WO2023011490A1 - 一种高屈服应力陶瓷立体光刻 3d 打印材料及其制备方法与应用 - Google Patents

一种高屈服应力陶瓷立体光刻 3d 打印材料及其制备方法与应用 Download PDF

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WO2023011490A1
WO2023011490A1 PCT/CN2022/109765 CN2022109765W WO2023011490A1 WO 2023011490 A1 WO2023011490 A1 WO 2023011490A1 CN 2022109765 W CN2022109765 W CN 2022109765W WO 2023011490 A1 WO2023011490 A1 WO 2023011490A1
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ceramic
yield stress
printing material
high yield
stereolithography
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French (fr)
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邢占文
李文利
刘卫卫
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苏州大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • 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
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • C04B35/01—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
    • 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
    • C04B35/01—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
    • C04B35/10—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 based on aluminium oxide
    • 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
    • C04B35/01—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
    • C04B35/447—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 based on phosphates, e.g. hydroxyapatite
    • 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
    • C04B35/01—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
    • C04B35/48—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 based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • 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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention belongs to ceramic 3D material technology, in particular to a high yield stress ceramic stereolithography 3D printing material and its preparation method and application.
  • SLA stereolithography 3D printing technology has the most advantages, mainly in: (1) Due to the principle of stereolithography technology, the surface quality is good; (2) The high solid content makes the performance after sintering excellent; (3) It can manufacture complex structures that are difficult to manufacture by traditional techniques.
  • An insurmountable problem faced by stereolithography 3D printing technology is that it is inevitable to add support structures when building the bottom surface and overhanging structures, so as to prevent the printing from being caused by gravity or shear stress caused by processes (such as scraping) during the printing process. Parts are deformed or damaged.
  • the invention discloses a high yield stress ceramic stereolithography 3D printing material and its preparation method and application.
  • the obtained high yield stress (referring to yield stress greater than 50Pa) ceramic material is stable and easy to store, and can be used in the 3D printing process.
  • Implementing a non-contact support strategy and greatly reducing post-processing can achieve high-quality surface finish and high product yield of ceramic parts.
  • a high yield stress ceramic stereolithography 3D printing material including acrylate compound, plasticizer, initiator, ceramic powder, dispersant, and polyamide wax.
  • the high yield stress ceramic stereolithography 3D printing material is composed of acrylate compound, plasticizer, initiator, ceramic powder, dispersant, and polyamide wax.
  • the invention discloses a preparation method of the above-mentioned high yield stress ceramic stereolithography 3D printing material, which comprises the following steps: mixing an acrylate compound, a plasticizer, an initiator, a ceramic powder, and a dispersant, adding polyamide wax, and then heating and shearing Cut and disperse to obtain high yield stress ceramic stereolithography 3D printing materials.
  • the acrylate compound includes acrylate monomers and/or acrylate prepolymers.
  • Acrylate monomers are isobornyl acrylate (IBOA), N-acryloylmorpholine (ACMO), hydroxyethyl methacrylate (HEMA), 1,6-hexanediol acrylate (HDDA), ethoxylated pentaerythritol tetra Acrylate (PPTTA), trimethylolpropane triacrylate (TMPTA) or a combination of several;
  • acrylate prepolymers are aliphatic epoxy acrylate prepolymers, aliphatic urethane acrylate prepolymers wait.
  • the plasticizer is dibutyl phthalate (DBP), polyethylene glycol (PEG), 2-phenoxyethanol (POE); preferably, the amount of the plasticizer is the weight of the acrylate compound 5 ⁇ 30 wt%, preferably 10-25 wt%.
  • the initiators include 1-hydroxycyclohexyl phenyl ketone (184), benzoin dimethyl ether (651), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), di One of phenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819);
  • the amount of the initiator is 1-5 wt% of the weight of the acrylate compound.
  • the dispersant includes existing dispersants such as BYK and Tego, such as BYK111, BYK110, BYK9076, BYK152, Dispers 750W, Dispers 655, Tego 688, Tego One or more of 755; preferably, the amount of dispersant is 0.2-8 wt%, preferably 1-5 wt%, of the ceramic powder.
  • the ceramic powder is one or more of alumina, zirconia, silicon oxide, hydroxyapatite, tricalcium phosphate, silicon nitride, and silicon carbide; preferably, high yield stress ceramic stereolithography 3D
  • the volume percentage of ceramic powder is greater than 40 wt%, such as 40-80 wt%, preferably 50-70 wt%, more preferably 55-70 wt%, most preferably 56-70 wt%.
  • the consumption of polyamide wax is 0.2 ⁇ 12% of the total weight of acrylate compound and plasticizer. wt%, preferably 1-10 wt%, more preferably 2-8 wt%, most preferably 3-6 wt%.
  • the temperature is 50-90°C, preferably 60-70°C, and the time is 15-60 minutes, preferably 20-45 minutes; the shear rate is 1500-5000rpm, preferably 2000-4000rpm.
  • the present invention discloses the application of the above high yield stress ceramic stereolithography 3D printing material as a ceramic 3D printing material; further, the present invention discloses the application of the above high yield stress ceramic stereolithography 3D printing material in the manufacture of 3D printing ceramic parts .
  • the dispersant has a very large limit on the type of ceramic powder, such as ANTI-TERRA-U 100 has a good dispersion effect on alumina, but it cannot build a high yield stress material system for silicon nitride powder and cannot implement a non-contact support strategy.
  • the present invention creatively improves the existing formulations, with acrylate monomers and/or prepolymers, photoinitiators, and ceramic powders as the main body, under the action of plasticizers, dispersants and polyamide waxes, through heating and shearing
  • the processing changes the original slurry form, and obtains a ceramic stereolithography 3D printing material with a high yield stress in a paste state, and the yield stress is 50-2000Pa.
  • the invention solves the disadvantages of poor stability of slurry printing materials, and the need to add contact supports on the bottom surface and specific overhanging structures during production (the process of removing supports can easily cause damage to the surface of parts), and also solves the problem that the existing non-contact support can be implemented.
  • the problem of low solid content of the ceramic printing material powder of the support strategy is that the formulation system of the present invention has universal applicability to various ceramic powders, which solves the problem that the types of ceramic powders in existing formulations are limited by dispersants.
  • Figure 1 is a macroscopic photo of the high yield stress ceramic stereolithography 3D printing material constructed in Example 1.
  • Fig. 2 is the oscillation test curve (amplitude scanning mode) of the high yield stress ceramic stereolithography 3D printing material constructed in Example 1.
  • Fig. 3 is a photograph of a solid spline obtained by using the printing material constructed in Example 1 through a ceramic stereolithography 3D printing process.
  • Fig. 4 is a photo of a solid spline obtained by using the printing material constructed in Comparative Example 1 through the ceramic stereolithography 3D printing process.
  • Fig. 5 is a photo of the solid spline obtained by using the printing material constructed in Comparative Example 2 through the ceramic stereolithography 3D printing process.
  • Fig. 6 is a photo of the degreased green body obtained by using the printing material constructed in Comparative Example 5 through the ceramic stereolithography 3D printing process.
  • Fig. 7 is a photo of the sintered green body obtained by using the printing material constructed in Comparative Example 5 through the ceramic stereolithography 3D printing process.
  • Fig. 8 is a photograph of a solid spline obtained by using the printing material constructed in Example 2 through the ceramic stereolithography 3D printing process.
  • Fig. 9 is a microscopic topography diagram of a dental crown manufactured by using the printing material constructed in Example 3 through a ceramic stereolithography 3D printing process and a non-contact support strategy.
  • Figure 10 is a macroscopic photo of the crown after sintering.
  • All the raw materials of the present invention are existing commercially available products, which meet the requirements of printing materials.
  • polyamide wax comes from Changxing Xiehe Polymer Materials Co., Ltd., and several grades such as RC820 and RC1020 are available; the methods involved in the manufacturing process, For example, stereolithography 3D printing molding, cleaning, degreasing, and sintering are all conventional technologies in this field.
  • the creativity of the present invention lies in proposing a new universal formula, thereby obtaining ceramic stereolithography 3D printing materials with high yield stress.
  • the system can achieve high solid content of ceramic powders, and shear under certain conditions such as temperature and time. cutting activation, that is, to obtain ceramic stereolithography 3D printing materials with high yield stress, which has the premise of implementing non-contact support strategy. Ceramic stereolithography 3D printing materials are difficult to construct, and then the high yield stress characteristics of the constructed printing materials can be used to implement a non-contact support strategy to obtain ceramic parts with excellent surface (especially the bottom) quality, abandoning the traditional addition of support When manufacturing by method, the integrity of the part cannot be guaranteed when removing these support structures, which can easily lead to problems such as poor surface quality, deformation and cracking. This is very beneficial for the manufacture of high-precision, high-surface-quality product-grade ceramic parts.
  • yield stress the minimum force that exerts an external force on the material, destroys the internal structure of the sample, and changes it from a static state to a flowing state.
  • yield stress is the critical value of the shear stress. Only when the shear stress exceeds After the yield point, the material cannot flow.
  • Test method Rheometer amplitude sweep mode. Through the test, the storage modulus G' and the loss modulus G'' of the material can be read. When the two moduli are no longer constant, the end of the linear viscoelastic region is reached. This point is called the Yield point, the corresponding stress value is the yield stress value.
  • the implementation steps of the non-contact support strategy place the support on the forming table; merge the printed part data and the gap data between the printed part/support in the 3D design software; import the merged data into the ceramic 3D printer after slicing to start
  • For printing first set a layer of high yield stress ceramic stereolithography 3D printing material on the upper surface of the support without curing, then print the part and cure it, remove the support after completion, and clean it to obtain a 3D printed part with a complex bottom surface structure .
  • the invention makes use of the high yield stress characteristics of the building material, so that the uncured material located in the gap between the printed part and the support has a supporting effect on the upper printed part, and realizes that the support is easy to separate from the part to be printed. A technical effect that leaves any marks on the surface of the part.
  • the specific data processing and printing process involved are conventional technologies.
  • Example 1 High yield stress alumina ceramic stereolithography 3D printing material, its preparation method is as follows: at room temperature, 45.2g HDDA, 6.5g PPTTA, 12.9g DBP, 1.0g initiator 184, 350g alumina ceramic powder, 6.8g of dispersant Dispers 750W was stirred and mixed (200rpm, 15 minutes), then 3.0g of polyamide wax was added, and then sheared and dispersed at 2500rpm at 70°C for 30 minutes to obtain high yield stress ceramic stereolithography 3D printing materials.
  • the density of alumina ceramic powder is 3.93g/cm 3
  • the density of organic components is 1.13 g/cm 3 .
  • the calculation shows that the volume percentage of alumina powder in the high yield stress alumina ceramic stereolithography 3D printing material is 60.2 vol %.
  • Figure 1 is a macroscopic photo of the above-mentioned high yield stress ceramic stereolithography 3D printing material
  • Figure 2 is the oscillation test curve (amplitude scanning mode) of the above high yield stress ceramic stereolithography 3D printing material, and the yield point corresponding to the yield point can be seen in the figure
  • the stress is 200Pa, which meets the implementation requirements of non-contact support.
  • Fig. 3 is a photo of the solid spline obtained by printing using the first embodiment and implementing the non-contact support strategy.
  • Comparative Example 1 On the basis of Example 1, the amount of polyamide wax was reduced to 0.5 g, and a ceramic stereoscopic 3D printing material was obtained under the same preparation process.
  • Fig. 4 is the macrophotograph of the solid spline made of the material of Comparative Example 1. It can be seen from the figure that when the non-contact support strategy is implemented, sliding occurs during the part production process, the shape is distorted, and the printing fails.
  • Comparative Example 2 On the basis of Example 1, the amount of polyamide wax was increased to 5.2 g. Under the same preparation process, ceramic stereolithography 3D printing materials with high yield stress can be obtained, and non-contact support strategies can be implemented, but During printing and molding, a large number of unevenly distributed pores of different sizes appear on the surface of the green body, which affects the performance of the final product ( Figure 5).
  • Comparative Example 3 On the basis of Example 1, replace the BYK111 dispersant with the same amount of BYK ANTI-TERRA-U 100 dispersant is used to prepare ceramic stereolithography 3D printing materials.
  • the maximum amount of alumina ceramic powder can only reach 46 vol%. At this time, the state of the material is extremely poor and it is difficult to lay flat on the forming table, and non-contact can not be implemented. Supporting strategy, ceramic stereolithography 3D printing cannot be performed.
  • Comparative Example 4 On the basis of Example 1, the polyamide wax is omitted, and the obtained product is a slurry, and no ceramic stereolithography 3D printing material with yield stress can be obtained.
  • Comparative Example 5 On the basis of Example 1, DBP is omitted to obtain a ceramic stereolithography 3D printing material. First, the solid content of the system will decrease (49 vol%, and if the ceramic powder continues to increase, the material will become sticky and not suitable for stereolithography. engraving process), and second, lamellar cracks are prone to occur when the green body is degreased ( Figure 6). In addition to lamellar cracks, it is easy to crack in the overall longitudinal direction during sintering ( Figure 7).
  • Comparative Example 6 Referring to the article published by the inventor (J Mater Sci (2021) 56:2887–2899), replace the alumina in the preparation method in the left column on page 2889 with silicon nitride ceramics with a volume percentage of 40% powder, and the rest remain unchanged, the obtained material properties are slurry, and ceramic stereolithography 3D printing materials with high yield stress cannot be obtained.
  • Embodiment 2 high yield stress alumina ceramic stereolithography 3D printing material, its preparation method is as follows: at room temperature, 45.0g HDDA, 6.0gPPTTA, 13.9g DBP, 1.0g initiator 184, 350g alumina ceramic powder, 7.5g dispersant BYK111 were stirred and mixed (200rpm, 15 minutes), then added 2.0g polyamide wax, and then sheared and dispersed at 2500rpm at 70°C for 30 minutes to obtain high yield stress Ceramic stereolithography 3D printing material, the measured yield stress is 82Pa.
  • Figure 8 is a macroscopic photo of the solid spline made of the material in Example 2. It can be seen from the figure that when the non-contact support strategy is implemented for the material in Example 2, a green body can also be obtained, and the main structure conforms to the design. However, compared with Example 1, it is difficult to remove the support and will remain on the surface of the part.
  • Example 3 Due to the small particle size of the powder (such as 90 ⁇ 150 nm) and large specific surface area (such as 10 ⁇ 15 m 2 /g), the solid content of zirconia ceramic printing materials reaching 50vol% is generally considered to be high solid. content.
  • the preparation method of high yield stress zirconia ceramic stereolithography 3D printing material is as follows: at room temperature, 11.4g IBOA, 15.2g HDDA, 11.4g TMPTA, 7.6g DBP, 0.7g 184 initiator, 7.4g BYK 9076 dispersant, 300g of zirconia ceramic powder was stirred and mixed (200rpm, 15 minutes), then 2.0g of polyamide wax was added, and then sheared and dispersed at 2500rpm at 70°C for 30 minutes to obtain a high yield stress ceramic stereolithography 3D printing material with a yield stress of 260Pa.
  • the density of the zirconia ceramic powder is 6.01g/cm 3
  • the density of the organic component is 1.12 g/cm 3
  • the calculation shows that the volume percentage of alumina is 50.4 vol%.
  • Figure 9a is the design drawing of the non-contact support, the upper part is the printing target (dental crown), and the lower part is the added non-contact support;
  • Figure 9b is the actual The photo of the printed body, the crown and the underlying support have not been separated, and there is only a high yield stress ceramic stereolithography 3D printing material between the support and the printed part (no curing and cross-linking);
  • Figure 9c is after the support is removed In the SEM photo of the support, it can be seen that the support outline is clear, which is actually the mating surface of the protruding part of the bottom surface of the crown;
  • Figure 9d is the SEM photo of the contact surface between the crown and the support after the support is removed. It can be seen that the 3D printing layer pattern is clear, and the surface Excellent, completely free from defects.
  • Figure 10 is a photo of the crown printed in Figure 9a at various angles after sintering (where a, b, c, and d indicate different angles). It can be seen that the surface quality of the final product is excellent, and there is no trace of support removal.
  • Embodiment 4 On the basis of Embodiment 1, a single factor change is made to obtain a high yield stress ceramic stereolithography 3D printing material, which has good non-contact support performance, and the surface quality of the printed part is good.
  • the single factor change is: (1) replace alumina with hydroxyapatite with a volume fraction of 40vol%, and the yield stress is 310 Pa, which is mainly used for medical treatment; (2) replace alumina with volume percentage to achieve 40vol% silicon nitride, yield stress is 420 Pa, for medical and industrial use; (3) replace initiator 184 with the same amount of photoinitiated Agent 1173 can also obtain a high yield stress printing material similar to that of Example 1.
  • Embodiment five high yield stress ceramic stereolithography 3D printing material, its preparation method is as follows: at room temperature, 5000g IBOA, 1000g TMPTA, 2000g HDDA, 1200g DBP, 160g initiator 184, 50500g alumina ceramic powder, 1000g dispersant BYK110 were stirred and mixed (200rpm, 15 minutes), then added 400g polyamide wax, and then sheared and dispersed at 2500rpm at 70°C for 30 minutes to obtain a high yield stress ceramic three-dimensional Lithographic 3D printing materials.
  • High yield stress ceramic stereolithography 3D printing material its preparation method is as follows: under normal temperature, 5Kg IBOA, 1Kg ACMO, 2Kg HDDA, 1500g POE, 160g initiator TPO, 55Kg alumina ceramic powder, 1.1kg dispersant Tego 688 were stirred and mixed (200rpm, 15 minutes), then added 450g polyamide wax, and then sheared and dispersed at 3000rpm at 70°C for 30 minutes to obtain high Yield stress ceramic stereolithography 3D printing materials.
  • the high-yield stress ceramic stereolithography 3D printing materials obtained by the above different formulations have available non-contact support performance, and the surface quality of the printed parts is good, which is obviously better than the second embodiment, but worse than the first embodiment.

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Abstract

一种高屈服应力陶瓷立体光刻3D打印材料，其制备方法为：将丙烯酸酯化合物、塑化剂、引发剂、陶瓷粉、分散剂混合后加入聚酰胺蜡，然后加热剪切分散。高屈服应力陶瓷打印材料在3D打印成型过程中能够实施非接触支撑策略，大幅减少后期处理工序，可以实现陶瓷制品高质量的表面光洁度与高的产品良率，并具有稳定无沉降、易存储的特性。

Description

一种高屈服应力陶瓷立体光刻3D打印材料及其制备方法与应用 技术领域
本发明属于陶瓷3D材料技术，具体涉及一种高屈服应力陶瓷立体光刻3D打印材料及其制备方法与应用。
 背景技术
陶瓷3D打印有很多方法，比如FDM挤出成型、SLS选择性激光烧结、SLM选区激光熔化、SLA立体光刻成型等，其中SLA立体光刻3D打印技术最具优势，主要表现在：（1）因采用立体光刻技术原理，表面质量好；（2）固含量高使得烧结后性能优异；（3）可以制造传统工艺难以制造的复杂结构。立体光刻3D打印技术面临的一个难以克服的问题是在建造底面及悬垂结构时不可避免地需要添加支撑结构，以防止打印过程中重力或工艺（如刮涂）等引起的剪切应力造成打印零件变形或损坏。然而，打印结束后移除这些支撑结构时无法保证零件完整性，极易导致表面质量变差、变形和开裂等问题。这对以原型评估为主要目的的快速制造可通过后处理的办法消除，但是关乎高精度、高表面质量产品级陶瓷零件的生产制造时却显得无能为力。针对陶瓷立体光刻3D打印，现有技术大都针对陶瓷浆料进行配方设计和体系研究，希望获得高固含量的同时降低粘度，这本身是一对矛盾；同时浆料材料在打印过程中需要添加直接接触支撑，对于复杂结构后处理过程带来繁琐步骤，同时损害陶瓷制品表面质量；而且由于固态陶瓷粉体与液态分散介质存在较大密度差，浆料体系中的粉体容易出现沉降或偏析，导致坯体打印不均匀且不利于储存。因此，有必要设计一种对零件具有自支撑力的高屈服应力陶瓷立体光刻3D打印材料，通过实施非接触支撑策略（支撑和零件中间使用高屈服应力3D打印材料填充起支撑作用），以获得具有良好表面质量的复杂结构陶瓷零件。
 技术问题
本发明公开了一种高屈服应力陶瓷立体光刻3D打印材料及其制备方法与应用，得到的高屈服应力（指屈服应力大于50Pa）陶瓷材料稳定不沉降、易存储，在3D打印成型过程能够实施非接触支撑策略，大幅减少后期处理，可以实现陶瓷制件高质量的表面光洁度与高的产品良率。
 技术解决方案
本发明采用如下技术方案：一种高屈服应力陶瓷立体光刻3D打印材料，包括丙烯酸酯化合物、塑化剂、引发剂、陶瓷粉、分散剂、聚酰胺蜡。优选的，所述高屈服应力陶瓷立体光刻3D打印材料由丙烯酸酯化合物、塑化剂、引发剂、陶瓷粉、分散剂、聚酰胺蜡组成。
本发明公开了上述高屈服应力陶瓷立体光刻3D打印材料的制备方法，包括以下步骤，将丙烯酸酯化合物、塑化剂、引发剂、陶瓷粉、分散剂混合后加入聚酰胺蜡，然后加热剪切分散，得到高屈服应力陶瓷立体光刻3D打印材料。
上述技术方案中，丙烯酸酯化合物包括丙烯酸酯单体和/或丙烯酸酯预聚物。丙烯酸酯单体为丙烯酸异冰片酯（IBOA）、N-丙烯酰吗啉（ACMO）、甲基丙烯酸羟乙酯（HEMA）、1,6-己二醇丙烯酸酯（HDDA）、乙氧化季戊四醇四丙烯酸酯（PPTTA）、三羟甲基丙烷三丙烯酸酯（TMPTA）中一种或几种的组合；丙烯酸酯预聚物为脂肪族环氧丙烯酸酯预聚物、脂肪族聚氨酯丙烯酸酯预聚物等。
本发明中，塑化剂为邻苯二甲酸二丁酯（DBP）、聚乙二醇（PEG）、2-苯氧基乙醇（POE）；优选的，塑化剂的用量为丙烯酸酯化合物重量的5～30 wt%，优选为10～25 wt%。
本发明中，引发剂包括1-羟基环己基苯基甲酮（184）、安息香双甲醚（651）、2-羟基-2-甲基-1-苯基-1-丙酮（1173）、二苯基-(2,4,6-三甲基苯甲酰)氧磷（TPO）、苯基双(2,4,6-三甲基苯甲酰基)氧化膦（819）中的一种；优选的，引发剂的用量为丙烯酸酯化合物重量的1～5 wt%。
本发明中，分散剂包括毕克、迪高等现有分散剂，比如BYK111、BYK110、BYK9076、BYK152、Dispers 750W、Dispers 655、Tego 688、Tego 755中的一种或几种；优选的，分散剂的用量为陶瓷粉重量的0.2～8 wt%，优选为1～5 wt%。
本发明中，陶瓷粉为氧化铝、氧化锆、氧化硅、羟基磷灰石、磷酸三钙、氮化硅、碳化硅中的一种或几种；优选的，高屈服应力陶瓷立体光刻3D打印材料中，陶瓷粉的体积百分数大于40 wt%，比如40～80 wt%，优选为50～70 wt%，进一步优选为55～70 wt%，最优为56～70 wt%。
本发明中，聚酰胺蜡的用量为丙烯酸酯化合物和塑化剂总重量的0.2～12 wt%，优选为1～10 wt%，进一步优选为2～8 wt%，最优选为3～6 wt%。
本发明中，加热剪切分散时，温度为50～90℃，优选60～70℃，时间为15～60分钟，优选20～45分钟；剪切速度为1500～5000rpm，优选2000～4000rpm。
本发明公开了上述高屈服应力陶瓷立体光刻3D打印材料作为陶瓷3D打印材料的应用；进一步的，本发明公开了上述高屈服应力陶瓷立体光刻3D打印材料在制造3D打印陶瓷零件中的应用。
 有益效果
现有技术鲜有公开可以实施非接触支撑策略的陶瓷立体光刻3D打印材料，且陶瓷粉固含量少有超过50 vol%（比如氧化铝）。对于常规陶瓷浆料，可以通过分散剂选取及配方设计提高粉体固含量，但是无法实施非接触支撑策略，因此不能保证打印陶瓷产品的表面质量；本发明首次公开了高屈服应力陶瓷立体光刻3D打印材料，可以达到陶瓷粉体超过55vol%的效果，尤其是，固含量达到60 vol%时依然可以实施非接触支撑策略，所得陶瓷零件表面质量优，这是本发明首创。
另外，现有技术公开的可实施非接触支撑策略的3D打印材料中，分散剂对陶瓷粉体类型的限定非常大，比如ANTI-TERRA-U 100对氧化铝具有较好的分散效果，但是对于氮化硅粉体则无法构建高屈服应力材料体系而不能实施非接触支撑策略。
本发明对现有配方进行创造性改进，以丙烯酸酯单体和/或预聚物、光引发剂、陶瓷粉为主体，在塑化剂、分散剂结合聚酰胺蜡的作用下，通过加热剪切处理，改变了原有的浆料形态，得到膏体状态的具有高屈服应力的陶瓷立体光刻3D打印材料，其屈服应力为50～2000Pa。本发明解决了浆料打印材料稳定性差，制作时需要在底面及特定悬垂结构添加接触式支撑（去支撑的过程极易造成零件表面的破坏）的缺点，同时还解决了现有可以实施非接触支撑策略的陶瓷打印材料粉体固含量偏低的问题。最为关键的是，本发明的配方体系对多种陶瓷粉具有普适性，解决了现有配方的陶瓷粉种类受分散剂限制的问题。
 附图说明
图1为实施例一构建的高屈服应力陶瓷立体光刻3D打印材料的宏观照片。
图2为实施例一构建的高屈服应力陶瓷立体光刻3D打印材料的振荡测试曲线（振幅扫描模式）。
图3为采用实施例一构建的打印材料通过陶瓷立体光刻3D打印工艺得到的实体样条照片。
图4为采用对比例一构建的打印材料通过陶瓷立体光刻3D打印工艺得到的实体样条照片。
图5为采用对比例二构建的打印材料通过陶瓷立体光刻3D打印工艺得到的实体样条照片。
图6为采用对比例五构建的打印材料通过陶瓷立体光刻3D打印工艺得到的坯体脱脂后的照片。
图7为采用对比例五构建的打印材料通过陶瓷立体光刻3D打印工艺得到的坯体烧结后的照片。
图8为采用实施例二构建的打印材料通过陶瓷立体光刻3D打印工艺得到的实体样条照片。
图9为采用实施例三构建的打印材料通过陶瓷立体光刻3D打印工艺和非接触支撑策略制造牙冠的微观形貌图。
图10为牙冠烧结后的宏观照片。
 本发明的实施方式
本发明的所有原料都是现有市售产品，符合打印材料的要求，比如聚酰胺蜡来自长兴协和高分子材料股份有限公司，RC820、RC1020等几个牌号都可以；制造过程中涉及的方法，比如立体光刻3D打印成型、清洗、脱脂、烧结都是本领域常规技术，本发明的创造性在于提出新的普适性的配方，从而得到了具有高屈服应力的陶瓷立体光刻3D打印材料。通过丙烯酸酯化合物、塑化剂、分散剂、聚酰胺蜡的选择配合，以及分子与陶瓷粉体之间的相互作用，使体系达到高的陶瓷粉固含量，在一定温度和时间等条件下剪切活化，即得到具有高屈服应力的陶瓷立体光刻3D打印材料，具备实施非接触支撑策略的前提，其细腻、滑爽、不流动、不坍塌、不漫流，解决了现有技术高屈服应力陶瓷立体光刻3D打印材料构建困难的问题，进而可以利用构建的打印材料的高屈服应力特点，实施非接触支撑策略，得到具有优异表面（尤其是底面）质量的陶瓷零件，摒弃了传统添加支撑方法制造时，移除这些支撑结构时无法保证零件完整性，极易导致表面质量变差、变形和开裂等问题。这对高精度、高表面质量产品级陶瓷零件的生产制造非常有益。
屈服应力定义：对材料施加外力，破坏样品内部结构，使其由静止状态转变为流动状态的最小作用力，在流变学中，屈服应力是剪切应力的临界值，只有当剪切应力超过屈服点之后，材料才能发生流动。测试方法：流变仪振幅扫描模式。通过测试，可以读取材料的储能模量G’和损耗模量G’’，当两个模量不再是恒定值时，就到达了线性粘弹区的终点，这个点被称为是屈服点，对应的应力值为屈服应力值。
非接触支撑策略的实施步骤：将支撑件放在成型台上；在三维设计软件中合并打印零件数据与打印零件/支撑件之间的间隙数据；将合并数据切片后导入到陶瓷3D打印机中开始打印，先在支撑件上表面设置一层高屈服应力陶瓷立体光刻3D打印材料，不固化，再打印零件、固化，完成后移除支撑件，清洗，即得到3D打印零件，具有复杂底面结构。本发明利用构建材料的高屈服应力特点，使得位于打印零件和支撑件间隙的未固化材料对上部打印零件具有支撑作用，实现了支撑件与所需打印的零件易于分离，移除时/后不会在零件表面留下任何痕迹的技术效果。涉及的具体数据处理以及打印过程为常规技术。
现有技术为尽可能减少打印零件与支撑的接触，一般会采用不同结构和形式的支撑方式，如在零件表面添加柱状支撑，存在的问题依然是去除支撑时导致零件下表面（与支撑接触的面）缺陷多。
实施例一：高屈服应力氧化铝陶瓷立体光刻3D打印材料，其制备方法如下：室温下，将45.2g HDDA、6.5g PPTTA、12.9g DBP、1.0g引发剂184、350g氧化铝陶瓷粉、6.8g分散剂Dispers 750W搅拌混合（200rpm、15分钟）后加入3.0g聚酰胺蜡，然后70℃下2500rpm剪切分散30分钟，得到高屈服应力陶瓷立体光刻3D打印材料。其中氧化铝陶瓷粉密度为3.93g/cm 3，有机组分密度为1.13 g/cm 3，计算可知，高屈服应力氧化铝陶瓷立体光刻3D打印材料中氧化铝粉体的体积百分数为60.2 vol%。
图1为上述高屈服应力陶瓷立体光刻3D打印材料的宏观照片；图2为上述高屈服应力陶瓷立体光刻3D打印材料的振荡测试曲线（振幅扫描方式），图中可见屈服点对应的屈服应力为200Pa，满足非接触支撑实施要求。图3为采用实施例一，实施非接触支撑策略，打印得到的实体样条照片。
对比例一：在实施例一的基础上，减小聚酰胺蜡用量至0.5g，同样的制备工艺下得到陶瓷立体光3D打印材料。
图4为对比例一材料制作实体样条的宏观照片。由图可见，在实施非接触支撑策略时，零件制作过程中出现滑动，形状失真，打印失败。
对比例二：在实施例一的基础上，增加聚酰胺蜡用量至5.2 g，同样的制备工艺下，能够得到具有高屈服应力的陶瓷立体光刻3D打印材料，可以实施非接触支撑策略，但是打印成型时，在坯体表面出现大量分布不均且大小不一的气孔，影响最终制件性能（图5）。
对比例三：在实施例一的基础上，将BYK111分散剂更换为等量的BYK ANTI-TERRA-U 100分散剂，制备陶瓷立体光刻3D打印材料，氧化铝陶瓷粉的用量最高仅能达到46 vol%，且此时材料状态极差难以在成型台铺平，无法实施非接触支撑策略，不能进行陶瓷立体光刻3D打印。
对比例四：在实施例一的基础上，省略聚酰胺蜡，得到的产品是浆料，得不到具有屈服应力的陶瓷立体光刻3D打印材料。
对比例五：在实施例一的基础上，省略DBP，得到陶瓷立体光刻3D打印材料，一是会造成体系固含量降低（49 vol%，继续增加陶瓷粉则出现材料粘稠不适合立体光刻工艺），二是坯体脱脂时容易产生层裂（图6），烧结时除了层裂还容易整体纵向产生开裂（图7）。
以上实施例以及对比例的配方见表1。
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。
对比例六：参考发明人已经发表的文章（J Mater Sci (2021) 56:2887–2899），将第2889页左栏的制备方法中的氧化铝更换为体积百分数为40%的氮化硅陶瓷粉，其余不变，得到的材料性状是浆料，得不到具有高屈服应力的陶瓷立体光刻3D打印材料。
实施例二：高屈服应力氧化铝陶瓷立体光刻3D打印材料，其制备方法如下：室温下，将45.0g HDDA、6.0g PPTTA、13.9g DBP、1.0g引发剂184、350g氧化铝陶瓷粉、7.5g分散剂BYK111搅拌混合（200rpm、15分钟）后加入2.0g聚酰胺蜡，然后70℃下2500rpm剪切分散30分钟，得到高屈服应力陶瓷立体光刻3D打印材料，测得其屈服应力为82Pa。
采用同样的打印方法和打印参数，图8为实施例二材料制作实体样条的宏观照片。由图可见，实施例二的材料在实施非接触支撑策略时，也能得到坯体，主体结构与设计符合，但是与实施例一相比，支撑去除困难，会在零件表面残留。
实施例三：由于粉体粒径细小（如90~150 nm）及较大的比表面积（如10~15 m 2/g），氧化锆陶瓷打印材料的固含量达到50vol%一般认为是高固含量。高屈服应力氧化锆陶瓷立体光刻3D打印材料的制备方法如下：常温下，将11.4g IBOA、15.2g HDDA、11.4g TMPTA、7.6g DBP、0.7g 184引发剂、7.4g BYK 9076分散剂、300g氧化锆陶瓷粉搅拌混合（200rpm、15分钟）后加入2.0g聚酰胺蜡，然后70℃下2500rpm剪切分散30分钟，得到高屈服应力陶瓷立体光刻3D打印材料，屈服应力为260Pa。其中氧化锆陶瓷粉密度为6.01g/cm 3，以有机组分密度为1.12 g/cm 3，计算可知，氧化铝的体积百分数为50.4 vol%。
将上述高屈服应力陶瓷立体光刻3D打印材料进行3D打印，图9a为非接触支撑设计图，上半部分是打印目标（牙冠），下半部分是添加的非接触支撑；图9b为实际打印坯体的照片，尚未对牙冠和底下的支撑进行分离，支撑与打印件之间仅为高屈服应力陶瓷立体光刻3D打印材料（未发生固化交联）；图9c为支撑取下之后的SEM照片，可以看到支撑轮廓清晰，实为牙冠底面凸出部位的配合面；图9d为牙冠上与支撑接触面去掉支撑之后的SEM照片，可以看到3D打印层纹清晰，表面优异，完全无缺损。
图10为图9a图纸打印的牙冠烧结后各个角度的照片（其中a、b、c、d表示不同角度），可见最终产品表面质量优异，没有支撑去除痕迹。
 实施例四：在实施例一的基础上做单因素变化，得到高屈服应力陶瓷立体光刻3D打印材料，具有良好的非接触支撑性能，打印件表面质量好。单因素变化为：（1）将氧化铝更换为体积分数做到40vol%的羟基磷灰石，屈服应力为310 Pa，主要用于医疗；（2）将氧化铝更换为体积百分数做到40vol%氮化硅，屈服应力为420 Pa，用于医疗和工业；（3）引发剂184更换为等量的光引发剂1173，也可以得到与实施例一近似的高屈服应力打印材料。
实施例五：高屈服应力陶瓷立体光刻3D打印材料，其制备方法如下：常温下，将5000g IBOA、1000g TMPTA、2000g HDDA、1200g DBP、160g引发剂184、50500g氧化铝陶瓷粉、1000 g分散剂BYK110搅拌混合（200rpm、15分钟）后加入400g聚酰胺蜡，然后70℃下2500rpm剪切分散30分钟，得到高屈服应力陶瓷立体光刻3D打印材料。
高屈服应力陶瓷立体光刻3D打印材料，其制备方法如下：常温下，将5Kg IBOA、1Kg ACMO、2Kg HDDA、1500g POE、160g引发剂TPO、55Kg氧化铝陶瓷粉、1.1kg分散剂Tego 688搅拌混合（200rpm、15分钟）后加入450g聚酰胺蜡，然后70℃下3000rpm剪切分散30分钟，得到高屈服应力陶瓷立体光刻3D打印材料。
上述不同配方得到的高屈服应力陶瓷立体光刻3D打印材料，具有可用的非接触支撑性能，打印件表面质量好，明显优于实施例二，但差于实施例一。

Claims (10)

  1. 一种高屈服应力陶瓷立体光刻3D打印材料，其特征在于，包括丙烯酸酯化合物、塑化剂、引发剂、陶瓷粉、分散剂、聚酰胺蜡。
  2. 根据权利要求1所述高屈服应力陶瓷立体光刻3D打印材料，其特征在于，丙烯酸酯化合物包括丙烯酸酯单体和/或丙烯酸酯预聚物；塑化剂为邻苯二甲酸二丁酯、聚乙二醇或者2-苯氧基乙醇；引发剂为光引发剂；陶瓷粉为氧化铝、氧化锆、氧化硅、羟基磷灰石、磷酸三钙、氮化硅、碳化硅中的一种或几种。
  3. 根据权利要求1所述高屈服应力陶瓷立体光刻3D打印材料，其特征在于，塑化剂的用量为丙烯酸酯化合物重量的5～30wt%；引发剂的用量为丙烯酸酯化合物重量的1～5wt%；聚酰胺蜡的用量为丙烯酸酯化合物和塑化剂总重量的0.2～12wt%。
  4. 根据权利要求1所述高屈服应力陶瓷立体光刻3D打印材料，其特征在于，分散剂的用量为陶瓷粉重量的0.2～8%。
  5. 根据权利要求1所述高屈服应力陶瓷立体光刻3D打印材料，其特征在于，高屈服应力陶瓷立体光刻3D打印材料中，陶瓷粉的体积百分数大于40%。
  6. 权利要求1所述高屈服应力陶瓷立体光刻3D打印材料的制备方法，其特征在于，包括以下步骤，将丙烯酸酯化合物、塑化剂、引发剂、陶瓷粉、分散剂混合后加入聚酰胺蜡，然后加热剪切分散，得到高屈服应力陶瓷立体光刻3D打印材料。
  7. 根据权利要求6所述高屈服应力陶瓷立体光刻3D打印材料的制备方法，其特征在于，加热的温度为50～90℃，时间为15～60分钟。
  8. 根据权利要求6所述高屈服应力陶瓷立体光刻3D打印材料的制备方法，其特征在于，剪切的速度为1500～5000rpm。
  9. 权利要求1所述高屈服应力陶瓷立体光刻3D打印材料作为陶瓷3D打印材料的应用或者在制造3D打印陶瓷零件中的应用。
  10. 根据权利要求9所述的应用，其特征在于，高屈服应力的屈服应力大于50Pa。
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