Near-infrared light direct curing additive manufacturing slurry and preparation method thereof

Abstract

The invention provides a near-infrared light direct curing additive manufacturing slurry and a preparation method thereof. The slurry comprises the following components in parts by weight: 2-15 parts of a first auxiliary agent, 10-85 parts of inorganic material powder, 0.01-5 parts of a dispersing agent and 0.01-5 parts of a photoinitiator. Wherein the first auxiliary agent serves as a curing monomer and a cross-linking agent in the slurry, the refractive index nD of the inorganic material powder is 1.5-2.8, and the slurry does not contain an up-conversion luminescent material. The slurry can be directly cured under the action of infrared light with the wavelength range of 850-1100 nm and the light source energy density of 3 W / cm < 2 >-15 W / cm < 2 >. The near-infrared light direct curing additive manufacturing technology has the advantages of being high in forming speed, high in single-layer thickness, high in precision, low in energy consumption, high in efficiency and the like, and a new solution is provided for large-scale industrial application of additive manufacturing.

Description

Technical Field

[0001] The present invention belongs to the scope of additive manufacturing, and specifically relates to a near-infrared light direct curing additive manufacturing slurry and a preparation method thereof. Background Art

[0002] Inorganic materials, such as metals and ceramics, are widely used in aviation, machinery, military, electronics, and chemical industries due to their excellent basic properties. Traditional metal or ceramic processing and forming methods are often based on molds or subtractive manufacturing, which has high production costs and cannot achieve large-scale production for parts with complex shapes and precise structures. Additive manufacturing technology provides a new solution for this.

[0003] As a branch technology of additive manufacturing technology, photo-curing additive manufacturing has the advantages of high efficiency, high precision and low energy consumption. Compared with other additive manufacturing processes that have problems such as long cycle, difficult processing and high cost in preparing complex structure metal and ceramic devices, photo-curing additive manufacturing has better economic and technical advantages in preparing complex structure metal or ceramic devices.

[0004] Generally speaking, the photocuring additive manufacturing slurry of metal or ceramic has a high powder addition amount, while the light source of the corresponding photocuring additive manufacturing equipment is ultraviolet light, which has insufficient penetration into such inorganic powders. In addition, the refractive index of powder for ultraviolet light is relatively large, and the refractive behavior is relatively complex, resulting in low curing depth and poor curing efficiency in photocuring additive manufacturing, which makes it impossible to achieve large-scale application of photocuring additive manufacturing of inorganic materials.

[0005] In order to solve the problem of low UV curing depth mentioned above, in recent years, the technology of using near-infrared light for photocuring has been explored. This type of technology usually requires adding upconversion luminescent materials to the slurry, converting near-infrared light into ultraviolet light, and then performing photocuring. As a result, the following disadvantages are brought about: First, most of the upconversion materials are compounds doped with rare earth ions, and the extraction and processing costs of rare earth elements are expensive; second, the production process cycle of upconversion materials with high luminous efficiency and suitable for near-infrared light curing is long and the yield is limited; third, the luminous intensity of upconversion materials is limited, and the energy density of the near-infrared light source is required to be high, resulting in high equipment costs.

[0006] Therefore, a new photocuring additive manufacturing slurry and preparation method are urgently needed to solve the above technical problems. Summary of the invention

[0007] In view of the above shortcomings, the present invention proposes a near-infrared light direct curing additive manufacturing slurry and a preparation method to solve the defects of the prior art such as low UV curing depth, poor curing efficiency, high cost, expensive infrared light curing upconversion materials and excessively high cost of high-power light source equipment.

[0008] The present invention provides a near-infrared light direct curing additive manufacturing slurry, which comprises, by weight: 2-15 parts of a first auxiliary agent, 10-85 parts of an inorganic material powder, 0.01-5 parts of a dispersant, and 0.01-5 parts of a photoinitiator;

[0009] Wherein, the slurry does not contain up-conversion luminescent material;

[0010] Wherein, the refractive index nD of the inorganic material powder is 1.5 to 2.8.

[0011] Among them, for inorganic material powders with a refractive index nD of 1.5 to <2.0, the wavelength of the near-infrared light source used during curing is 850nm to <980nm; for inorganic material powders with a refractive index of 2.0 to 2.8, the wavelength of the near-infrared light source used during curing is 980nm to 1100nm. The slurry can be in the wavelength range of 850-1100nm, the light source energy density is 3W / cm 2 ~15W / cm 2 Directly cured under the action of infrared light.

[0012] Wherein, the particle size D of the inorganic material powder is 50 0.1-50μm.

[0013] Wherein, the near-infrared light direct curing additive manufacturing slurry further includes a dye and / or a solvent.

[0014] Wherein, when the near-infrared light direct curing additive manufacturing slurry is a white system, for example, the inorganic material powder in the slurry includes Al 2 O 3 Powder, ZrO 2 In the case of one or more of powder, hydroxyapatite, and glass powder, the slurry may also contain a dye, and the amount of the dye is 0.5-2 parts by weight; the dye includes one or more of carbon black, iron blue, chromium oxide green, iron oxide brown, and ultramarine; adding a dye to the white system slurry helps to absorb near-infrared light and thus promotes curing behavior.

[0015] Among them, when the first auxiliary agent in the near-infrared light direct curing additive manufacturing slurry is an aqueous system, for example, when the first auxiliary agent in the slurry includes one or more of hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), and polyethylene glycol diacrylate (PEGDA), the slurry may also contain an aqueous solvent, and the amount of the aqueous solvent is 5-10 parts by weight, and the aqueous solvent includes one or more of water, ethanol, ethylene glycol, dipropylene glycol butyl ether (DPNB), and propylene glycol methyl ether (PM).

[0016] The first auxiliary agent acts as a curing monomer and a cross-linking agent in the near-infrared light direct curing additive manufacturing slurry.

[0017] Among them, the first auxiliary agent includes one or more of 1,6-hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), polyethylene glycol diacrylate (PEGDA), tripropylene glycol diacrylate (TPGDA), hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PET4A), and polyurethane acrylate (PUA).

[0018] Wherein, the inorganic material powder includes Al 2 O 3 Powder, SiC powder, Si 3 N 4 Powder, ZrO 2 One or more of powder, hydroxyapatite, WC powder, glass powder, aluminum powder, copper powder, nickel powder, tungsten powder, stainless steel powder, and cemented carbide powder.

[0019] Wherein, the photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, trimethylbenzoyl-diphenylphosphine oxide, 2,4-diethylthiazolone, and bis(2,6-difluoro-3-pyrrolephenyl)titanocene.

[0020] Wherein, the dispersant includes one or more of XYS-710, XYS-2800, XYS-5800, SP-710, KOS110, SP-1344, P5398, P5318, P5362, Span 85, and TEGO655.

[0021] Among them, the near-infrared light direct curing additive manufacturing slurry preferably comprises: the first auxiliary agent contains both the first auxiliary agent A and the first auxiliary agent B, the first auxiliary agent A is at least one of tripropylene glycol diacrylate (TPGDA) and trimethylolpropane triacrylate (TMPTA), and the first auxiliary agent B is at least one of 1,6-hexanediol diacrylate (HDDA), polyethylene glycol diacrylate (PEGDA), and dipropylene glycol diacrylate (DPGDA); at the same time, the slurry contains one or more of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and bis 2,6-difluoro-3-pyrrolephenyl dititanocene as photoinitiators; and the refractive index range of the inorganic material powder in the slurry is 1.5 to <2.0; at this time, the wavelength range of the light source used for curing is 850 to <980nm. Among them, the first auxiliary agent A is used as a curing monomer, and the first auxiliary agent B is used as a cross-linking agent.

[0022] Among them, the near-infrared light direct curing additive manufacturing slurry preferably comprises: the first auxiliary agent contains both the first auxiliary agent C and the first auxiliary agent D, the first auxiliary agent C is at least one of pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PET4A), and polyurethane acrylate (PUA), and the first auxiliary agent D is at least one of polyethylene glycol diacrylate (PEGDA), hydroxyethyl acrylate (HEA), and hydroxyethyl methacrylate (HEMA); at the same time, the slurry contains one or more of trimethylbenzoyl-diphenylphosphine oxide, 2,4-diethylthiazolone, and bis-2,6-difluoro-3-pyrrolephenyl dititanocene as photoinitiators; and the refractive index range of the inorganic material powder in the slurry is 1.5 to 2.8; at this time, the wavelength range of the light source used for curing is 980 to 1100 nm. Among them, in the first auxiliary agent, the first auxiliary agent C is used as a curing monomer, and the first auxiliary agent D is used as a cross-linking agent.

[0023] The present invention also provides a method for preparing the above-mentioned near-infrared light direct curing additive manufacturing slurry, comprising: mixing the slurry raw materials evenly to obtain the near-infrared light direct curing additive manufacturing slurry; the slurry raw materials include a first auxiliary agent, a photoinitiator, an inorganic material powder and a dispersant.

[0024] Among them, the preparation method of the near-infrared light direct curing additive manufacturing slurry preferably includes: first mixing the first auxiliary agent and the photoinitiator, and after the photoinitiator is completely dissolved, successively adding the dispersant and the inorganic material powder, and mixing them evenly, thereby obtaining the near-infrared light direct curing additive manufacturing slurry.

[0025] The present invention also provides a method for manufacturing a three-dimensional structure product by direct near-infrared light curing, comprising:

[0026] (1) obtaining the above-mentioned near-infrared light direct curing additive manufacturing slurry;

[0027] (2) performing a debubbling treatment on the near-infrared light direct curing additive manufacturing slurry to obtain a debubbled slurry;

[0028] (3) adding the debubbled slurry into a near-infrared light-curing additive manufacturing device for 3D printing to obtain a green body of a three-dimensional structured product;

[0029] (4) debinding and sintering the green body to obtain a three-dimensional structure product;

[0030] Wherein, in the step (2), the degassing treatment includes degassing the slurry; the time of the degassing treatment is 1-2 minutes.

[0031] In step (3), the light source used for curing is near-infrared light with a wavelength range of 850-1100 nm and an energy density of 3 W / cm 2 ~15W / cm 2 .

[0032] Wherein, in the step (3), the 3D printing is preferably performed using stereolithography (SLA) technology or digital light processing (DLP) technology.

[0033] Wherein, in the step (4), before debinding and sintering the green body of the three-dimensional structure product, the green body of the three-dimensional product is cleaned and dried.

[0034] The present invention also provides a three-dimensional structure product prepared by the method for manufacturing a three-dimensional structure product by direct curing of near-infrared light.

[0035] The curing thickness of conventional inorganic powders produced by UV-curing additive manufacturing is about 30 to 200 microns, while the curing thickness of three-dimensional structure products produced by the present invention can reach about 1000 microns, and even up to 2000 microns.

[0036] The present invention has the following beneficial technical effects:

[0037] (1) In the near-infrared light direct curing additive manufacturing slurry described in the present invention, there is no need to add up-conversion luminescent materials, and near-infrared light direct curing can be used to manufacture three-dimensional products. Therefore, while inheriting the advantages of high efficiency, high precision and low energy consumption of curing additive manufacturing, near-infrared light is used as the light source to improve the laser penetration ability, and by using inorganic powder materials with a specific refractive index to enhance the absorption of near-infrared light, the photothermal conversion of near-infrared light by inorganic powder is used to dissociate the photoinitiator to initiate the curing of the slurry. Specifically, through the absorption of near-infrared light by inorganic powder, light energy is converted into heat energy. Under the irradiation of near-infrared light of a certain intensity, the instantaneous heat energy converted by the inorganic powder can cause the photoinitiator to dissociate and generate free radicals, thereby initiating the curing of the slurry, and realizing the rapid curing additive manufacturing of inorganic materials.

[0038] (2) Compared with the traditional UV-curing additive manufacturing technology, the present invention uses near-infrared light as the light source, and near-infrared light has stronger penetration ability than ultraviolet light. Therefore, the method of the present invention improves the curing efficiency and curing depth of inorganic material slurry curing molding, that is, the curing depth is deeper (the curing depth is increased from 30 to 200 μm to 1 to 2 mm) and the curing efficiency is higher (from the conventional 11 mm / h to 72 mm / h to 357 mm / h to 715 mm / h), thereby greatly improving the printing speed.

[0039] (3) Compared with the traditional near-infrared light-curing additive manufacturing technology, the present invention does not need to add up-conversion luminescent materials. Therefore, it has the following advantages: a. Wide material applicability: All components of the slurry are materials widely used in the current industrial field, and there are no special requirements for inorganic powders; b. Low material cost, near-infrared light curing can be achieved without rare earth synthesized up-conversion materials; c. Low equipment cost: The laser wavelength is high, and the price is lower than that of ultraviolet light sources of the same power; the laser power is low, and the price is lower than that of near-infrared light sources based on up-conversion materials.

[0040] (4) The near-infrared light direct curing additive manufacturing technology described in the present invention has the advantages of fast speed (printing speed can reach 357mm / h~715mm / h), high layer thickness (single layer thickness can reach 1~2mm), low energy consumption (compared with near-infrared light curing additive manufacturing based on upconversion materials, the light source energy density is lower), and low cost (mainly reflected in materials and equipment), providing a new solution for the large-scale industrial application of curing additive manufacturing.

[0041] (5) The present invention is easy to operate and has a low threshold. Unlike other inorganic material powder additive manufacturing methods, the method of the present invention has no special requirements for powder fluidity and powder morphology, breaking the limitations of conventional inorganic material powder additive manufacturing methods and having wide applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is the solidified morphology of the copper metal slurry single layer prepared in Example 1.

[0043] Figure 2 This is the solidified morphology of the single layer of alumina slurry prepared in Example 4.

[0044] Figure 3 The solidified morphologies of single layers of different sizes of the copper metal slurry prepared in Example 1 are shown.

[0045] Figure 4 This is the solidified morphology of the WC-Co slurry single layer prepared in Comparative Example 5.

[0046] Figure 5 It is the infrared spectra of each slurry of Examples 1, 2, 4, and 7 before and after near-infrared light curing.

[0047] Figure 6 It is a comparison of the absorbance of the photoinitiator and the inorganic powders of Examples 1, 5, and 8 in the 300-1100 nm band.

[0048] Figure 7 It is a comparison of the absorbance of the photoinitiator and the slurries of Examples 1, 5, and 8 in the 300-1100 nm band. DETAILED DESCRIPTION

[0049] The present invention will be described in further detail below in conjunction with specific embodiments. However, it should be understood that these embodiments are only for illustration and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims of the present application.

[0050] In the following embodiments, the 3D printing is performed using stereolithography (SLA) technology.

[0051] Example 1. Preparation of copper heat sink

[0052] (1) Preparation of copper metal slurry: PEGDA (1.8 parts by weight) and PETA (1.4 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes, and then dispersant XYS-2800 (0.1 parts by weight), photoinitiator trimethylbenzoyl-diphenylphosphine oxide (0.05 parts by weight) and bis-2,6-difluoro-3-pyrrolophenyl titanocene (0.2 parts by weight) were added and placed in an ultrasonic dissolver for 15 minutes to fully dissolve them. Finally, copper powder (16 parts by weight, refractive index nD is 2.2) was added and placed in a mixer and stirred for 1 minute to mix them evenly. At this point, the preparation of copper metal slurry was completed.

[0053] (2) The copper metal slurry is placed in a centrifugal mixer for degassing to avoid defects in the printing process.

[0054] (3) Add the slurry into the near-infrared light-curing additive manufacturing equipment and quickly print the copper heat sink blank (such as Figure 1 The energy density of the near-infrared light source is 5W / cm 2 , wavelength is 980nm, the maximum single layer thickness of printing is about 1.1mm, and the molding speed is 396mm / h.

[0055] (4) The formed green body is removed from the printing platform, and the residual resin is cleaned with alcohol, and then placed at a temperature of 40°C for 0.5 hours to completely dry the green body. Finally, the green body is placed in a debinding sintering furnace in a hydrogen atmosphere, and the temperature is increased to 400°C at a heating rate of 2°C / min and kept for 1 hour for debinding, and then the temperature is continued to be increased to 1020°C at a heating rate of 4°C / min for 2 hours to obtain a copper heat sink device.

[0056] Example 2: Preparation of Aluminum Turbine Blades

[0057] (1) Preparation of aluminum slurry: TMPTA (1.3 parts by weight) and HDDA (1.7 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant SP-1344 (0.35 parts by weight) and bis(2,6-difluoro-3-pyrrolphenyl) titanocene (0.2 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve the mixture. Finally, aluminum powder (15 parts by weight, with a refractive index of 1.5) was added and stirred in a mixer for 1 minute to mix the mixture evenly. Thus, the aluminum slurry was prepared.

[0058] (2) The aluminum metal slurry is subjected to vacuum stirring and degassing treatment to avoid defects in the printing process.

[0059] (3) The slurry is added to the near-infrared light-curing additive manufacturing equipment to quickly print the aluminum turbine blade blank. The energy density of the near-infrared light source is 8W / cm 2 , wavelength is 850nm, the maximum single layer thickness of printing is about 0.7mm, and the molding speed is 252mm / h.

[0060] (4) The formed body is removed from the printing platform, and the residual resin is cleaned with alcohol, and then the body is kept at 40°C for 0.5 hours to completely dry the body. Finally, the body is placed in an inert atmosphere debinding sintering furnace, and the temperature is increased to 400°C at a heating rate of 1°C / min and kept for 1 hour for debinding, and then the temperature is continued to be increased to 630°C at a heating rate of 3°C / min and sintered for 2 hours to obtain an aluminum turbine blade device.

[0061] Example 3: Preparation of Nickel Metal Electrode

[0062] (1) Preparation of nickel metal slurry: TPGDA (2.1 parts by weight) and PET4A (2.4 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant SP-710 (0.1 parts by weight) and photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (0.5 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve the mixture. Finally, nickel powder (22 parts by weight, with a refractive index nD of 1.9) was added and stirred in a mixer for 1 minute to mix the mixture evenly. Thus, the nickel metal slurry was prepared.

[0063] (2) The nickel metal slurry is subjected to vacuum degassing treatment to avoid defects in the printing process.

[0064] (3) The slurry is added to a near-infrared light-curing additive manufacturing device to quickly print a nickel metal electrode blank. The energy density of the near-infrared light source is 7W / cm 2 , wavelength is 950nm, the maximum single layer thickness of printing is about 0.9mm, and the molding speed is 324mm / h.

[0065] (4) The formed green body is removed from the printing platform, and the residual resin is cleaned with alcohol, and then placed at a temperature of 40°C for 0.5 hours to completely dry the green body. Finally, the green body is placed in an inert atmosphere debinding sintering furnace, and the temperature is increased to 390°C at a heating rate of 3°C / min for 1 hour for debinding, and then the temperature is continued to be increased to 1300°C at a heating rate of 8°C / min for 2 hours to obtain a nickel metal electrode device.

[0066] Embodiment 4, A1 2 O 3 Preparation of porous sintered ceramic plates

[0067] (1) Preparation of Al 2 O 3 Slurry: PEGDA (2 parts by weight) and PETA (2.5 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes, and then dispersant XYS-5800 (0.1 parts by weight), photoinitiator bis-2,6-difluoro-3-pyrrolephenyl titanocene (0.4 parts by weight) and trimethylbenzoyl-diphenylphosphine oxide (0.1 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve them. Finally, Al 2 O 3 The powder (25 parts by weight, refractive index nD is 2.5) is then placed in a mixer and stirred for 1 minute to make it evenly mixed. 2 O 3 The slurry preparation is completed.

[0068] (2) Al 2 O 3 The slurry is placed in a centrifugal mixer for degassing to avoid defects during the printing process.

[0069] (3) Add the slurry into the near-infrared light-curing additive manufacturing equipment and quickly print the Al 2 O 3 Ceramic porous sintered plate body (such as Figure 2 The energy density of the near-infrared light source is 10W / cm 2 , wavelength is 980nm, the maximum single layer thickness of printing is about 1.1mm, and the molding speed is 396mm / h.

[0070] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 460°C at a heating rate of 5°C / min and kept at that temperature for 1 hour for debinding, and then continued to heat to 1200°C at a heating rate of 10°C / min for 2 hours to obtain Al 2 O 3 Ceramic porous sintered plate device.

[0071] Example 5. Preparation of WC nozzle

[0072] (1) Preparation of WC slurry: HEA (3.5 parts by weight) and PET4A (2.5 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant XYS-2800 (0.1 parts by weight) and photoinitiator bis (2,6-difluoro-3-pyrrolphenyl) titanocene (1.5 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve them. Finally, WC powder (30 parts by weight, refractive index nD is 2.2) was added and stirred in a mixer for 1 minute to mix them evenly. At this point, the WC slurry was prepared.

[0073] (2) Place the WC slurry in a centrifugal mixer for degassing to avoid defects during the printing process.

[0074] (3) Add the slurry into the near-infrared light-curing additive manufacturing equipment and quickly print the WC nozzle blank. The energy density of the near-infrared light source is 5W / cm 2 , wavelength is 1064nm, the maximum single layer thickness of printing is about 1mm, and the molding speed is 360mm / h.

[0075] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 420°C at a heating rate of 5°C / min and kept for 1 hour for debinding, and then continued to be heated to 1450°C at a heating rate of 10°C / min for 2 hours to obtain a WC nozzle device.

[0076] Example 6, ZrO 2 Preparation of ceramic bearings

[0077] (1) Preparation of ZrO 2Slurry: HDDA (2.6 parts by weight) and TMPTA (1.9 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes, and then dispersant XYS-710 (0.1 parts by weight), photoinitiator bis-2,6-difluoro-3-pyrrolphenyl titanocene (0.5 parts by weight) and 2,4-diethylthiazolone photoinitiator (0.5 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve them. Finally, ZrO 2 The powder (28 parts by weight, refractive index nD is 2.2) was placed in a mixer and stirred for 1 min to make it uniformly mixed. 2 The slurry preparation is completed.

[0078] (2)Place ZrO 2 The slurry is placed in a centrifugal mixer for degassing to avoid defects during the printing process.

[0079] (3) Add the slurry into the near-infrared light-curing additive manufacturing equipment and quickly print ZrO 2 Ceramic bearing blank. The energy density of the near-infrared light source is 10W / cm 2 , wavelength is 980nm, the maximum single layer thickness of printing is about 0.75mm, and the molding speed is 270mm / h.

[0080] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 390°C at a heating rate of 5°C / min and kept at that temperature for 1 hour for debinding, and then continued to be heated to 1600°C at a heating rate of 10°C / min for 2 hours to obtain ZrO 2 Ceramic bearing components.

[0081] Example 7: Preparation of 316L stainless steel three-dimensional structure device

[0082] (1) Preparation of 316L slurry: DPGDA (2 parts by weight) and PETA (1.5 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant SP-710 (0.1 parts by weight), photoinitiator bis-2,6-difluoro-3-pyrrolophenyl titanocene (0.4 parts by weight) and trimethylbenzoyl-diphenylphosphine oxide photoinitiator (0.2 parts by weight) were added and placed in an ultrasonic dissolver for 15 minutes to fully dissolve. Finally, 316L stainless steel powder (18 parts by weight, refractive index nD is 2.8) was added and placed in a mixer and stirred for 1 minute to mix evenly. At this point, the preparation of 316L slurry was completed.

[0083] (2) Place the 316L slurry in a centrifugal mixer for degassing to avoid defects during the printing process.

[0084] (3) The slurry is added to the near-infrared light-curing additive manufacturing equipment to quickly print a 316L stainless steel three-dimensional structure device blank. The energy density of the near-infrared light source is 8W / cm 2 , wavelength is 1064nm, the maximum single layer thickness of printing is about 0.8mm, and the molding speed is 288mm / h.

[0085] (4) The formed body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the body. Finally, the body was placed in an inert atmosphere debinding sintering furnace, heated to 400°C at a heating rate of 3°C / min and kept for 1 hour for debinding, and then continued to be heated to 1350°C at a heating rate of 8°C / min for 2 hours to obtain a 316L stainless steel three-dimensional structure device.

[0086] Example 8. Preparation of SiC ceramic filter

[0087] (1) Preparation of SiC slurry. HDDA (1.2 parts by weight) and PEGDA (3.1 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant P5398 (0.1 parts by weight) and photoinitiator bis-2,6-difluoro-3-pyrrolephenyl titanocene (0.5 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve them. Finally, SiC powder (27 parts by weight, refractive index nD is 2.6) was added and stirred in a mixer for 1 minute to mix them evenly. At this point, the preparation of SiC slurry was completed.

[0088] (2) The SiC slurry is subjected to vacuum stirring and degassing treatment to avoid defects in the printing process.

[0089] (3) The slurry is added to a near-infrared light-curing additive manufacturing device to quickly print a SiC ceramic filter blank. The energy density of the near-infrared light source is 10 W / cm 2 , wavelength is 980nm, the maximum single layer thickness of printing is about 0.85mm, and the molding speed is 306mm / h.

[0090] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 420°C at a heating rate of 3°C / min for 1 hour for debinding, and then continued to be heated to 1300°C at a heating rate of 5°C / min for 2 hours to obtain a SiC ceramic filter device.

[0091] Example 9: Preparation of WC-Co cemented carbide drill

[0092] (1) Preparation of WC-Co slurry. PEGDA (3.5 parts by weight) and PUA (2.1 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Then, dispersant SP-1344 (0.1 parts by weight) and photoinitiator bis-2,6-difluoro-3-pyrrolephenyl titanocene (0.7 parts by weight) and 2,4-diethylthiazolone (0.5 parts by weight) were added and placed in an ultrasonic dissolver for 15 minutes to fully dissolve. Finally, WC-Co powder (31 parts by weight, refractive index nD is 2.4) was added and stirred in a mixer for 1 minute to mix evenly. At this point, the WC-Co slurry was prepared.

[0093] (2) The WC-Co slurry is placed in a centrifugal mixer for degassing to avoid defects during the printing process.

[0094] (3) The slurry is added to the near-infrared light-curing additive manufacturing equipment to quickly print the WC-Co drill blank. The energy density of the near-infrared light source is 5W / cm 2 , wavelength is 980nm, the maximum single layer thickness of printing is about 1.2mm, and the molding speed is 432mm / h.

[0095] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 430°C at a heating rate of 3°C / min for 1 hour for debinding, and then continued to be heated to 1400°C at a heating rate of 5°C / min for 1 hour to obtain a WC-Co cemented carbide drill bit device.

[0096] Embodiment 10, A1 2 O 3 Preparation of porous sintered ceramic plates

[0097] In this embodiment, the preparation process is basically the same as that of Example 4, except that the curing monomer and the cross-linking agent are changed to TMPTA and HDDA. The preparation process is as follows:

[0098] (1) Preparation of Al 2 O 3Slurry: HDDA (2 parts by weight) and TMPTA (2.5 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes, and then dispersant XYS-5800 (0.1 parts by weight), bis-2,6-difluoro-3-pyrrolephenyl titanocene (0.4 parts by weight) and trimethylbenzoyl-diphenylphosphine oxide (0.1 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve them. Finally, Al 2 O 3 The powder (25 parts by weight, refractive index nD is 2.5) is then placed in a mixer and stirred for 1 minute to make it evenly mixed. 2 O 3 The slurry preparation is completed.

[0099] (2) Al 2 O 3 The slurry is placed in a centrifugal mixer for degassing to avoid defects during the printing process.

[0100] (3) Add the slurry into the near-infrared light-curing additive manufacturing equipment and quickly print the Al 2 O 3 Ceramic porous sintered plate blank. The energy density of the near-infrared light source is 10W / cm 2 , wavelength is 980nm, the maximum single layer thickness of printing is about 0.8mm, and the molding speed is 288mm / h.

[0101] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 460°C at a heating rate of 5°C / min and kept at that temperature for 1 hour for debinding, and then continued to heat to 1200°C at a heating rate of 10°C / min for 2 hours to obtain Al 2 O 3 Ceramic porous sintered plate device.

[0102] Example 11: Preparation of Aluminum Turbine Blades

[0103] In this embodiment, the preparation process is basically the same as that of Example 4, except that the curing monomer and the cross-linking agent are changed to HDDA and PEGDA. The preparation process is as follows:

[0104] (1) Preparation of aluminum slurry: HDDA (1.3 parts by weight) and PEGDA (1.7 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant SP-1344 (0.35 parts by weight) and bis(2,6-difluoro-3-pyrrolphenyl) titanocene (0.2 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve the mixture. Finally, aluminum powder (15 parts by weight, with a refractive index of 1.5) was added and stirred in a mixer for 1 minute to mix the mixture evenly. Thus, the aluminum slurry was prepared.

[0105] (2) The aluminum metal slurry is subjected to vacuum stirring and degassing treatment to avoid defects in the printing process.

[0106] (3) The slurry is added to the near-infrared light-curing additive manufacturing equipment to quickly print the aluminum turbine blade blank. The energy density of the near-infrared light source is 8W / cm 2 , wavelength is 850nm, the maximum single layer thickness of printing is about 0.4mm, and the molding speed is 144mm / h.

[0107] (4) The formed body is removed from the printing platform, and the residual resin is cleaned with alcohol, and then the body is kept at 40°C for 0.5 hours to completely dry the body. Finally, the body is placed in an inert atmosphere debinding sintering furnace, and the temperature is increased to 400°C at a heating rate of 1°C / min and kept for 1 hour for debinding, and then the temperature is continued to be increased to 630°C at a heating rate of 3°C / min and sintered for 2 hours to obtain an aluminum turbine blade device.

[0108] Comparative Example 1: Preparation of Copper Heat Sink

[0109] In this comparative example, the preparation process is basically the same as in Example 1, except that the light source of the additive manufacturing equipment is changed to ultraviolet light (355 nm). The preparation process is as follows:

[0110] (1) Preparation of copper metal slurry: HDDA (1.8 parts by weight) and TMPTA (1.4 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant XYS-2800 (0.1 parts by weight), photoinitiator trimethylbenzoyl-diphenylphosphine oxide (0.05 parts by weight) and bis-2,6-difluoro-3-pyrrolphenyl titanocene (0.2 parts by weight) were added and placed in an ultrasonic dissolver for 15 minutes to fully dissolve. Finally, copper powder (16 parts by weight, refractive index nD is 2.2) was added and stirred in a mixer for 1 minute to mix evenly. At this point, the preparation of copper metal slurry was completed.

[0111] (2) The copper metal slurry is placed in a centrifugal mixer for degassing to avoid defects in the printing process.

[0112] (3) Add the slurry into the UV curing additive manufacturing equipment and quickly print the copper heat sink blank. The energy density of the UV light source is 1W / cm 2 , wavelength is 355nm, the maximum single layer thickness of printing is about 0.04mm, and the molding speed is 14.4mm / h.

[0113] (4) The formed green body is removed from the printing platform, and the residual resin is cleaned with alcohol, and then placed at a temperature of 40°C for 0.5 hours to completely dry the green body. Finally, the green body is placed in a debinding sintering furnace in a hydrogen atmosphere, and the temperature is increased to 400°C at a heating rate of 2°C / min and kept for 1 hour for debinding, and then the temperature is continued to be increased to 1020°C at a heating rate of 4°C / min for 2 hours to obtain a copper heat sink device.

[0114] Compared with Example 1, the maximum single-layer thickness of Comparative Example 1 is only 0.04 mm, much lower than 1.1 mm of Example 1, and the molding speed is only 14.4 mm / h, much lower than 396 mm / h of Example 1.

[0115] Comparative Example 2, Al 2 O 3 Preparation of porous sintered ceramic plates

[0116] In this comparative example, the preparation process is basically the same as in Example 4, except that the light source of the additive manufacturing equipment is changed to ultraviolet light (405 nm). The preparation process is as follows:

[0117] (1) Preparation of Al 2 O 3 Slurry: PEGDA (2 parts by weight) and PETA (2.5 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes, and then dispersant XYS-5800 (0.1 parts by weight), photoinitiator bis-2,6-difluoro-3-pyrrolephenyl titanocene (0.4 parts by weight) and trimethylbenzoyl-diphenylphosphine oxide (0.1 parts by weight) were added and ultrasonicated in an ultrasonic dissolver for 15 minutes to fully dissolve them. Finally, Al 2 O 3 The powder (25 parts by weight, refractive index nD is 2.5) is then placed in a mixer and stirred for 1 minute to make it evenly mixed. 2 O 3 The slurry preparation is completed.

[0118] (2) Al 2 O 3 The slurry is placed in a centrifugal mixer for degassing to avoid defects during the printing process.

[0119] (3) Add the slurry into the UV-curing additive manufacturing equipment and quickly print the Al 2 O3 Ceramic porous sintered plate blank. The energy density of the ultraviolet light source is 1.5W / cm 2 , wavelength is 405nm, the maximum single layer thickness of printing is about 0.2mm, and the molding speed is 72mm / h.

[0120] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 460°C at a heating rate of 5°C / min and kept at that temperature for 1 hour for debinding, and then continued to heat to 1200°C at a heating rate of 10°C / min for 2 hours to obtain Al 2 O 3 Ceramic porous sintered plate device.

[0121] Compared with Example 4, the maximum single-layer thickness of Comparative Example 2 is only 0.2 mm, much lower than 1.1 mm of Example 1, and the molding speed is only 72 mm / h, much lower than 396 mm / h of Example 1.

[0122] Comparative Example 3: Preparation of WC-Co Carbide Drill

[0123] In this comparative example, the preparation process is basically the same as in Example 9, except that the energy density of the light source of the additive manufacturing equipment is reduced to 2W / cm 2 , the preparation process is as follows:

[0124] (1) Preparation of WC-Co slurry. PEGDA (3.5 parts by weight) and PUA (2.1 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant SP-1344 (0.1 parts by weight) and photoinitiator bis-2,6-difluoro-3-pyrrolephenyl titanocene (0.7 parts by weight) and 2,4-diethylthiazolone (0.5 parts by weight) were added and placed in an ultrasonic dissolver for 15 minutes to fully dissolve. Finally, WC-Co powder (31 parts by weight, refractive index nD is 2.4) was added and stirred in a mixer for 1 minute to mix evenly. At this point, the WC-Co slurry was prepared.

[0125] (2) The WC-Co slurry is placed in a centrifugal mixer for degassing to avoid defects during the printing process.

[0126] (3) The slurry is added to the near-infrared light-curing additive manufacturing equipment to quickly print the WC-Co drill blank. The energy density of the near-infrared light source is 2W / cm 2 , wavelength is 980nm, the maximum single layer thickness of printing is about 0.2mm, and the molding speed is 72mm / h.

[0127] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 430°C at a heating rate of 3°C / min for 1 hour for debinding, and then continued to be heated to 1400°C at a heating rate of 5°C / min for 1 hour to obtain a WC-Co cemented carbide drill bit device.

[0128] Compared with Example 9, the maximum single-layer thickness of Comparative Example 3 is reduced to 0.2 mm, which is lower than 1.2 mm in Example 9, and the molding speed is reduced to 72 mm / h, which is lower than 432 mm / h in Example 9.

[0129] Comparative Example 4: Preparation of WC-Co Carbide Drill

[0130] In this embodiment, the preparation process is basically the same as in Example 9, except that the photoinitiator is changed to a thermal initiator azobisisobutyronitrile. The preparation process is as follows:

[0131] (1) Preparation of WC-Co slurry. PEGDA (3.5 parts by weight) and PUA (2.1 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes. Dispersant SP-1344 (0.1 parts by weight) and azobisisobutyronitrile (1.2 parts by weight) were added and placed in an ultrasonic dissolver for 15 minutes to fully dissolve. Finally, WC-Co powder (31 parts by weight, refractive index nD is 2.4) was added and stirred in a mixer for 1 minute to mix evenly. At this point, the WC-Co slurry was prepared.

[0132] (2) The WC-Co slurry is placed in a centrifugal mixer for degassing to avoid defects during the printing process.

[0133] (3) The slurry is added to the near-infrared light-curing additive manufacturing equipment to quickly print the WC-Co drill blank. The energy density of the near-infrared light source is 5W / cm 2 , wavelength is 980nm, the maximum single layer thickness of printing is about 1.0mm, and the molding speed is 360mm / h.

[0134] (4) The formed green body was removed from the printing platform, and the residual resin was cleaned with alcohol, and then kept at 40°C for 0.5 hours to completely dry the green body. Finally, the green body was placed in an inert atmosphere debinding sintering furnace, heated to 430°C at a heating rate of 3°C / min for 1 hour for debinding, and then continued to be heated to 1400°C at a heating rate of 5°C / min for 1 hour to obtain a WC-Co cemented carbide drill bit device.

[0135] Compared with Example 9, the maximum single layer thickness of Comparative Example 4 is reduced to 1.0 mm, which is lower than 1.2 mm of Example 9, and the molding speed is reduced to 360 mm / h, which is lower than 432 mm / h of Example 9. After the initiator is replaced with a thermal initiator, the temperature of some areas of the sample is too high during the printing process, which makes the organic system prone to over-reaction under the thermal initiator, which is specifically manifested as: the actual accuracy is worse than that of Example 9, and there is a slight coking phenomenon in the concentrated temperature area of ​​the green body.

[0136] Comparative Example 5: Preparation of WC-Co Carbide Drill

[0137] In this embodiment, the preparation process is basically the same as in Example 9, except that the energy density of the light source of the additive manufacturing equipment is increased to 16W / cm 2 , the preparation process is as follows:

[0138] 1) Preparation of WC-Co slurry. PEGDA (3.5 parts by weight) and PUA (2.1 parts by weight) were mixed and dispersed in a high-speed disperser for 5 minutes, and then dispersant SP-1344 (0.1 parts by weight) and photoinitiator bis-2,6-difluoro-3-pyrrolephenyl titanocene (0.7 parts by weight) and 2,4-diethylthiazolone (0.5 parts by weight) were added and placed in an ultrasonic dissolver for 15 minutes to fully dissolve it. Finally, WC-Co powder (31 parts by weight, refractive index nD is 2.4) was added and stirred in a mixer for 1 minute to mix it evenly. At this point, the WC-Co slurry was prepared.

[0139] (2) The WC-Co slurry is placed in a centrifugal mixer for degassing to avoid defects during the printing process.

[0140] (3) When the slurry is added to the near-infrared light-curing additive manufacturing equipment, the blank cannot be printed normally. The single-layer morphology is as follows Figure 4 As shown, most of them are charred.

[0141] Compared with Example 9, in Comparative Example 5, the sample temperature was too high due to the excessively high energy density of the light source of the equipment, resulting in large-scale carbonization of the organic system and thus failure to print.

[0142] In addition, according to Figure 5 Comparison of the infrared spectra of the slurries before and after near-infrared light curing shows that the -1 The characteristic peak of carbon-carbon double bond at the position has obvious changes. Table 1 shows the changes in the double bond infrared peak area of ​​the slurry of different embodiments before and after near-infrared light curing. It can be seen from Table 1 that there is a conversion of double bonds in the organic system during the curing process, proving that the process is photocuring. At the same time, according to Figure 6 and Figure 7Comparing the absorbance variation trends of different powders and their slurries in the 300-1100nm wavelength range, it can be seen that the slurry system begins to show a significant increase in absorbance at 850nm compared to the powder. This shows that the slurry system is more conducive to the absorption of near-infrared light, increasing the efficiency of photothermal conversion, and thus improving the curing efficiency of the organic system.

[0143] Table 1 Comparison of double bond infrared peak areas of different slurries before and after near infrared light curing

[0144]

[0145] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A near-infrared light direct curing additive manufacturing slurry, which comprises, by weight: 2-15 parts of a first auxiliary agent, 10-85 parts of an inorganic material powder, 0.01-5 parts of a dispersant, and 0.01-5 parts of a photoinitiator; in, The slurry does not contain up-conversion luminescent material; Wherein, the first auxiliary agent acts as a curing monomer and a cross-linking agent in the slurry; Wherein, the refractive index nD of the inorganic material powder is 1.5-2.

8.

2. The near-infrared light direct curing additive manufacturing slurry as claimed in claim 1, in, The near-infrared light direct curing additive manufacturing slurry further includes a dye and / or a solvent.

3. The near-infrared light direct curing additive manufacturing slurry according to claim 1, wherein the inorganic material powder comprises Al 2 O 3 Powder, SiC powder, Si 3 N 4 Powder, ZrO 2 One or more of powder, hydroxyapatite, WC powder, glass powder, aluminum powder, copper powder, nickel powder, tungsten powder, stainless steel powder, and cemented carbide powder.

4. The near-infrared light direct curing additive manufacturing slurry according to claim 1, in, The first auxiliary agent contains both a first auxiliary agent A and a first auxiliary agent B, wherein the first auxiliary agent A is at least one of tripropylene glycol diacrylate (TPGDA) and trimethylolpropane triacrylate (TMPTA), and the first auxiliary agent B is at least one of 1,6-hexanediol diacrylate (HDDA), polyethylene glycol diacrylate (PEGDA), and dipropylene glycol diacrylate (DPGDA); at the same time, the slurry contains one or more of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and bis (2,6-difluoro-3-pyrrolephenyl) titanocene as photoinitiators; and the refractive index range of the inorganic material powder in the slurry is 1.5 to <2.

0.

5. The near-infrared light direct curing additive manufacturing slurry as claimed in claim 1, in, The first auxiliary agent contains both a first auxiliary agent C and a first auxiliary agent D, wherein the first auxiliary agent C is at least one of pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PET4A), and polyurethane acrylate (PUA), and the first auxiliary agent D is at least one of polyethylene glycol diacrylate (PEGDA), hydroxyethyl acrylate (HEA), and hydroxyethyl methacrylate (HEMA); at the same time, the slurry contains one or more of trimethylbenzoyl-diphenylphosphine oxide, 2,4-diethylthiazolone, and bis-2,6-difluoro-3-pyrrolphenyl titanocene as photoinitiators; and the refractive index range of the inorganic material powder in the slurry is 2.0 to 2.

8.

6. The method for preparing the near-infrared light direct curing additive manufacturing slurry according to any one of claims 1 to 5, include: The slurry raw materials are mixed evenly to obtain the near-infrared light direct curing additive manufacturing slurry; the slurry raw materials include a first auxiliary agent, a photoinitiator, an inorganic material powder and a dispersant.

7. A method for manufacturing three-dimensional structure products by direct curing with near-infrared light, include: (1) obtaining the near-infrared light direct curing additive manufacturing slurry as described in any one of claims 1 to 5; (2) performing a debubbling treatment on the near-infrared light direct curing additive manufacturing slurry to obtain a debubbled slurry; (3) adding the debubbled slurry into a near-infrared light-curing additive manufacturing device for 3D printing to obtain a green body of a three-dimensional structured product; (4) debinding and sintering the green body to obtain a three-dimensional structure product; In step (3), the light source used for curing is near-infrared light with a wavelength range of 850-1100 nm and an energy density of 3 W / cm 2 ~15W / cm 2 .

8. The method for manufacturing a three-dimensional structure product by direct near-infrared light curing as claimed in claim 7, in, In the step (1), the near-infrared light direct curing additive manufacturing slurry as claimed in claim 4 is obtained, and the wavelength of the light source used for curing in the step (3) is 850-<980nm.

9. The method for manufacturing a three-dimensional structure product by direct near-infrared light curing as claimed in claim 7, in, In the step (1), the near-infrared light direct curing additive manufacturing slurry as claimed in claim 5 is obtained, and the wavelength of the light source used for curing in the step (3) is 980-1100nm.

10. A three-dimensional structural product, prepared by the method for manufacturing a three-dimensional structural product by near-infrared light direct curing as described in any one of claims 7 to 9.

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