3D PRINTING MATERIAL, PREPARATION METHOD AND USE THEREOF

Abstract

Disclosed are a 3D printing material, a preparation method and use thereof. The 3D printing material is linear, and it comprises, in percent by volume, 16 to 82% of a non-metal material, 17.9 to 83% of a first binder and 0.1 to 1% of a second binder. The material is obtained by pre-treating the non-metallic material, then mixing with the first binder, and extruding.

Claims

1. A 3D printing material, comprising: a non-metallic material 16 to 82 vol %; a first binder 17.9 to 83 vol %; and a second binder 0.1 to 1 vol %, wherein the 3D printing material is linear.

2. The 3D printing material according to claim 1, wherein, the linear 3D printing material has a diameter in the range of 0.1 to 5 mm.

3. The 3D printing material according to claim 1, wherein, the non-metal material has a size distribution D90 of 0.5 to 1.0 μm.

4. The 3D printing material according to claim 1, wherein, the non-metal material is selected from any one or a combination of at least two of oxide ceramic materials, carbide ceramic materials, nitride ceramic materials, and graphite materials.

5. A preparation method for the 3D printing material according to claim 1, wherein, the preparation method comprises the following steps: (1) mixing a formulated amount of the non-metallic material with a formulated amount of the second binder and then granulating to obtain pellets; (2) mixing the pellets with a formulated amount of the first binder, to obtain a mixture; and (3) extruding the mixture, to obtain the 3D printing material.

6. The preparation method according to claim 5, wherein, the non-metal material in Step (1) has a size distribution D90 of 0.5 to 1.0 μm.

7. The preparation method according to claim 5 or 6, wherein, the preparation method for the 3D printing material comprises the following steps: (1) mixing the formulated amount of the non-metallic material with a size distribution D90 of 0.5 to 1.0 μm with the formulated amount of the second binder and then performing spray drying granulation to obtain pellets with a size distribution D90 of 30 to 100 μm; (2) mixing-milling the pellets with the formulated amount of the first binder, with a chamber temperature of 165 to 220° C. and a mixing-milling time of 0.5 to 2 h during mixing-milling, to obtain the mixture; (3) extruding the mixture, to obtain the 3D printing material.

8. A 3D printing method, wherein, the 3D printing method uses the 3D printing material according to claim 1.

9. The 3D printing method according to claim 8, wherein, the 3D printing method comprises the following steps: (1) taking the 3D printing material as a raw material to print a raw blank with a preset shape through a 3D printer; (2) degreasing the raw blank to obtain a brown blank; and (3) sintering the brown blank to obtain a molded part.

10. The use 3D printing method according to claim 9, wherein, the degreasing in Step (2) removes over 80 wt % of the total amount of the first binder and the second binder.

11. The 3D printing method according to claim 9 or 10, wherein, the 3D printing method comprises the following steps: (1) taking the 3D printing material as the raw material to print the raw blank with the preset shape through the 3D printer; (2) degreasing the raw blank, and removing over 80 wt % of the total amount of the first binder and the second binder, to obtain the brown blank; and (3) sintering the brown blank at a sintering temperature of 1200 to 1500° C. and a time of 2 to 3 h to obtain a sintered part, and post processing the sintered part to obtain a molded part.

12. A method of increasing non-metal content in a 3D printing material, wherein, the method uses the 3D printing material according to claim 1.

13. The 3D printing material according to claim 1, wherein the first binder is selected from plastic-based binders and/or wax-based binders.

14. The 3D printing material according to claim 1, wherein the second binder is selected from thermosetting polymer materials and/or thermoplastic polymer materials.

15. The 3D printing material according to claim 1, wherein the thermosetting polymer materials are selected from any one or a combination of at least two of phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, organic silicone resin, and polyurethane, and the thermoplastic polymer materials are selected from any one or a combination of at least two of polypropylene, polyvinyl chloride, polystyrene, polyoxymethylene, polycarbonate, polyamide, acrylic plastic, polysulfone, and polyphenylene oxide.

16. The preparation method according to claim 5, wherein the pellets in Step (1) have a size distribution D90 of 30 to 100 μm.

17. The preparation method according to claim 5, wherein: the granulating in Step (1) is spray drying granulation, the mixing in Step (2) comprises mixing-milling, a chamber temperature during the mixing-milling is 165 to 220° C., and a mixing-milling time is 0.5 to 2 h, and preferably is 1 h.

18. The 3D printing method according to claim 9, wherein: the degreasing in Step (2) is selected from any one or a combination of at least two of thermal degreasing, water degreasing, catalytic degreasing, and solvent degreasing, and a catalyst of the catalytic degreasing is nitric acid and/or oxalic acid.

19. The 3D printing method according to claim 9, wherein: a sintering temperature in Step (3) is 1200 to 1500° C., and a sintering time in Step (3) is 2 to 3 h.

20. The 3D printing method according to claim 9, wherein post-processing is performed after sintering in Step (3).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0078] FIG. 1 is a process flow chart of 3D printing provided by one implementation of the present application.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

[0079] In the following, the technical solution of the embodiments of the present disclosure is further explained in detail combining with the accompanying drawings and by means of specific implementations.

[0080] A 3D printing method, as shown in FIG. 1, comprises the following steps:

[0081] (1) preparing a linear 3D printing material, taking the 3D printing material as a raw material to print a raw blank with a preset shape through a 3D printer;

[0082] (2) degreasing the raw blank, and removing over 80 wt % of the first binder, to obtain a brown blank; and

[0083] (3) sintering the brown blank at a sintering temperature of 1200 to 1500° C. and a time of 2 to 3 h to obtain a sintered part, and post processing the sintered part to obtain a molded part.

[0084] The preparing a linear 3D printing material further comprises the following steps:

[0085] (1) mixing a non-metallic material with a size distribution D90 of 0.5 to 1.0 μm with a second binder and then performing spray drying granulation to obtain pellets with a size distribution D90 of 30 to 100 μm;

[0086] (2) mixing the pellets in Step (1) with a first binder, with a chamber temperature of 165 to 220° C. and a mixing time of 0.5 to 2 h during mixing, to obtain a mixture; and

[0087] (3) extruding the mixture, to obtain the 3D printing material.

Embodiment 1

[0088] A high-solid content non-metal 3D printing material, is linear, and it comprises, in percent by volume, 44 vol % of a zirconia ceramic powder, 55.5 vol % of a first binder and 0.5 vol % of a second binder.

[0089] The preparation method of the high-solid content non-metal 3D printing material comprises the following steps:

[0090] (1) The zirconia ceramic powder with a size distribution D90 of 0.5 to 1.0 μm was mixed with the second binder (a phenolic resin solution) and then spray drying granulated at 120° C. to form semi-solidified powder agglomerate particles which has a size distribution D90 of 30 to 100 μm;

[0091] (2) The zirconia ceramic powder was mixed with the first binder, the first binder comprises: 85 wt % polyoxymethylene, 11 wt % backbone polymer, 1 wt % plasticizer, 0.5 wt % antioxidant, 0.5 wt % heat stabilizer, 1 wt % toughening agent, and 1 wt % lubricant polymer; the raw materials was added into an internal mixer, mixing-milling at 180° C. for 1 h;

[0092] (3) The mixed material obtained in Step (1) was extruded to a linear material with a diameter of 1.75 mm, then cooled to obtain the high-solid content non-metal 3D printing material which was wound to a coil shape to reserve.

[0093] The printing method using the high-solid content non-metal 3D printing material comprises the following steps:

[0094] (1) the linear feed was taken as a raw material to print a raw blank with a preset shape through a 3D printer;

[0095] (2) the raw blank obtained in Step (1) was degreased for 4 h at 110° C. and using nitric acid as the medium, to remove the first binder and obtain a brown blank;

[0096] (3) the brown blank obtained in Step (2) was placed in a high-temperature atmospheric furnace to sinter at 1450° C. for 3 h, and cooled to obtain a zirconia ceramic product.

[0097] The performance of the molded part is: due to the structure of the powder agglomerates is increased and the total surface area of the powder is reduced, the powder is easy to form agglomerates, and the thickness of the polymer film increases to cause a high fluidity of the feed (>MFI 1200), and it is wound in the shape of a coil with high toughness, suitable for automatic feeding processing.

Embodiment 2

[0098] A high-solid content non-metal 3D printing material, is linear, and it comprises, in percent by volume, 40 vol % of a zirconia ceramic powder, 59.2 vol % of a first binder and 0.8 vol % of a second binder.

[0099] The preparation method of the high-solid content non-metal 3D printing material comprises the following steps:

[0100] (1) The zirconia ceramic powder with a size distribution D90 of 0.5 to 1.0 μm was mixed with the second binder (a phenolic resin solution) and then spray drying granulated at 120° C. to form semi-solidified powder agglomerates which are pellets having a size distribution D90 of 30 to 100 μm;

[0101] (2) The zirconia ceramic powder was mixed with the first binder, the first binder comprises: 85 wt % polyoxymethylene, 11 wt % backbone polymer, 1 wt % plasticizer, 0.5 wt % antioxidant, 0.5 wt % heat stabilizer, 1 wt % toughening agent, and 1 wt % lubricant polymer; the raw materials was added into an internal mixer, mixing-milling at 180° C. for 1 h;

[0102] (3) The mixed material obtained in Step (1) was extruded to a linear material with a diameter of 1.75 mm, then cooled to obtain the high-solid content non-metal feed for 3D printing, the linear feed was wound to a coil shape to reserve.

[0103] The printing method using the high-solid content non-metal 3D printing material comprises the following steps:

[0104] (1) the linear feed was taken as a raw material to print a raw blank with a preset shape through a 3D printer;

[0105] (2) the raw blank obtained in Step (1) was degreased for 4 h at 110° C. and using nitric acid as the medium, to remove the first binder and obtain a brown blank;

[0106] (3) the brown blank obtained in Step (2) was placed in a high-temperature atmospheric furnace to sinter at 1450° C. for 3 h, and cooled to obtain a zirconia ceramic product.

[0107] The performance of the molded part is: due to the structure of the powder agglomerates is increased and the total surface area of the powder is reduced, the powder is easy to form agglomerates, and the thickness of the polymer film increases to cause a high fluidity of the feed (>MFI 1200), and it is wound in the shape of a coil with high toughness, suitable for automatic feeding processing.

Embodiment 3

[0108] A high-solid content non-metal 3D printing material, is linear, and it comprises, in percent by volume, 50 vol % of an alumina-zirconia ceramic powder, 49 vol % of a first binder and 1.0 vol % of a second binder.

[0109] The preparation method of the high-solid content non-metal 3D printing material comprises the following steps:

[0110] (1) The alumina-zirconia ceramic powder with a size distribution D90 of 0.5 to 1.0 μm was mixed with the second binder (a phenolic resin solution) and then spray drying granulated at 120° C. to form semi-solidified powder agglomerate particles which are pellets having a size distribution D90 of 30 to 100 μm;

[0111] (2) The alumina-zirconia ceramic powder was mixed with the first binder, the first binder comprises: 85 wt % polyoxymethylene, 11 wt % backbone polymer, 1 wt % plasticizer, 0.5 wt % antioxidant, 0.5 wt % heat stabilizer, 1 wt % toughening agent, and 1 wt % lubricant polymer; the raw materials was added into an internal mixer, mixing-milling at 180° C. for 1 h;

[0112] (3) The mixed material obtained in Step (1) was extruded to a linear material with a diameter of 1.75 mm, then cooled to obtain the high-solid content non-metal feed for 3D printing, the linear feed was wound to a coil shape to reserve.

[0113] The printing method using the high-solid content non-metal 3D printing material comprises the following steps:

[0114] (1) the linear feed was taken as a raw material to print a raw blank with a preset shape through a 3D printer;

[0115] (2) the raw blank obtained in Step (1) was degreased for 4 h at 110° C. and using nitric acid as the medium, to remove the first binder and obtain a brown blank;

[0116] (3) the brown blank obtained in Step (2) was placed in a high-temperature atmospheric furnace to sinter at 1500° C. for 3 h, and cooled to obtain an alumina-zirconia ceramic product.

[0117] The performance of the molded part is: due to the structure of the powder agglomerates is increased and the total surface area of the powder is reduced, the powder is easy to form agglomerates, and the thickness of the polymer film increases to cause a high fluidity of the feed (>MFI 1200), and it is wound in the shape of a coil with high toughness, suitable for automatic feeding processing.

Embodiment 4

[0118] A high-solid content non-metal 3D printing material, is linear, and it comprises, in percent by volume, 16 vol % of a graphite material, 83.4 vol % of a first binder and 0.6 vol % of a second binder.

[0119] The preparation method of the high-solid content non-metal 3D printing material comprises the following steps:

[0120] (1) The graphite material with a size distribution D90 of 0.5 to 1.0 μm was mixed with the second binder (a phenolic resin solution) and then spray drying granulated at 120° C. to form semi-solidified powder agglomerate particles which are pellets having a size distribution D90 of 30 to 100 μm;

[0121] (2) The graphite material was mixed with the first binder, the first binder comprises: 85 wt % polyoxymethylene and paraffin, 11 wt % backbone polymer, 1 wt % plasticizer, 0.5 wt % antioxidant, 0.5 wt % heat stabilizer, 1 wt % toughening agent, and 1 wt % lubricant polymer; the raw materials was added into an internal mixer, mixing-milling at 165° C. for 2 h;

[0122] (3) The mixed material obtained in Step (1) was extruded to a linear material with a diameter of 0.1 mm, then cooled to obtain the high-solid content non-metal 3D printing material which was wound to a coil shape to reserve.

[0123] The printing method using the high-solid content non-metal 3D printing material comprises the following steps:

[0124] (1) the linear feed was taken as a raw material to print a raw blank with a preset shape through a 3D printer;

[0125] (2) the raw blank obtained in Step (1) was degreased for 24 h at 110° C. and using a petrochemical agent as the medium, to remove the first binder and obtain a brown blank;

[0126] (3) the brown blank obtained in Step (2) was placed in a high-temperature vacuum furnace to sinter at 1850° C. for 3 h, and cooled to obtain a graphite product.

[0127] The performance of the molded part is: due to the structure of the powder agglomerates is increased and the total surface area of the powder is reduced, the powder is easy to form agglomerates, and the thickness of the polymer film increases to cause a high fluidity of the feed (>MFI 1200), and it is wound in the shape of a coil with high toughness, suitable for automatic feeding processing.

Embodiment 5

[0128] A high-solid content non-metal 3D printing material, is linear, and it comprises, in percent by volume, 82 vol % of a silicon nitride ceramic powder, 17.9 vol % of a first binder and 0.1 vol % of a second binder.

[0129] The preparation method of the high-solid content non-metal 3D printing material comprises the following steps:

[0130] (1) The silicon nitride ceramic powder with a size distribution D90 of 0.5 to 1 μm was mixed with the second binder (a phenolic resin solution) and then spray drying granulated at 120° C. to form semi-solidified powder agglomerate particles which are pellets having a size distribution D90 of 30 to 100 μm;

[0131] (2) The silicon nitride ceramic powder was mixed with the first binder, the first binder comprises: 85 wt % polyoxymethylene, 11 wt % backbone polymer, 1 wt % plasticizer, 0.5 wt % antioxidant, 0.5 wt % heat stabilizer, 1 wt % toughening agent, and 1 wt % lubricant polymer; the raw materials was added into an internal mixer, mixing-milling at 220° C. for 0.5 h;

[0132] (3) The mixed material obtained in Step (1) was extruded to a linear material with a diameter of 5 mm, then cooled to obtain the high-solid content non-metal 3D printing material which was wound to a coil shape to reserve.

[0133] The printing method using the high-solid content non-metal 3D printing material comprises the following steps:

[0134] (1) the linear feed was taken as a raw material to print a raw blank with a preset shape through a 3D printer;

[0135] (2) the raw blank obtained in Step (1) was degreased for 4 h at 110° C. and using nitric acid as the medium, to remove the first binder and obtain a brown blank;

[0136] (3) the brown blank obtained in Step (2) was placed in a high-temperature vacuum furnace to sinter at 1800° C. for 2.5 h, and cooled to obtain a silicon nitride ceramic product.

[0137] The performance of the molded part is: due to the structure of the powder agglomerates is increased and the total surface area of the powder is reduced, the powder is easy to form agglomerates, and the thickness of the polymer film increases to cause a high fluidity of the feed (>MFI 1200), and it is wound in the shape of a coil with high toughness, suitable for automatic feeding processing.

Embodiment 6

[0138] A high-solid content non-metal 3D printing material has the same components and preparation method as those of Embodiment 3, except that the 50% alumina-zirconia ceramic powder was replaced with 55% silicon carbide ceramic powder and the volume percentage of the first binder was adaptively adjusted.

[0139] The 3D printing material obtained according to the above method was used, and the printing method of Embodiment 3 was utilized to mold an alumina toughened zirconia ceramic product. The performance of the molded part is: due to the structure of the powder agglomerates is increased and the total surface area of the powder is reduced, the powder is easy to form agglomerates, and the thickness of the polymer film increases to cause a high fluidity of the feed (>MFI 1200), and it is wound in the shape of a coil with high toughness, suitable for automatic feeding processing.

Embodiment 7

[0140] A preparation method of the 3D printing material is the same as in Embodiment 3, except that the pellets obtained in Step (1) has a size distribution D90 of 5 to 20 μm.

[0141] The 3D printing material obtained according to the above method was used, and the printing method of Embodiment 3 was utilized to mold an alumina toughened zirconia ceramic product. The performance of the molded part is: due to the structure of the powder agglomerates is increased and the total surface area of the powder is reduced, the powder is easy to form agglomerates, and the thickness of the polymer film increases to cause a high fluidity of the feed (>MFI 1200), and it is wound in the shape of a coil with high toughness, suitable for automatic feeding processing.

Embodiment 8

[0142] A preparation method of the 3D printing material is the same as in Embodiment 3, except that the pellets obtained in Step (1) has a size distribution D90 of 120 to 180 μm.

[0143] The 3D printing material obtained according to the above method was used, and the printing method of Embodiment 3 was utilized to mold an alumina toughened zirconia ceramic product. The performance of the molded part is: due to the structure of the powder agglomerates is increased and the total surface area of the powder is reduced, the powder is easy to form agglomerates, and the thickness of the polymer film increases to cause a high fluidity of the feed (>MFI 1200), and it is wound in the shape of a coil with high toughness, suitable for automatic feeding processing.

[0144] Comparison 1

[0145] A preparation method of a 3D printing material is the same as in Embodiment 3, except that 50 vol % alumina-zirconia ceramic powder was directly mixed with 50 vol % first binder without preprocessing by the second binder.

[0146] The 3D printing material obtained according to the above method was used, and the printing method of Embodiment 3 was utilized to mold an alumina toughened zirconia ceramic product. The performance of the molded part is: due to the total surface area of the ultrafine powder is high, the powder is not easy to form agglomerates, and the thickness of the polymer film is thin, causing a poor fluidity of the feed (<MFI 200), and its toughness is poor and is easy to break, and cannot be wound into a coil shape.

[0147] The size shrinkage and product yield of the 3D printed products obtained in Embodiments 1-8 were tested, and the results were as follows: compared with the 3D printed products obtained in the prior art, the 3D printed products obtained in Embodiments 1-8 had small high-temperature sintering shrinkage and less variation, and 10 to 30% increase on the product yield.

[0148] The second binder in Embodiments 1-8 were replaced with other thermosetting polymer materials, for example thermosetting polymer materials selected from any one or a combination of two of phenolic resin, urea-formaldehyde resin, melamine resin, unsaturated polyester resin, epoxy resin, organic silicone resin, and polyurethane; or replaced with other thermoplastic polymer materials, for example thermoplastic polymer materials selected from any one or a combination of two of polypropylene, polyvinyl chloride, polystyrene, polyoxymethylene, polycarbonate, polyamide, acrylic plastic, polysulfone, and polyphenylene oxide. Compared with the 3D printed products obtained in the prior art, the obtained 3D printed products had small high-temperature sintering shrinkage and less variation, and 10 to 30% increase on the product yield.

[0149] The applicant declares that the above are only specific implementations of this application, but the scope of protection of this application is not limited thereto, and those skilled in the art should understand that changes or substitutions that disclosed in this application and that can easily come up to any person skilled in the art fall within the scope of protection and disclosure of this application.