing process, resulting in insufficient binder and reduced fluidity.
  • the thermoplastic polymer material is selected from any one or at least two of polypropylene, polyvinyl chloride, polystyrene, polyoxymethylene, polycarbonate, polyamide, acrylic, polysulfone or polyphenylene ether. Combination of species. Typical but non-limiting combinations are polypropylene and polyvinyl chloride, polystyrene, polyoxymethylene and polycarbonate, polyamide and acrylic plastics, polysulfone and polyphenylene ether.
  • the thermoplastic polymer material may also be other polyolefins and copolymers thereof.
  • the second object of the present application is to provide a method for preparing a 3D printing material as described above, which comprises the following steps:
  • the particle size distribution D90 of the non-metal material in the step (1) is 0.5 to 1.0 ⁇ m (refer to particles having a particle diameter of 0.5 to 1.0 ⁇ m or less, accounting for 90% by weight of the total material), such as 0.6 ⁇ m, 0.7 ⁇ m, 0.8 ⁇ m or 0.9 ⁇ m. Wait.
  • the particle size distribution D90 of the pellet obtained in the step (1) is 30 to 100 ⁇ m (refer to particles having a particle diameter of 30 to 100 ⁇ m or less, accounting for 90% by weight of the total material), such as 40 ⁇ m, 45 ⁇ m, 50 ⁇ m, 55 ⁇ m, 62 ⁇ m, 67 ⁇ m, 69 ⁇ m, 70 ⁇ m, 75 ⁇ m, 80 ⁇ m, 90 ⁇ m or 95 ⁇ m, etc., preferably 30 to 50 ⁇ m.
  • the granulation in the step (1) is spray drying granulation, and the spray-dry granulation can obtain the desired particle size distribution powder quickly and safely.
  • step (2) comprises kneading.
  • the kneading machine has a cavity temperature of 165 to 220 ° C, preferably 175 to 200 ° C, such as 170 ° C, 175 ° C, 180 ° C, 185 ° C, 190 ° C, 195 ° C or 210 ° C, etc. Further preferably 185 ° C;
  • the kneading time is 0.5 to 2 h, such as 0.6 h, 0.8 h, 1 h, 1.2 h, 1.5 h, 1.8 h or 2 h, etc., preferably 1 h.
  • the method for preparing the 3D printing material includes the following steps:
  • the preparation method of the 3D printing material provided by the embodiment of the invention firstly pre-processes the ultra-fine non-metal powder of D90 in the range of 0.5-1.0 ⁇ m, that is, the non-metal powder is immersed in the solvent containing the thermosetting polymer, and then Through the spray drying process, the semi-cured powder group is formed at 120-140 ° C, so that the powder can form a large group and the overall surface area thereof is greatly reduced, and then uniformly mixed with the first binder and extruded. High solid content linear 3D printing materials. After the pretreatment of the solvent containing the second binder described above, a linear 3D printing material having a high solid content and high toughness can be obtained at the same first binder content.
  • a third object of the present application is to provide a 3D printing method using the 3D printing material as described above.
  • the 3D printing method includes the following steps:
  • the degreasing according to the step (2) is such that more than 80% of the total binder (the total amount of the first binder and the second binder) can be separated from the product, and the higher the amount of degreasing, the poor cracking in the sintering process in the latter stage It will be greatly reduced, such as 82 wt%, 85 wt%, 88 wt%, 89 wt%, 90 wt%, 92 wt% or 95 wt%, and the like.
  • the degreasing step (2) is selected from the group consisting of thermal degreasing, water degreasing, catalytic degreasing or solvent degreasing, or a combination of at least two, typical but non-limiting combinations such as thermal degreasing and water degreasing, catalysis Degreasing and solvent degreasing, thermal degreasing, water degreasing and catalytic degreasing.
  • the catalytically degreased catalyst is nitric acid and/or oxalic acid.
  • the sintering temperature in the step (3) is 1200 to 1500 ° C, such as 1210 ° C, 1220 ° C, 1230 ° C, 1240 ° C, 1250 ° C, 1300 ° C, 1350 ° C, 1400 ° C, 1450 ° C or 1480 ° C, etc. It is preferably 1300 to 1450 °C.
  • the sintering time in the step (3) is 2 to 3 hours, such as 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3h.
  • post-processing is performed, and those skilled in the art can post-process the sintered parts according to actual conditions, and the manner of post-processing can be selected independently.
  • the 3D printing method includes the following steps:
  • the brown billet is sintered to obtain a sintered part, the sintering temperature is 1200 to 1500 ° C, and the time is 2 to 3 h, and the sintered part is post-processed to obtain a molded piece.
  • the 3D printing method provided by the embodiment of the invention combines the powder injection molding technology with the 3D printing technology to obtain a linear high solid content non-metal 3D printing material, which can be applied to 3D printing according to the printing article.
  • the amount of material required for the layer is fed, which saves the raw materials; at the same time, the precision of the surface of the product can be controlled by selecting different wire diameters of the feed and controlling the heating temperature; and the feed prepared by the embodiment of the invention adopts an ordinary thermocouple. It melts when heated and does not require expensive photocuring printer equipment.
  • a fourth object of the present application is to provide a method for improving the non-metal content in a 3D printing material, which employs a 3D printing material as described above.
  • the method comprises the steps of:
  • the volume percentage of the non-metallic material in the 3D printing material can reach 82%.
  • the volume percentage of the non-metal material in the 3D printing material is 16-82%, such as 16%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%. %, 65%, 70%, 75% or 80%, etc.
  • the solid content of the non-metal material in the 3D printing material provided by the embodiment of the invention is remarkably improved, and the obtained 3D printing product has small shrinkage and low variation in high-temperature sintering, and the product yield is improved by 10 to 30%;
  • the existing powder injection molding technology is combined with the 3D printing technology photosensitive resin, the raw material is wasted due to the curing form of the feed, the equipment is complicated and expensive, and the precision is insufficient.
  • the 3D printing material provided by the embodiment of the present invention can control the thickness of the 3D printing layer by controlling different wire diameters and controlling the heating temperature to improve the precision of the surface of the product and the quality of the product.
  • the 3D printing material provided by the embodiment of the invention can be heated and melted by a simple thermocouple, which does not require complicated and expensive laser heating equipment, reduces energy consumption, reduces production cost, and can be widely used for 3D printing. .
  • the preparation method of the 3D printing material provided by the embodiment of the invention significantly improves the solid content of the non-metal material in the 3D printing material, and can make the non-metal content reach 82 wt%, and the method is simple and easy;
  • the 3D printing method provided by the embodiment of the present invention combines powder injection molding technology and 3D printing technology, can quickly print and manufacture complex products, shorten the development process, and realize mass production popularization.
  • FIG. 1 is a flow chart of a 3D printing process provided by an embodiment of the present application.
  • a 3D printing method as shown in FIG. 1, includes the following steps:
  • the brown billet is sintered to obtain a sintered part, the sintering temperature is 1200 to 1500 ° C, and the time is 2 to 3 h, and the sintered part is post-processed to obtain a molded piece.
  • the preparation of the linear 3D printing material may further include the following steps:
  • a high solid content non-metallic 3D printing material which is linear and comprises 44 vol% zirconia ceramic powder, 55.5 vol% of a first binder and a second binder of 0.5 vol% by volume.
  • the preparation method of the high solid content non-metal 3D printing material comprises the following steps:
  • the zirconia ceramic powder having a particle size distribution D90 of 0.5 to 1.0 ⁇ m is mixed with a second binder (phenolic resin solution), spray-dried and granulated, and dried at a temperature of 120 ° C to obtain a semi-cured powder.
  • a second binder phenolic resin solution
  • the particle size distribution D90 is 30 ⁇ 100 ⁇ m
  • the first binder comprising: polyoxymethylene 85 wt%, backbone polymer 11 wt%, plasticizer 1 wt%, antioxidant 0.5 wt%, heat stable 0.5wt% agent, toughener 1wt%, lubricant polymer 1wt%; the raw materials are added to the mixer, kneaded at 180 ° C for 1h;
  • the printing method using the high solid content non-metal 3D printing material includes the following steps:
  • the green body obtained in the step (1) is degreased at 110 ° C for 10 h using nitric acid as a medium, and the first binder is removed to obtain a brown billet;
  • the brown blank obtained in the step (2) is placed in a high-temperature atmosphere furnace, sintered at 1450 ° C for 3 hours, and cooled to obtain a zirconia ceramic product.
  • the performance of the molded part is as follows: the powder structure is reduced to reduce the total powder surface area, so the powder group is easy to form a dough, and the thickness of the polymer film is increased to make the liquidity of the feed high (>MFI 1200), the volume It has a disk shape and high toughness, which is suitable for automatic feeding processing.
  • a high solid content non-metallic 3D printing material which is linear and comprises 40 vol% zirconia ceramic powder, 59.2 vol% of a first binder and a second binder of 0.8 vol% by volume.
  • the preparation method of the high solid content non-metal 3D printing material comprises the following steps:
  • the zirconia ceramic powder having a particle size distribution D90 of 0.5 to 1.0 ⁇ m is mixed with a second binder (phenolic resin solution), and then spray-dried and granulated at a temperature of 120 ° C to obtain a semi-cured powder.
  • the first binder comprising: polyoxymethylene 85 wt%, backbone polymer 11 wt%, plasticizer 1 wt%, antioxidant 0.5 wt%, heat stable 0.5wt% agent, toughener 1wt%, lubricant polymer 1wt%; the raw materials are added to the mixer, kneaded at 180 ° C for 1h;
  • the line is The feed is wound into a disk shape for backup.
  • the printing method using the high solid content non-metal 3D printing material includes the following steps:
  • the green body obtained in the step (1) is degreased at 110 ° C for 10 h using nitric acid as a medium, and the first binder is removed to obtain a brown billet;
  • the brown blank obtained in the step (2) is placed in a high-temperature atmosphere furnace, sintered at 1450 ° C for 3 hours, and cooled to obtain a zirconia ceramic product.
  • the performance of the molded part is as follows: the powder structure is reduced to reduce the total powder surface area, so the powder group is easy to form a dough, and the thickness of the polymer film is increased to make the liquidity of the feed high (>MFI 1200), the volume It has a disk shape and high toughness, which is suitable for automatic feeding processing.
  • a high solid content non-metallic 3D printing material which is linear and comprises 50 vol% alumina-zirconia ceramic powder and 49 vol% of first binder and second binder 1.0 vol% by volume percent .
  • the preparation method of the high solid content non-metal 3D printing material comprises the following steps:
  • Alumina-zirconia ceramic powder having a particle size distribution D90 of 0.5 to 1.0 ⁇ m is mixed with a second binder (phenolic resin solution), spray-dried and granulated, and dried at a temperature of 120 ° C to obtain semi-curing.
  • the first binder comprising: polyoxymethylene 85 wt%, backbone polymer 11 wt%, plasticizer 1 wt%, antioxidant 0.5 wt% , the heat stabilizer 0.5wt%, the toughener 1wt%, the lubricant polymer 1wt%; the raw materials are added to the internal mixer, and kneaded at 180 ° C for 1h;
  • the line is The feed is wound into a disk shape for backup.
  • the printing method using the high solid content non-metal 3D printing material includes the following steps:
  • the green body obtained in the step (1) is degreased at 110 ° C for 10 h using nitric acid as a medium, and the first binder is removed to obtain a brown billet;
  • the brown blank obtained in the step (2) is placed in a high-temperature atmosphere furnace, sintered at 1500 ° C for 3 hours, and cooled to obtain an alumina-toughened zirconia ceramic product.
  • the performance of the molded part is as follows: the powder structure is reduced to reduce the total powder surface area, so the powder group is easy to form a dough, and the thickness of the polymer film is increased to make the liquidity of the feed high (>MFI 1200), the volume It has a disk shape and high toughness, which is suitable for automatic feeding processing.
  • a high solid content non-metallic 3D printing material which is linear and comprises 16 vol% graphite material, 83.4 vol% of a first binder and a second binder of 0.6 vol% by volume.
  • the preparation method of the high solid content non-metal 3D printing material comprises the following steps:
  • the graphite material with the first binder, the first binder comprising: 85 wt% of polyoxymethylene and paraffin, 11 wt% of backbone polymer, 1 wt% of plasticizer, 0.5 wt% of antioxidant, Heat stabilizer 0.5 wt%, toughener 1 wt%, lubricant polymer 1 wt%; the raw materials were added to an internal mixer, and kneaded at 165 ° C for 2 h;
  • the printing method using the high solid content non-metal 3D printing material includes the following steps:
  • the green body obtained in the step (1) is degreased at 110 ° C using a petrochemical solvent for 24 hours, and the first binder is removed to obtain a brown billet;
  • the performance of the molded part is as follows: the powder structure is reduced to reduce the total powder surface area, so the powder group is easy to form a dough, and the thickness of the polymer film is increased to make the liquidity of the feed high (>MFI 1200), the volume It has a disk shape and high toughness, which is suitable for automatic feeding processing.
  • a high solid content non-metal 3D printing material which is linear and comprises 82 vol% silicon nitride ceramic powder, 17.9 vol% of first binder and second binder 0.1 vol% by volume percent .
  • the preparation method of the high solid content non-metal 3D printing material comprises the following steps:
  • the silicon nitride ceramic powder (2) mixing the silicon nitride ceramic powder with the first binder, the first binder comprising: polyoxymethylene 85 wt%, backbone polymer 11 wt%, plasticizer 1 wt%, antioxidant 0.5 wt%, Heat stabilizer 0.5wt%, toughener 1wt%, lubricant polymer 1wt%; the raw materials are added to the internal mixer, and kneaded at 220 ° C for 0.5h;
  • the printing method using the high solid content non-metal 3D printing material includes the following steps:
  • the green body obtained in the step (1) is degreased at 110 ° C for 10 h using nitric acid as a medium, and the first binder is removed to obtain a brown billet;
  • the brown blank obtained in the step (2) is placed in a high-temperature vacuum furnace, sintered at 1800 ° C for 2.5 h, and cooled to obtain a silicon nitride ceramic product.
  • the performance of the molded part is as follows: the powder structure is reduced to reduce the total powder surface area, so the powder group is easy to form a dough, and the thickness of the polymer film is increased to make the liquidity of the feed high (>MFI 1200), the volume It has a disk shape and high toughness, which is suitable for automatic feeding processing.
  • the alumina-toughened zirconia ceramic product was molded by the printing method described in Example 3 using the 3D printing material obtained by the above method.
  • the performance of the molded part is as follows: the powder structure is reduced to reduce the total powder surface area, so the powder group is easy to form a dough, and the thickness of the polymer film is increased to make the liquidity of the feed high (>MFI 1200), the volume It has a disk shape and high toughness, which is suitable for automatic feeding processing.
  • a method for preparing a 3D printing material is the same as in the third embodiment except that the pellet having a particle size distribution D90 of 5 to 20 ⁇ m is obtained in the step (1).
  • the alumina-toughened zirconia ceramic product was molded by the printing method described in Example 3 using the 3D printing material obtained by the above method.
  • the performance of the molded part is as follows: the powder structure is reduced to reduce the total powder surface area, so the powder group is easy to form a dough, and the thickness of the polymer film is increased to make the liquidity of the feed high (>MFI 1200), the volume It has a disk shape and high toughness, which is suitable for automatic feeding processing.
  • a method for preparing a 3D printing material is the same as in Embodiment 3 except that the pellet having a particle size distribution D90 of 120 to 180 ⁇ m is obtained in the step (1).
  • the alumina-toughened zirconia ceramic product was molded by the printing method described in Example 3 using the 3D printing material obtained by the above method.
  • the performance of the molded part is as follows: the powder structure is reduced to reduce the total powder surface area, so the powder group is easy to form a dough, and the thickness of the polymer film is increased to make the liquidity of the feed high (>MFI 1200), the volume It has a disk shape and high toughness, which is suitable for automatic feeding processing.
  • a method for preparing a 3D printing material except that the second binder is not pretreated, that is, 50 vol% alumina-zirconia ceramic powder is directly mixed with 50 vol% of the first binder, and the rest and the examples 3 is the same.
  • the alumina-toughened zirconia ceramic product was molded by the printing method described in Example 3 using the 3D printing material obtained by the above method.
  • the performance of the molded part is: because the total surface area of the ultrafine powder is high, it is not easy to form a dough under a quantitative polymer content, and the polymer film thickness is thin, resulting in poor fluidity of the feed ( ⁇ MFI 200 ), its toughness is easy to break and cannot be drawn into a coil shape.
  • the dimensional shrinkage and product yield of the 3D printed product obtained in Examples 1-8 were tested. As a result, the high-temperature sintering size of the 3D printed product obtained in Examples 1-8 was compared with the 3D printed product obtained in the prior art. The shrinkage is small and the variation is small, and the product yield is increased by 10 to 30%.
  • the second binder in Examples 1-8 is replaced with any other thermosetting polymer material such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin or polyurethane. Or a combination of at least two; or replaced with other thermoplastic polymer materials such as polypropylene, polyvinyl chloride, polystyrene, polyoxymethylene, polycarbonate, polyamide, acrylic, polysulfone or polyphenylene ether Any one or a combination of at least two.
  • the obtained 3D printing products have small shrinkage and low variation in high-temperature sintering, and the product yield is improved by 10 to 30%.

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Abstract

一种3D打印用料、其制备方法和用途， 3D打印用料为线状，按体积百分含量，包括16～82％的非金属材料、17.9～83％的第一粘结剂和第二粘结剂0.1～1％；其通过将非金属材料预处理后与第一粘结剂混合，挤出得到。

Description

一种3D打印用料、其制备方法和用途 技术领域
本申请属于3D打印技术领域，涉及一种3D打印用料、其制备方法和用途。
背景技术
3D打印(3D printing)技术又称三维打印技术，是一种以数字模型文件为基础，运用粉末状或塑料等可粘合材料，通过逐层打印的方式来构造物体的技术。它无需机械加工或任何模具，就能直接从计算机图形数据中生成任何形状的零件，从而极大地缩短产品的研制周期，提高生产率和降低生产成本。诸如灯罩、身体器官、珠宝、根据球员脚型定制的足球靴、赛车零件、固态电池以及为个人定制的手机、小提琴等产品都可以用该技术制造出来。
3D打印技术实际上是一系列快速原型成型技术的统称，其基本原理都是叠层制造，由快速原型机在X-Y平面内通过扫描形式形成工件的截面形状，而在Z坐标间断地作层面厚度的位移，最终形成三维制件。目前市场上的快速成型技术分为3DP技术、SLA(全称Service-Level Agreement)立体光固化技术、SLS(全称Selective Laser Sintering)选择性激光烧结技术、DMLS(全称Direct Metal Laser-Sintering)直接金属激光烧结技术及FDM(全称Fused Deposition Modeling)熔融层积成型技术等。
3D打印技术最早应用在塑料材料上。FDM熔融层积成型技术是目前主要方式，它是将热熔性材料加热融化，同时三维喷头在计算机的控制下，根据截面轮廓信息，将材料选择性地涂敷在工作台上，快速冷却后形成一层截面。一层成型完成后，机器工作台下降一个高度(即分层厚度)继续成型，直至形成 整个实体造型。其成型材料种类多，成型件精度较高、价格便宜，主要适用于成型小塑料件。然而这种方式产生的塑料产品强度低并不能满足客户的要求。为了增加产品的强度，改善产品的性能，DMLS技术采用合金粉体材料为原料，利用金属经聚焦后之能量激光将原料熔融后进行3D打印迭层。其具有高精度、高强度，速度快，成品表面光滑等特点，一般应用于航空航天以及工业用配件制造行业，可用于高阶模具设计等。但激光烧结设备复杂，制备过程能耗高，综合考虑产品分辨率、设备费用、产品外观要求及量产能力等因素，目前仍无法大量普及应用且不适合高熔点的非金属材料使用。所以目前非金属材料的3D打印方式一般是使用SLA(全称Service-Level Agreement)立体光固化技术来满足目前工业的需求，此工艺需要经过成型、脱脂、烧结等制程。而且使用浆料状态故其产品的烧结收缩率偏大，热变形也大。
CN106270510A中公开了一种利用塑料3D打印机打印制造金属/合金零件的方法，该方法包括烧结原材料前处理、原材料包覆、粉末还原、3D打印、脱脂、烧结等步骤。CN106426916A中公开了一种3D打印方法，包括：混合粉末状待加工材料及粉末状尼龙材料；采用选择性激光烧结技术熔化所述尼龙材料以粘结所述待加工材料形成生坯；加热所述生坯进行热脱脂以使所述尼龙材料挥发；加热所述生坯至所述待加工材料的烧结温度以对所述生坯进行烧结；将所述生坯的环境温度降至室温以得到致密零件。上述两种方法虽然都将粉末注塑成型和3D打印技术相结合，但是其喂料模式均为粉状或颗粒状，主要存在以下缺点：使用粉状或颗粒状的原料进行3D打印时，需要将原料由下至上逐层在全区铺展涂布，大大增加了喂料量，造成了材料的浪费。在熔融过程中由于热区过大，材料之间易熔融交联，使用激光加热熔解结合时，因高分子材料的熔点低而易造成周边材料也被加热熔融，进而影响其产品精度及外观。同时 粉体状或颗粒状喂料的形态不规则，因此无法进行有效均匀的涂布，易造成产品表面厚度不均。
CN104669407A公开了陶瓷打印的方式是在每一层石蜡上添加陶瓷粉体，这种方式容易造层分析及产品接合强度问题。随后有浆料陶瓷粉体的模式被提出，进而演化至光固化浆料模式。光固化浆料为维持其高流动性以达到快速稳定铺排工作台面，其陶瓷粉体固含量偏低，导致后制程烧结收缩率偏高使得产品容易变形。
CN105728729A公开了一种金属/陶瓷粉末成形方法，包括步骤如下：将热塑性粘结剂与金属粉末或者陶瓷粉末混合，并挤出成型用于熔融沉积型3D打印机的打印材料。但是，该成型方法得到的打印材料的粉体固含量无法提升，只能达到14％～15％，且使用该打印材料打印出的产品的高温烧结收缩率高达47％～48％，而正常CIM中的高温烧结收缩率在20％～30％，随着黏结剂的增多产品在高温烧结容易变形扭曲，因此不利于量产。
CN106984805A公开了一种3D打印用喂料及其制备方法和应用，所述喂料为高分子粘结剂包裹的金属粉体，呈线状。所述线状喂料经由3D打印机打印出预设形状的生坯后，依次经过脱脂、烧结，可得到结构复杂、精度高的金属产品。但是，该制备方法无法用于非金属材料，因为金属粉体粒度分布D90在20～25μm(指粒径在20～25μm以下的颗粒占总物料的90wt％)，而非金属粉体粒度分布D90在0.5～1.0μm(粗粒径的非金属粉体得到的3D打印用料会导致产品存在烧结致密性问题，密度会偏低，机械性能也会降低)，所以单位重量下的非金属粉体的总体表面积远大于金属粉体的总体表面积，在相同的高分子粘结剂的含量下非金属材料的流动性远低于金属材料的流动性。在此情况下无法将非金属材料制备成高固含量的线材，进而用于3D打印。因此，使非金属材料可 以运用此工艺技术来达到与金属材料相同的效果是业者努力的方向。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于提供一种3D打印用料、其制备方法和用途，所述3D打印用料中非金属材料的固含量显著提升，其得到的3D打印产品高温烧结尺寸收缩小且变异少，产品良率提升；同时避免了现有粉末注射成型技术与3D打印技术光敏树酯结合时，因喂料固化形态而导致的原料浪费、设备复杂昂贵和精度不足等问题，其制备方法简单，可广泛用于3D打印。
本申请如无特殊说明，所述vol％是指体积百分含量，wt％是指质量百分含量。
为达此目的，本申请采用以下技术方案：
本申请的目的之一在于提供一种3D打印用料，所述3D打印用料为线状，按体积百分含量，包括如下组分：
非金属材料                           16～82％；
第一粘结剂                           17.9～83％
第二粘结剂                           0.1～1％。
所述3D打印用料中非金属材料的体积百分含量为16～82％，如16％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％或82％等；第一粘结剂的体积百分含量为17.9～83％，如17.9％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％、80％或82％等；第二粘结剂的体积百分含量为0.1～1％，如0.2％、0.3％、0.5％、0.8％或0.9％等。
本领域技术人员公知，所述3D打印用料中的组分总的体积百分含量之和 应为100％。
所述3D打印用料中非金属材料的固含量显着提升，其得到的3D打印产品高温烧结尺寸收缩小且变异少，产品良率提升；同时避免了现有粉末注射成型技术与3D打印技术光敏树酯结合时，因喂料固化形态而导致的原料浪费、设备复杂昂贵和精度不足等问题。
本领域技术人员公知，所述第一粘结剂和第二粘结剂在制备打印件后的脱脂及高温烧结过程中能够脱除。
本发明实施例提供的3D打印用料应用于3D打印时，可以根据打印件每层所需的用料量进行供料，节省了原料；同时可以通过选择不同线径以及控制加热温度来控制产品表面的精度；且所述3D打印用料采用普通的热电偶加热即可熔融，不需要昂贵的光固化打印机设备。
所述线状3D打印用料的直径为0.1～5mm，如0.1mm、0.5mm、1mm、1.5mm、2mm、2.5mm、3mm、3.5mm、4mm、4.5mm或5mm等，优选为1～3mm，更优选为1.75mm。
所述非金属材料的粒度分布D90为0.5～1.0μm(指粒径为0.5～1.0μm以下的颗粒占总物料的90wt％)，如0.6μm、0.7μm、0.8μm或0.9μm等。粉体粒径越小其单位重量的表面积越大，要得到相同流动性的高分子含量越高所以其开模放大率(Oversizing factor，OSF)越大；同时在混练过程中易因粉体摩擦热造成高分子裂解产生刺鼻辛辣味，故使用第二黏结剂可以维持细粉的烧结特性外又可以得到低OSF高流动性。
优选地，所述非金属材料选自氧化物陶瓷材料、碳化物陶瓷材料、氮化物陶瓷材料或石墨材料中的任意一种或至少两种的组合，典型但非限制性的组合如氧化物陶瓷材料与碳化物陶瓷材料，氧化物陶瓷材料与氮化物陶瓷材料，碳 化物陶瓷材料与石墨材料。
所述氧化物陶瓷材料优选为氧化铝陶瓷、氧化锆陶瓷或压电陶瓷中的任意一种或至少两种的组合，典型但非限制性的组合如氧化铝陶瓷与氧化锆陶瓷，氧化铝陶瓷、氧化锆陶瓷和压电陶瓷。
所述碳化物陶瓷材料优选为碳化硅陶瓷、碳化钨陶瓷、碳化钒陶瓷、碳化钛陶瓷、碳化钽陶瓷或碳化硼陶瓷中的任意一种或至少两种的组合，典型但非限制性的组合如碳化硅陶瓷与碳化钨陶瓷，碳化钒陶瓷、碳化钛陶瓷与碳化钽陶瓷，碳化硼陶瓷，碳化硅陶瓷、碳化钨陶瓷与碳化钒陶瓷。
所述氮化物陶瓷材料优选为氮化铝陶瓷、氮化硅陶瓷、氮化硼陶瓷、氮化钛陶瓷或氮化铬陶瓷中的任意一种或至少两种的组合，典型但非限制性的组合如氮化铝陶瓷与氮化硅陶瓷，氮化硼陶瓷、氮化钛陶瓷与氮化铬陶瓷。
所述压电陶瓷，如钛锆酸铅(PZT)陶瓷系列、钛酸锶铋(SBT)陶瓷系列。
优选地，所述第一粘结剂选自塑基粘结剂和/或蜡基粘结剂。
所述塑基粘结剂的主填充剂优选为聚甲醛(POM)，所述蜡基粘结剂的主填充剂优选为石蜡(PW)。
优选地，所述第二粘结剂选自热固性高分子材料和/或热塑性高分子材料，优选为热固性高分子材料。
优选地，所述热固性高分子材料选自酚醛树脂、脲醛树脂、三聚氰胺树脂、不饱和聚酯树脂、环氧树脂、有机硅树脂或聚氨酯中的任意一种或至少两种的组合。典型但非限制性的组合如酚醛树脂、脲醛树脂与三聚氰胺树脂，不饱和聚酯树脂与环氧树脂，有机硅树脂与聚氨酯。主要设计要点是热固性高分子结团后在后续密练过程中不会粉碎造成黏结剂不足而降低流动性。
优选地，所述热塑性高分子材料选自聚丙烯、聚氯乙烯、聚苯乙烯、聚甲 醛、聚碳酸酯、聚酰胺、丙烯酸类塑料、聚砜或聚苯醚中的任意一种或至少两种的组合。典型但非限制性的组合如聚丙烯与聚氯乙烯，聚苯乙烯、聚甲醛与聚碳酸酯，聚酰胺与丙烯酸类塑料，聚砜与聚苯醚。所述热塑性高分子材料还可以是其它聚烯烃及其共聚物。
本申请的目的之二在于提供一种如上所述的3D打印用料的制备方法，所述制备方法包括如下步骤：
(1)将配方量的非金属材料与配方量的第二粘结剂混合后进行造粒，得到粒料；
(2)将所述粒料与配方量的第一粘结剂混合，得到混合料；
(3)将所述混合料挤出，得到所述3D打印用料。
步骤(1)所述非金属材料的粒度分布D90为0.5～1.0μm(指粒径为0.5～1.0μm以下的颗粒占总物料的90wt％)，如0.6μm、0.7μm、0.8μm或0.9μm等。
步骤(1)得到的粒料的粒度分布D90为30～100μm(指粒径为30～100μm以下的颗粒占总物料的90wt％)，如40μm、45μm、50μm、55μm、62μm、67μm、69μm、70μm、75μm、80μm、90μm或95μm等，优选为30～50μm。
优选地，步骤(1)所述造粒为喷雾干燥造粒，所述喷雾干燥造粒可以快速安全有效得到所要的粒度分布粉体。
优选地，步骤(2)所述混合包括混炼。
优选地，所述混炼时混炼机的腔体温度为165～220℃，优选为175～200℃，如170℃、175℃、180℃、185℃、190℃、195℃或210℃等，进一步优选为185℃；
优选地，所述混炼的时间为0.5～2h，如0.6h、0.8h、1h、1.2h、1.5h、1.8h或2h等，优选为1h。
作为优选的技术方案，所述3D打印用料的制备方法包括如下步骤：
(1)将配方量的粒度分布D90为0.5～1.0μm的非金属材料与配方量的第二粘结剂混合后进行喷雾干燥造粒，得到粒度分布D90为30～100μm的粒料；
(2)将所述粒料与配方量的第一粘结剂进行混炼，混炼时腔体的温度为165～220℃，混炼时间为0.5～2h，得到混合料；
(3)将所述混合料挤出，得到所述3D打印用料。
本发明实施例提供的3D打印用料的制备方法首先将D90在0.5～1.0μm的超细非金属粉体进行预处理制程，即将非金属粉体置于含热固性高分子的溶剂内浸泡后再经喷雾干燥制程，以120～140℃形成半固化粉团，使其粉体可以形成较大团状且其总体表面积大幅减少，之后再将其与第一粘结剂混合均匀，挤出，得到高固含量的线状3D打印用料。经过上述含有第二粘结剂的溶剂的预处理，才能在相同的第一粘结剂含量下得到高固含量及高韧性的线状3D打印用料。
本申请的目的之三在于提供一种3D打印方法，所述3D打印方法使用如上所述的3D打印用料。
作为优选的技术方案，所述3D打印方法包括如下步骤：
(1)以3D打印用料为原料，经由3D打印机打印出预设形状的生坯；
(2)将生坯进行脱脂，得到褐坯；
(3)将褐坯进行烧结，得到成型件。
步骤(2)所述脱脂使得80％以上的总粘结剂(第一粘结剂和第二粘结剂的总量)可以脱离产品，其脱脂量越高，在后段烧结制程的开裂不良会大幅降低，如82wt％、85wt％、88wt％、89wt％、90wt％、92wt％或95wt％等。
优选地，步骤(2)所述脱脂选自热脱脂、水脱脂、催化脱脂或溶剂脱脂中 的任意一种或至少两种的组合，典型但非限制性的组合如热脱脂与水脱脂，催化脱脂与溶剂脱脂，热脱脂、水脱脂与催化脱脂。
优选地，所述催化脱脂的催化剂为硝酸和/或草酸。
优选地，步骤(3)所述烧结的温度为1200～1500℃，如1210℃、1220℃、1230℃、1240℃、1250℃、1300℃、1350℃、1400℃、1450℃或1480℃等，优选为1300～1450℃。
优选地，步骤(3)所述烧结的时间为2～3h，如2h、2.1h、2.2h、2.3h、2.4h、2.5h、2.6h、2.7h、2.8h、2.9h或3h等。
优选地，步骤(3)所述烧结后还进行后加工，本领域技术人员可根据实际情况对烧结件进行后加工，后加工的方式可自主选择。
作为优选的技术方案，所述3D打印方法包括如下步骤：
(1)以3D打印用料为原料，经由3D打印机打印出预设形状的生坯；
(2)将生坯进行脱脂，脱除80wt％以上的总粘结剂，得到褐坯；
(3)将褐坯进行烧结，得到烧结件，烧结的温度为1200～1500℃，时间为2～3h，将烧结件进行后加工，得到成型件。
本发明实施例提供的3D打印方法将粉末注射成型技术与3D打印技术相结合，得到一种线状的高固含量非金属3D打印用料，将其应用于3D打印时，可以根据打印件每层所需的用料量进行供料，节省了原料；同时可以通过选择喂料的不同线径以及控制加热温度来控制产品表面的精度；且本发明实施例制备的喂料采用普通的热电偶加热即可熔融，不需要昂贵的光固化打印机设备。
本申请的目的之四在于提供一种提高3D打印用料中非金属含量的方法，所述方法采用如上所述的3D打印用料。
优选地，所述方法包括如下步骤：
(1)将配方量的非金属材料与配方量的第二粘结剂混合后进行造粒，得到粒料；
(2)将所述粒料与配方量的第一粘结剂混合，得到混合料；
(3)将所述混合料挤出，得到非金属材料的体积百分含量不小于16％的3D打印用料。所述3D打印用料中非金属材料的体积百分含量可达到82％。所述3D打印用料中非金属材料的体积百分含量为16～82％，如16％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％或80％等。
本发明实施例所述的数值范围不仅包括上述例举的点值，还包括没有例举出的上述数值范围之间的任意的点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
与现有技术相比，本发明实施例的有益效果为：
(1)本发明实施例提供的3D打印用料中非金属材料的固含量显著提升，其得到的3D打印产品高温烧结尺寸收缩小且变异少，产品良率提升10～30％；同时避免了现有粉末注射成型技术与3D打印技术光敏树酯结合时，因喂料固化形态而导致的原料浪费、设备复杂昂贵和精度不足等问题。
(2)本发明实施例提供的3D打印用料可以通过控制不同线径以及控制加热温度来控制3D打印层的厚度进而提高产品表面的精度及产品的质量。
(3)本发明实施例提供的3D打印用料可通过简单的热电偶进行加热熔融处理，不需要复杂且昂贵的激光加热设备，减少了能耗，降低了生产成本，可广泛用于3D打印。
(4)本发明实施例提供的3D打印用料的制备方法显著提升了3D打印用料中非金属材料的固含量，能够使得非金属含量达到82wt％，方法简单，易行；
(5)本发明实施例提供的3D打印方法将粉末注射成型技术和3D打印技术相结合，可以快速打印制作复杂的产品，缩短开发流程，实现量产普及化。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
图1为本申请一种实施方式提供的3D打印工艺流程图。
具体实施方式
下面结合附图并通过具体实施方式来进一步说明本发明实施例的技术方案。
一种3D打印方法，如图1所示，包括如下步骤：
(1)制备线状3D打印用料，以3D打印用料为原料，经由3D打印机打印出预设形状的生坯；
(2)将生坯进行脱脂，脱除第一粘结剂的80wt％以上，得到褐坯；
(3)将褐坯进行烧结，得到烧结件，烧结的温度为1200～1500℃，时间为2～3h，将烧结件进行后加工，得到成型件。
所述制备线状3D打印用料还可包括如下步骤：
(1)将粒度分布D90为0.5～1.0μm的非金属材料与第二粘结剂混合后进行喷雾干燥造粒，得到粒度分布D90为30～100μm的粒料；
(2)将上述(1)的粒料与第一粘结剂进行混炼，混炼时腔体的温度为165～220℃，混炼时间为0.5～2h，得到混合料；
(3)将所述混合料挤出，得到所述3D打印用料。
实施例1
一种高固含量非金属3D打印用料，其为线状，按体积百分含量包括 44vol％氧化锆陶瓷粉、55.5vol％的第一粘结剂和第二粘结剂0.5vol％。
所述高固含量非金属3D打印用料的制备方法包括如下步骤：
(1)将粒度分布D90为0.5～1.0μm的氧化锆陶瓷粉与第二粘结剂(酚醛树酯溶液)混合后进行喷雾干燥造粒，以120℃的温度干燥，获得半固化态的粉团颗粒，其粒度分布D90为30～100μm；
(2)将氧化锆陶瓷粉与第一粘结剂混合，所述第一粘结剂包括：聚甲醛85wt％、骨干高分子11wt％、增塑剂1wt％、抗氧化剂0.5wt％、热稳定剂0.5wt％、增韧剂1wt％、润滑剂高分子1wt％；将所述原料加入密炼机中，在180℃下混炼1h；
(3)利用挤出机将步骤(1)混炼后得到的材料挤出为直径为1.75mm的线状材料，冷却后得到所述高固含量非金属3D打印用料，将所述线状料卷绕为盘状备用。
利用所述高固含量非金属3D打印用料的打印方法包括如下步骤：
(1)将所述线状喂料作为原料，经由3D打印机打印出预设形状的生坯；
(2)将步骤(1)得到的生坯在110℃下，使用硝酸为介质脱脂4h，脱除第一粘结剂，得到褐坯；
(3)将步骤(2)得到的褐坯置于高温大气炉中，在1450℃下烧结3h，冷却后得到氧化锆陶瓷产品。
所述成型件的性能为：因增加粉团结构降低总粉体表面积，故粉团容易结成团状，且其高分子膜厚度增加使其喂料的流动性高(＞MFI 1200)，卷成线盘状，其韧性高，适合自动送料加工。
实施例2
一种高固含量非金属3D打印用料，其为线状，按体积百分含量包括40vol％氧化锆陶瓷粉、59.2vol％的第一粘结剂和第二粘结剂0.8vol％。
所述高固含量非金属3D打印用料的制备方法包括如下步骤：
(1)将粒度分布D90为0.5～1.0μm的氧化锆陶瓷粉与第二粘结剂(酚醛树酯溶液)混合后在温度为120℃条件下进行喷雾干燥造粒，得到半固化态的粉团，其粒度分布D90为30～100μm的粒料；
(2)将氧化锆陶瓷粉与第一粘结剂混合，所述第一粘结剂包括：聚甲醛85wt％、骨干高分子11wt％、增塑剂1wt％、抗氧化剂0.5wt％、热稳定剂0.5wt％、增韧剂1wt％、润滑剂高分子1wt％；将所述原料加入密炼机中，在180℃下混炼1h；
(3)利用挤出机将步骤(1)混炼后得到的材料挤出为直径为1.75mm的线状材料，冷却后得到所述高固含量非金属3D打印用喂料，将所述线状喂料卷绕为盘状备用。
利用所述高固含量非金属3D打印用料的打印方法包括如下步骤：
(1)将所述线状喂料作为原料，经由3D打印机打印出预设形状的生坯；
(2)将步骤(1)得到的生坯在110℃下，使用硝酸为介质脱脂4h，脱除第一粘结剂后得到褐坯；
(3)将步骤(2)得到的褐坯置于高温大气炉中，在1450℃下烧结3h，冷却后得到氧化锆陶瓷产品。
所述成型件的性能为：因增加粉团结构降低总粉体表面积，故粉团容易结成团状，且其高分子膜厚度增加使其喂料的流动性高(＞MFI 1200)，卷成线盘状，其韧性高，适合自动送料加工。
实施例3
一种高固含量非金属3D打印用料，其为线状，按体积百分含量包括50vol％氧化铝-氧化锆陶瓷粉和49vol％的第一粘结剂和第二粘结剂1.0vol％。
所述高固含量非金属3D打印用料的制备方法包括如下步骤：
(1)将粒度分布D90为0.5～1.0μm的氧化铝-氧化锆陶瓷粉与第二粘结剂(酚醛树酯溶液)混合后进行喷雾干燥造粒，以120℃的温度干燥，获得半固化态的粉团颗粒，其粒度分布D90为30～100μm的粒料；
(2)将氧化铝-氧化锆陶瓷粉与第一粘结剂混合，所述第一粘结剂包括：聚甲醛85wt％、骨干高分子11wt％、增塑剂1wt％、抗氧化剂0.5wt％、热稳定剂0.5wt％、增韧剂1wt％、润滑剂高分子1wt％；将所述原料加入密炼机中，在180℃下混炼1h；
(3)利用挤出机将步骤(1)混炼后得到的材料挤出为直径为1.75mm的线状材料，冷却后得到所述高固含量非金属3D打印用喂料，将所述线状喂料卷绕为盘状备用。
利用所述高固含量非金属3D打印用料的打印方法包括如下步骤：
(1)将所述线状喂料作为原料，经由3D打印机打印出预设形状的生坯；
(2)将步骤(1)得到的生坯在110℃下，使用硝酸为介质脱脂4h，脱除第一粘结剂后得到褐坯；
(3)将步骤(2)得到的褐坯置于高温大气炉中，在1500℃下烧结3h，冷却后得到氧化铝增韧氧化锆陶瓷产品。
所述成型件的性能为：因增加粉团结构降低总粉体表面积，故粉团容易结成团状，且其高分子膜厚度增加使其喂料的流动性高(＞MFI 1200)，卷成线盘状，其韧性高，适合自动送料加工。
实施例4
一种高固含量非金属3D打印用料，其为线状，按体积百分含量包括16vol％石墨材料、83.4vol％的第一粘结剂和第二粘结剂0.6vol％。
所述高固含量非金属3D打印用料的制备方法包括如下步骤：
(1)将粒度分布D90为0.5～1.0μm的石墨材料与第二粘结剂(酚醛树酯溶液)混合，在120℃的条件下进行喷雾干燥造粒，获得半固化态的粉团颗粒，其粒度分布D90为30～100μm的粒料；
(2)将石墨材料与第一粘结剂混合，所述第一粘结剂包括：聚甲醛及石腊合计85wt％、骨干高分子11wt％、增塑剂1wt％、抗氧化剂0.5wt％、热稳定剂0.5wt％、增韧剂1wt％、润滑剂高分子1wt％；将所述原料加入密炼机中，在165℃下混炼2h；
(3)利用挤出机将步骤(1)混炼后得到的材料挤出为直径为0.1mm的线状材料，冷却后得到所述高固含量非金属3D打印用料，将所述线状料卷绕为盘状备用。
利用所述高固含量非金属3D打印用料的打印方法包括如下步骤：
(1)将所述线状喂料作为原料，经由3D打印机打印出预设形状的生坯；
(2)将步骤(1)得到的生坯在110℃下，使用石化剂为溶剂脱脂24h，脱除第一粘结剂，得到褐坯；
(3)将步骤(2)得到的褐坯置于高温真空炉中，在1850℃下烧结3h，冷却后得到石墨产品。
所述成型件的性能为：因增加粉团结构降低总粉体表面积，故粉团容易结成团状，且其高分子膜厚度增加使其喂料的流动性高(＞MFI 1200)，卷成线盘状，其韧性高，适合自动送料加工。
实施例5
一种高固含量非金属3D打印用料，其为线状，按体积百分含量包括82vol％氮化硅陶瓷粉体、17.9vol％的第一粘结剂和第二粘结剂0.1vol％。
所述高固含量非金属3D打印用料的制备方法包括如下步骤：
(1)将粒度分布D90为0.5～1.0μm的氮化硅陶瓷粉体与第二粘结剂(酚醛树酯溶液)混合，在120℃的条件下进行喷雾干燥造粒，获得半固化态的粉团颗粒，其粒度分布D90为30～100μm的粒料；
(2)将氮化硅陶瓷粉体与第一粘结剂混合，所述第一粘结剂包括：聚甲醛85wt％、骨干高分子11wt％、增塑剂1wt％、抗氧化剂0.5wt％、热稳定剂0.5wt％、增韧剂1wt％、润滑剂高分子1wt％；将所述原料加入密炼机中，在220℃下混炼0.5h；
(3)利用挤出机将步骤(1)混炼后得到的材料挤出为直径为5mm的线状材料，冷却后得到所述高固含量非金属3D打印用料，将所述线状料卷绕为盘状备用。
利用所述高固含量非金属3D打印用料的打印方法包括如下步骤：
(1)将所述线状喂料作为原料，经由3D打印机打印出预设形状的生坯；
(2)将步骤(1)得到的生坯在110℃下，使用硝酸为介质脱脂4h，脱除第一粘结剂，得到褐坯；
(3)将步骤(2)得到的褐坯置于高温真空炉中，在1800℃下烧结2.5h，冷却后得到氮化硅陶瓷产品。
所述成型件的性能为：因增加粉团结构降低总粉体表面积，故粉团容易结成团状，且其高分子膜厚度增加使其喂料的流动性高(＞MFI 1200)，卷成线盘状，其韧性高，适合自动送料加工。
实施例6
一种高固含量非金属3D打印用料，其组分及制备方法除将50％氧化铝-氧化锆陶瓷粉替换为55％碳化硅陶瓷粉体，并适应性调整第一粘结剂的体积百分含量外，其余与实施例3相同。
使用上述方法得到的3D打印用料，利用实施例3所述打印方法成型氧化铝增韧氧化锆陶瓷产品。所述成型件的性能为：因增加粉团结构降低总粉体表面积，故粉团容易结成团状，且其高分子膜厚度增加使其喂料的流动性高(＞MFI 1200)，卷成线盘状，其韧性高，适合自动送料加工。
实施例7
一种3D打印用料的制备方法除步骤(1)得到粒度分布D90为5～20μm的粒料外，其余与实施例3相同。
使用上述方法得到的3D打印用料，利用实施例3所述打印方法成型氧化铝增韧氧化锆陶瓷产品。所述成型件的性能为：因增加粉团结构降低总粉体表面积，故粉团容易结成团状，且其高分子膜厚度增加使其喂料的流动性高(＞MFI 1200)，卷成线盘状，其韧性高，适合自动送料加工。
实施例8
一种3D打印用料的制备方法除步骤(1)得到粒度分布D90为120～180μm的粒料外，其余与实施例3相同。
使用上述方法得到的3D打印用料，利用实施例3所述打印方法成型氧化铝增韧氧化锆陶瓷产品。所述成型件的性能为：因增加粉团结构降低总粉体表面积，故粉团容易结成团状，且其高分子膜厚度增加使其喂料的流动性高(＞MFI  1200)，卷成线盘状，其韧性高，适合自动送料加工。
对比例1
一种3D打印用料的制备方法，除不进行第二粘结剂的预处理，即直接将50vol％氧化铝-氧化锆陶瓷粉与50vol％的第一粘结剂混合外，其余与实施例3相同。
使用上述方法得到的3D打印用料，利用实施例3所述打印方法成型氧化铝增韧氧化锆陶瓷产品。所述成型件的性能为：因超细粉体总表面积高，故在定量的高分子含量下不容易结成团状，且其高分子膜厚度薄，导致喂料的流动性差(＜MFI 200)，其韧性差易断裂无法拉成线盘状。
对实施例1-8得到的3D打印产品的尺寸收缩及产品良率进行测试，结果为：实施例1-8得到的3D打印产品相较于现有技术得到的3D打印产品，其高温烧结尺寸收缩小且变异少，产品良率提升10～30％。
将实施例1-8中的第二粘结剂替换为其它热固性高分子材料如，酚醛树脂、脲醛树脂、三聚氰胺树脂、不饱和聚酯树脂、环氧树脂、有机硅树脂或聚氨酯中的任意一种或至少两种的组合；或替换为其它的热塑性高分子材料，如聚丙烯、聚氯乙烯、聚苯乙烯、聚甲醛、聚碳酸酯、聚酰胺、丙烯酸类塑料、聚砜或聚苯醚中的任意一种或至少两种的组合。制得的3D打印产品相较于现有技术得到的3D打印产品，高温烧结尺寸收缩小且变异少，产品良率提升10～30％。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，均落在本申请的保护范围和公开范围之内。

Claims (12)

  1. 一种3D打印用料，其中，所述3D打印用料为线状，按体积百分含量，其包括如下组分：
    非金属材料   16～82％；
    第一粘结剂   17.9～83％
    第二粘结剂   0.1～1％。
  2. 根据权利要求1所述的3D打印用料，其中，所述线状3D打印用料的直径为0.1～5mm。
  3. 根据权利要求2所述的3D打印用料，其中，所述非金属材料的粒度分布D90为0.5～1.0μm。
  4. 根据权利要求2所述的3D打印用料，其中，所述非金属材料选自氧化物陶瓷材料、碳化物陶瓷材料、氮化物陶瓷材料或石墨材料中的任意一种或至少两种的组合；
    优选地，所述第一粘结剂选自塑基粘结剂和/或蜡基粘结剂；
    优选地，所述第二粘结剂选自热固性高分子材料和/或热塑性高分子材料，优选为热固性高分子材料；
    优选地，所述热固性高分子材料选自酚醛树脂、脲醛树脂、三聚氰胺树脂、不饱和聚酯树脂、环氧树脂、有机硅树脂或聚氨酯中的任意一种或至少两种的组合；
    优选地，所述热塑性高分子材料选自聚丙烯、聚氯乙烯、聚苯乙烯、聚甲醛、聚碳酸酯、聚酰胺、丙烯酸类塑料、聚砜或聚苯醚中的任意一种或至少两种的组合。
  5. 根据权利要求1至4中任一项所述的3D打印用料的制备方法，其中，所述制备方法包括如下步骤：
    (1)将配方量的非金属材料与配方量的第二粘结剂混合后进行造粒，得到粒料；
    (2)将所述粒料与配方量的第一粘结剂混合，得到混合料；
    (3)将所述混合料挤出，得到所述3D打印用料。
  6. 根据权利要求5所述的制备方法，其中，步骤(1)所述非金属材料的粒度分布D90为0.5～1.0μm；
    优选地，步骤(1)所述粒料的粒度分布D90为30～100μm，优选为30～50μm；
    优选地，步骤(1)所述造粒为喷雾干燥造粒；
    优选地，步骤(2)所述混合包括混炼；
    优选地，所述混炼时腔体的温度为165～220℃，优选为175～200℃，进一步优选为185℃；
    优选地，所述混炼的时间为0.5～2h，优选为1h。
  7. 根据权利要求5或6所述的制备方法，其中，所述3D打印用料的制备方法包括如下步骤：
    (1)将配方量的粒度分布D90为0.5～1.0μm的非金属材料与配方量的第二粘结剂混合后进行喷雾干燥造粒，得到粒度分布D90为30～100μm的粒料；
    (2)将所述粒料与配方量的第一粘结剂进行混炼，混炼时腔体的温度为165～220℃，混炼时间为0.5～2h，得到混合料；
    (3)将所述混合料挤出，得到所述3D打印用料。
  8. 一种3D打印方法，其中，所述3D打印方法使用权利要求1至4中任一项所述的3D打印用料。
  9. 根据权利要求8所述的3D打印方法，其中，所述3D打印方法包括如下步骤：
    (1)以3D打印用料为原料，经由3D打印机打印出预设形状的生坯；
    (2)将生坯进行脱脂，得到褐坯；
    (3)将褐坯进行烧结，得到成型件。
  10. 根据权利要求9所述的用途，其中，步骤(2)所述脱脂脱除第一粘结剂和第二粘结剂总量的80wt％以上；
    优选地，步骤(2)所述脱脂选自热脱脂、水脱脂、催化脱脂或溶剂脱脂中的任意一种或至少两种的组合；
    优选地，所述催化脱脂的催化剂为硝酸和/或草酸；
    优选地，步骤(3)所述烧结的温度为1200～1500℃，优选为1300～1450℃；
    优选地，步骤(3)所述烧结的时间为2～3h；
    优选地，步骤(3)所述烧结后还进行后加工。
  11. 根据权利要求9或10所述的3D打印方法，其中，所述3D打印方法包括如下步骤：
    (1)以3D打印用料为原料，经由3D打印机打印出预设形状的生坯；
    (2)将生坯进行脱脂，脱除第一粘结剂和第二粘结剂总量的80wt％以上，得到褐坯；
    (3)将褐坯进行烧结，得到烧结件，烧结的温度为1200～1500℃，时间为2～3h，将烧结件进行后加工，得到成型件。
  12. 一种提高3D打印用料中非金属含量的方法，其中，所述方法采用权利要求1至4中任一项所述的3D打印用料。
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