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

Abstract

The present invention provides a near-infrared light direct-curing additive manufacturing slurry and a preparation method thereof. Calculated by weight parts, the slurry comprises: 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. Among them, the first auxiliary agent acts as a curing monomer and a crosslinking 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 upconversion luminescent material. The slurry can be directly cured under the action of infrared light with a wavelength range of 850-1100 nm and a light source energy density of 3 W / cm<supgt;2< / supgt> to 15 W / cm<supgt;2< / supgt>. The near-infrared light direct-curing additive manufacturing technology of the present invention has the advantages of fast forming speed, high single-layer thickness and high precision, low energy consumption and high efficiency, providing a new solution for the large-scale industrial application of additive manufacturing.

Description

Technical Field

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

[0002] Inorganic materials, such as metal and ceramic materials, are widely used in the fields of aviation, machinery, military industry, electronics, and chemical industry due to their excellent basic properties. Traditional metal or ceramic processing and forming methods are often based on molds or subtractive manufacturing, with high production costs, and large-scale production cannot be achieved for the preparation of 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, light-curing additive manufacturing has the advantages of high efficiency, high precision, and low energy consumption. Compared with other additive manufacturing processes, which have problems such as long cycle, difficult processing, and high cost in preparing complex-structure metal and ceramic devices, preparing complex-structure metal or ceramic devices by light-curing additive manufacturing has better economic and technical advantages.

[0004] Generally speaking, light-curing additive manufacturing slurries of metals or ceramics have a high powder addition amount, and the light source of the corresponding light-curing additive manufacturing equipment is ultraviolet light, and the penetration of ultraviolet light into such inorganic powders is insufficient. In addition, the refractive index of the powder for ultraviolet light is relatively large, and the refraction behavior is relatively complex, resulting in problems such as low curing depth and poor curing efficiency in light-curing additive manufacturing, thus making the light-curing additive manufacturing of inorganic materials unable to be applied on a large scale.

[0005] In order to solve the above problem of low ultraviolet light curing depth, in recent years, there has been an exploration of technologies using near-infrared light for light curing. Such technologies usually require adding upconversion luminescent materials to the slurry to convert near-infrared light into ultraviolet light for light curing. Thus, the following disadvantages are brought: First, the vast majority of 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 a relatively high energy density of the near-infrared light source is required, resulting in high equipment costs.

[0006] Therefore, there is an urgent need for a new light-curing additive manufacturing slurry and a preparation method to solve the above technical problems. Summary of the Invention

[0007] Aiming at the above deficiencies, the present invention proposes a near-infrared light direct-curing additive manufacturing slurry and a preparation method thereof to solve the defects in the prior art such as low ultraviolet light curing depth, poor curing efficiency, high cost, expensive upconversion materials for infrared light curing, and high cost of high-power light source equipment.

[0008] The present invention provides a near-infrared light direct-curing additive manufacturing slurry. In terms of parts by weight, the slurry comprises: 2-15 parts of a first additive, 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 an up-conversion luminescent material;

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

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

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

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

[0014] wherein, when the near-infrared light direct-curing additive manufacturing slurry is a white system, for example, when the inorganic material powder in the slurry comprises one or more of Al 2 O 3 powder, ZrO 2 powder, hydroxyapatite, and glass powder, the slurry may further contain a dye, and the dosage of the dye is 0.5-2 parts by weight; the dye comprises 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 the absorption of near-infrared light and thus promotes the curing behavior.

[0015] wherein, when the first additive in the near-infrared light direct-curing additive manufacturing slurry is a water-based system, for example, when the first additive in the slurry comprises one or more of hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), and polyethylene glycol diacrylate (PEGDA), the slurry may further contain a water-based solvent, the dosage of the water-based solvent is 5-10 parts by weight, and the water-based solvent comprises one or more of water, ethanol, ethylene glycol, dipropylene glycol butyl ether (DPNB), and propylene glycol methyl ether (PM).

[0016] Among them, the first additive acts as a curing monomer and a crosslinking agent in the near-infrared light direct-curing additive manufacturing slurry.

[0017] Among them, the first additive 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] Among them, the inorganic material powder includes Al 2 O 3 powder, SiC powder, Si 3 N 4 powder, ZrO 2 powder, hydroxyapatite, WC powder, glass powder, aluminum powder, copper powder, nickel powder, tungsten powder, stainless steel powder, cemented carbide powder, etc., one or more of them.

[0019] Among them, the photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, trimethylbenzoyl-diphenylphosphine oxide, 2,4-diethylthiazolethione, and bis(2,6-difluoro-3-pyrrolylphenyl)titanocene dichloride.

[0020] Among them, 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 preferred composition of the near-infrared light direct-curing additive manufacturing slurry includes: in the first additive, both the first additive A and the first additive B are contained. The first additive A is at least one of tripropylene glycol diacrylate (TPGDA) and trimethylolpropane triacrylate (TMPTA), and the first additive 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 phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and bis(2,6-difluoro-3-pyrrolylphenyl)titanocene dichloride 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 <980 nm. Among them, the first additive A serves as a curing monomer, and the first additive B serves as a crosslinking agent.

[0022] Among them, the preferred composition of the near-infrared light direct-curing additive manufacturing slurry includes: in the first additive, both the first additive C and the first additive D are contained. The first additive C is at least one of pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PET4A), and polyurethane acrylate (PUA), and the first additive D is at least one of polyethylene glycol diacrylate (PEGDA), 2-hydroxyethyl acrylate (HEA), and 2-hydroxyethyl methacrylate (HEMA); meanwhile, the slurry contains one or more of trimethylbenzoyl-diphenylphosphine oxide, 2,4-diethylthiazolone, and bis(2,6-difluoro-3-pyrrolylphenyl)titanocene dichloride 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 additive, the first additive C serves as a curing monomer and the first additive D serves as a crosslinking agent.

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

[0024] Among them, the preferred preparation method of the near-infrared light direct-curing additive manufacturing slurry includes: first mixing the first additive and the photoinitiator, and after the photoinitiator is completely dissolved, adding the dispersant and the inorganic material powder successively and mixing evenly to obtain 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 near-infrared light direct-curing, including:

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

[0027] (2) Performing a defoaming treatment on the near-infrared light direct-curing additive manufacturing slurry to obtain the slurry after defoaming treatment;

[0028] (3) Adding the slurry after defoaming treatment into a near-infrared light-curing additive manufacturing device and performing 3D printing to obtain a green body of the three-dimensional structure product;

[0029] (4) Performing debinding and sintering on the green body to manufacture the three-dimensional structure product;

[0030] Among them, in the step (2), the defoaming treatment includes performing a degassing treatment on the slurry; the time of the defoaming treatment is 1 - 2 min.

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

[0032] Among them, in the step (3), the 3D printing preferably adopts stereolithography (SLA) or digital light processing (DLP) technology for 3D printing.

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

[0034] The present invention also provides a three-dimensional structure product prepared by the method of directly curing and manufacturing a three-dimensional structure product with the above-mentioned near-infrared light.

[0035] The curing thickness of the ultraviolet light curing additive manufacturing of conventional inorganic powders is about 30 - 200 microns, while the curing thickness of the additive manufacturing of a three-dimensional structure product by curing with the present invention can reach about 1000 microns, and can even reach 2000 microns at most.

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

[0037] (1) In the near-infrared light direct-curing additive manufacturing slurry of the present invention, without adding an up-conversion luminescent material, the direct curing of near-infrared light can be used to manufacture a three-dimensional product. Thus, 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, which improves the laser penetration ability. Moreover, by using an inorganic powder material with a specific refractive index to enhance the absorption of near-infrared light, the photothermal conversion of the inorganic powder to near-infrared light is utilized to dissociate the photoinitiator to initiate the curing of the slurry. Specifically, the absorption of near-infrared light by the inorganic powder converts light energy into heat energy. Under the irradiation of near-infrared light with a certain intensity, the instantaneous heat energy converted by the inorganic powder can dissociate the photoinitiator to 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 ultraviolet light 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. Thus, the curing efficiency and curing depth of the inorganic material slurry curing and forming are improved by the method of the present invention, that is, the curing depth is deeper (the curing depth is increased from 30 - 200 μm to 1 - 2 mm), and the curing efficiency is higher (increased from the conventional 11 mm / h - 72 mm / h to 357 mm / h - 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. Thus, it has the following advantages: a. Wide material compatibility: Each component of the slurry is a material 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 with 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 of the present invention has the advantages of high speed (the printing speed can reach 357 mm / h to 715 mm / h), high layer thickness (the single-layer thickness can reach 1 to 2 mm), low energy consumption (the light source energy density is lower compared with near-infrared light curing additive manufacturing based on up-conversion materials), 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 operation of the present invention is simple and the threshold is low. Different from other additive manufacturing methods for inorganic material powders, the method of the present invention has no special requirements for the fluidity and powder morphology of the powders, breaking the limitations of conventional additive manufacturing methods for inorganic material powders and having wide applicability. Description of the Drawings

[0042] Figure 1 It is the single-layer curing morphology of the copper metal slurry prepared in Example 1.

[0043] Figure 2 It is the single-layer curing morphology of the alumina slurry prepared in Example 4.

[0044] Figure 3 It is the single-layer curing morphology of different sizes of the copper metal slurry prepared in Example 1.

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

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

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

[0048] Figure 7 It is the comparison of the absorbance of the photoinitiator and the slurries in Examples 1, 5, and 8 in the wavelength range of 300 to 1100 nm. Detailed Embodiments

[0049] The present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that these embodiments are only for illustration and not for limiting 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 can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims of this application.

[0050] In the following embodiments, the 3D printing is carried out by using stereolithography (SLA) technology for 3D printing.

[0051] Example 1: Preparation of a copper heat sink

[0052] (1) Preparation of copper metal slurry: Mix PEGDA (1.8 parts by weight) and PETA (1.4 parts by weight), disperse them under a high-speed disperser for 5 minutes, then add dispersant XYS-2800 (0.1 part by weight), photoinitiator trimethylbenzoyl-diphenylphosphine oxide (0.05 part by weight) and bis(2,6-difluoro-3-pyrrolophenyl)titanocene (0.2 part by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 minutes to fully dissolve them. Finally, add copper powder (16 parts by weight, refractive index nD is 2.2), and then place it in a mixer and stir for 1 minute to make it evenly mixed. Thus, the copper metal slurry is prepared.

[0053] (2) Place the copper metal slurry in a centrifugal stirrer for degassing treatment to avoid defects during printing.

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

[0055] (4) Take out the formed blank from the printing platform, wash its residual resin with alcohol, and then keep it at a temperature of 40 °C for 0.5 hours to completely dry the blank. Finally, place the blank in a debinding and sintering furnace under a hydrogen atmosphere, raise the temperature to 400 °C at a heating rate of 2 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1020 °C at a heating rate of 4 °C / min and sinter for 2 hours to obtain a copper heat sink device.

[0056] Example 2: Preparation of an aluminum turbine blade

[0057] (1) Preparation of aluminum metal paste: Mix TMPTA (1.3 parts by weight) and HDDA (1.7 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant SP-1344 (0.35 parts by weight) and bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.2 parts by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add aluminum powder (15 parts by weight, refractive index nD is 1.5), and then place it in a mixer and stir for 1 min to make it evenly mixed. Thus, the aluminum metal paste is prepared.

[0058] (2) Perform vacuum stirring and degassing treatment on the aluminum metal paste to avoid defects during the printing process.

[0059] (3) Add the paste into a near-infrared light-curing additive manufacturing device to quickly print an aluminum turbine blade blank. Among them, the energy density of the near-infrared light source is 8 W / cm 2 , the wavelength is 850 nm, the maximum single-layer printing thickness is about 0.7 mm, and the forming speed is 252 mm / h.

[0060] (4) Take out the formed blank from the printing platform, wash the residual resin with alcohol, and then keep it at a temperature of 40 °C for 0.5 hours to completely dry the blank. Finally, place the blank in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 400 °C at a heating rate of 1 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 630 °C at a heating rate of 3 °C / min for sintering for 2 hours to obtain an aluminum turbine blade device.

[0061] Example 3, Preparation of Nickel Metal Electrode

[0062] (1) Preparation of nickel metal paste: Mix TPGDA (2.1 parts by weight) and PET4A (2.4 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant SP-710 (0.1 parts by weight) and photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (0.5 parts by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add nickel powder (22 parts by weight, refractive index nD is 1.9), and then place it in a mixer and stir for 1 min to make it evenly mixed. Thus, the nickel metal paste is prepared.

[0063] (2) Perform vacuum degassing treatment on the nickel metal paste to avoid defects during the printing process.

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

[0065] (4) Remove the formed green body from the printing platform, clean the residual resin with alcohol, and then keep it at a temperature of 40 °C for 0.5 hours to completely dry the green body. Finally, place the green body in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 390 °C at a heating rate of 3 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1300 °C at a heating rate of 8 °C / min for sintering for 2 hours to obtain a nickel metal electrode device.

[0066] Example 4, Al 2 O 3 Preparation of ceramic porous sintered plate

[0067] (1) Preparation of Al 2 O 3 slurry: Mix PEGDA (2 parts by weight) and PETA (2.5 parts by weight), disperse them under a high-speed disperser for 5 min, then add a dispersant XYS-5800 (0.1 part by weight), a photoinitiator bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.4 part by weight) and trimethylbenzoyl-diphenylphosphine oxide (0.1 part by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add Al 2 O 3 powder (25 parts by weight, refractive index nD is 2.5), and then place it in a mixer and stir for 1 min to mix it evenly. Thus, the Al 2 O 3 slurry is prepared.

[0068] (2) Place the Al 2 O 3 slurry in a centrifugal stirrer for degassing treatment to avoid defects during printing.

[0069] (3) Add the slurry to a near-infrared light-curing additive manufacturing device to quickly print an Al 2 O 3 ceramic porous sintered plate green body (as shown in Figure 2 ). Among them, the energy density of the near-infrared light source is 10 W / cm 2 , the wavelength is 980 nm, the maximum single-layer printing thickness is about 1.1 mm, and the forming speed is 396 mm / h.

[0070] (4) Remove the formed green body from the printing platform, clean the residual resin with alcohol, and then keep it at a temperature of 40 °C for 0.5 hours to completely dry the green body. Finally, place the green body in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 460 °C at a heating rate of 5 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1200 °C at a heating rate of 10 °C / min for sintering for 2 hours to obtain an Al 2 O 3 ceramic porous sintered plate device.

[0071] Example 5 Preparation of WC Nozzle

[0072] (1) Prepare WC slurry: Mix HEA (3.5 parts by weight) and PET4A (2.5 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant XYS-2800 (0.1 part by weight) and photoinitiator bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (1.5 parts by weight), place them in an ultrasonic dissolver and ultrasonicate for 15 min to fully dissolve them. Finally, add WC powder (30 parts by weight, refractive index nD is 2.2), and then place it in a mixer and stir for 1 min to mix evenly. Thus, the WC slurry is prepared.

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

[0074] (3) Add the slurry to a near-infrared light-curing additive manufacturing device to quickly print a WC nozzle green body. Among them, the energy density of the near-infrared light source is 5 W / cm 2 , the wavelength is 1064 nm, the maximum single-layer printing thickness is about 1 mm, and the forming speed is 360 mm / h.

[0075] (4) Remove the formed green body from the printing platform, clean the residual resin with alcohol, and then keep it at a temperature of 40 °C for 0.5 hours to completely dry the green body. Finally, place the green body in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 420 °C at a heating rate of 5 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1450 °C at a heating rate of 10 °C / min for sintering for 2 hours to obtain a WC nozzle device.

[0076] Example 6 Preparation of ZrO 2 Ceramic Bearing

[0077] (1) Prepare ZrO 2Slurry: Mix HDDA (2.6 parts by weight) and TMPTA (1.9 parts by weight), disperse the mixture under a high-speed disperser for 5 min, then add dispersant XYS-710 (0.1 part by weight), photoinitiator bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.5 part by weight) and 2,4-diethylthiazole ketone photoinitiator (0.5 part by weight), and place the mixture in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve it. Finally, add ZrO 2 powder (28 parts by weight, refractive index nD is 2.2), then place the mixture in a mixer and stir for 1 min to make it evenly mixed. Thus, the ZrO 2 slurry is prepared.

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

[0079] (3) Add the slurry to a near-infrared light-curing additive manufacturing device to quickly print a ZrO 2 ceramic bearing green body. Among them, the energy density of the near-infrared light source is 10 W / cm 2 , the wavelength is 980 nm, the maximum single-layer printing thickness is about 0.75 mm, and the forming speed is 270 mm / h.

[0080] (4) Take out the formed green body from the printing platform, clean the residual resin with alcohol, then place it under the condition of 40 °C for heat preservation for 0.5 h to completely dry the green body. Finally, place the green body in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 390 °C at a heating rate of 5 °C / min and hold for 1 h for debinding, and then continue to raise the temperature to 1600 °C at a heating rate of 10 °C / min for sintering for 2 h to obtain a ZrO 2 ceramic bearing device.

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

[0082] (1) Prepare 316L slurry: Mix DPGDA (2 parts by weight) and PETA (1.5 parts by weight), disperse the mixture under a high-speed disperser for 5 min, then add dispersant SP-710 (0.1 part by weight), photoinitiator bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.4 part by weight) and trimethylbenzoyl-diphenylphosphine oxide photoinitiator (0.2 part by weight), and place the mixture in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve it. Finally, add 316L stainless steel powder (18 parts by weight, refractive index nD is 2.8), then place the mixture in a mixer and stir for 1 min to make it evenly mixed. Thus, the 316L slurry is prepared.

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

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

[0085] (4) Take out the formed green body from the printing platform, wash the residual resin with alcohol, then keep it at a temperature of 40 °C for 0.5 hours to completely dry the green body. Finally, place the green body in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 400 °C at a heating rate of 3 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1350 °C at a heating rate of 8 °C / min for sintering for 2 hours to obtain a 316L stainless steel three-dimensional structure device.

[0086] Example 8: Preparation of SiC Ceramic Filter

[0087] (1) Prepare the SiC slurry. Mix HDDA (1.2 parts by weight) and PEGDA (3.1 parts by weight), disperse them under a high-speed disperser for 5 min, then add a dispersant P5398 (0.1 part by weight) and a photoinitiator bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.5 part by weight), place them in an ultrasonic dissolver and ultrasonicate for 15 min to fully dissolve them. Finally, add SiC powder (27 parts by weight, refractive index nD is 2.6), and then place it in a mixer and stir for 1 min to mix evenly. Thus, the SiC slurry is prepared.

[0088] (2) Conduct vacuum stirring and degassing treatment on the SiC slurry to avoid defects during printing.

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

[0090] (4) Take out the formed green body from the printing platform, wash the residual resin with alcohol, then keep it at a temperature of 40 °C for 0.5 hours to completely dry the green body. Finally, place the green body in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 420 °C at a heating rate of 3 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1300 °C at a heating rate of 5 °C / min for sintering for 2 hours to obtain a SiC ceramic filter device.

[0091] Example 9: Preparation of WC-Co Cemented Carbide Drill Bit

[0092] (1) Prepare WC-Co slurry. Mix PEGDA (3.5 parts by weight) and PUA (2.1 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant SP-1344 (0.1 part by weight), photoinitiator bis(2,6-difluoro-3-pyrrolophenyl)titanocene (0.7 part by weight), and 2,4-diethylthiazole (0.5 part by weight) (0.5 part by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add WC-Co powder (31 parts by weight, refractive index nD is 2.4), and then place it in a mixer and stir for 1 min to make it evenly mixed. Thus, the WC-Co slurry is prepared.

[0093] (2) Place the WC-Co slurry in a centrifugal stirrer for degassing treatment to avoid defects during the printing process.

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

[0095] (4) Take out the formed blank from the printing platform, wash its residual resin with alcohol, and then place it at a temperature of 40 °C for heat preservation for 0.5 h to completely dry the blank. Finally, place the blank in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 430 °C at a heating rate of 3 °C / min and hold for 1 h for debinding, and then continue to raise the temperature to 1400 °C at a heating rate of 5 °C / min for sintering for 1 h to obtain a WC-Co cemented carbide drill bit device.

[0096] Example 10: Preparation of Al 2 O 3 Ceramic Porous Sintered Plate

[0097] In this example, the preparation process is basically the same as that in Example 4, except that the curing monomer and crosslinking agent are modified to TMPTA and HDDA. The preparation process is as follows:

[0098] (1) Prepare Al 2 O 3Slurry: Mix HDDA (2 parts by weight) and TMPTA (2.5 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant XYS-5800 (0.1 part by weight), bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.4 part by weight) and trimethylbenzoyl-diphenylphosphine oxide (0.1 part by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add Al 2 O 3 powder (25 parts by weight, refractive index nD is 2.5), then place it in a mixer and stir for 1 min to make it evenly mixed. Thus, the Al 2 O 3 slurry is prepared.

[0099] (2) Place the Al 2 O 3 slurry in a centrifugal mixer for degassing treatment to avoid defects during printing.

[0100] (3) Add the slurry to a near-infrared light-curing additive manufacturing device to quickly print an Al 2 O 3 ceramic porous sintered plate blank. Among them, the energy density of the near-infrared light source is 10 W / cm 2 , the wavelength is 980 nm, the maximum single-layer printing thickness is about 0.8 mm, and the forming speed is 288 mm / h.

[0101] (4) Take out the formed blank from the printing platform, wash its residual resin with alcohol, then place it under the condition of 40 °C for heat preservation for 0.5 h to completely dry the blank. Finally, place the blank in a debinding and sintering furnace with an inert atmosphere, raise the temperature to 460 °C at a heating rate of 5 °C / min and hold for 1 h for debinding, and then continue to raise the temperature to 1200 °C at a heating rate of 10 °C / min for sintering for 2 h to obtain an Al 2 O 3 ceramic porous sintered plate device.

[0102] Example 11. Preparation of Aluminum Turbine Blades

[0103] In this example, the preparation process is basically the same as that in Example 4, except that the curing monomer and crosslinking agent are modified to HDDA and PEGDA. The preparation process is as follows:

[0104] (1) Preparation of aluminum metal paste: Mix HDDA (1.3 parts by weight) and PEGDA (1.7 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant SP-1344 (0.35 parts by weight) and bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.2 parts by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve. Finally, add aluminum powder (15 parts by weight, refractive index nD is 1.5), and then place it in a mixer and stir for 1 min to make it evenly mixed. Thus, the aluminum metal paste is prepared.

[0105] (2) Perform vacuum stirring and degassing treatment on the aluminum metal paste to avoid defects during the printing process.

[0106] (3) Add the paste into a near-infrared light-curing additive manufacturing device to quickly print an aluminum turbine blade blank. Among them, the energy density of the near-infrared light source is 8 W / cm 2 , the wavelength is 850 nm, the maximum single-layer printing thickness is about 0.4 mm, and the forming speed is 144 mm / h.

[0107] (4) Take out the formed blank from the printing platform, wash the residual resin with alcohol, and then keep it at a temperature of 40 °C for 0.5 hours to completely dry the blank. Finally, place the blank in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 400 °C at a heating rate of 1 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 630 °C at a heating rate of 3 °C / min for sintering 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 that of Example 1, except that the light source of the additive manufacturing device is changed to ultraviolet light (355 nm). The preparation process is as follows:

[0110] (1) Preparation of copper metal paste: Mix HDDA (1.8 parts by weight) and TMPTA (1.4 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant XYS-2800 (0.1 parts by weight), photoinitiator trimethylbenzoyl-diphenylphosphine oxide (0.05 parts by weight) and bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.2 parts by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve. Finally, add copper powder (16 parts by weight, refractive index nD is 2.2), and then place it in a mixer and stir for 1 min to make it evenly mixed. Thus, the copper metal paste is prepared.

[0111] (2) Place the copper metal paste in a centrifugal mixer for degassing treatment to avoid defects during the printing process.

[0112] (3) Add the slurry into the ultraviolet-curing additive manufacturing equipment and rapidly print to obtain a copper heat sink blank. Among them, the energy density of the ultraviolet light source is 1 W / cm 2 , the wavelength is 355 nm, the maximum single-layer printing thickness is about 0.04 mm, and the forming speed is 14.4 mm / h.

[0113] (4) Take out the formed blank from the printing platform, clean its residual resin with alcohol, then place it at 40 °C for heat preservation for 0.5 hour to completely dry the blank. Finally, place the blank in a debinding and sintering furnace under a hydrogen atmosphere, raise the temperature to 400 °C at a heating rate of 2 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1020 °C at a heating rate of 4 °C / min for sintering for 2 hours to obtain a copper heat sink device.

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

[0115] Comparative Example 2, Preparation of Al 2 O 3 Ceramic porous sintered plate

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

[0117] (1) Prepare Al 2 O 3 Slurry: Mix PEGDA (2 parts by weight) and PETA (2.5 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant XYS-5800 (0.1 part by weight), photoinitiator bis(2,6-difluoro-3-pyrrolylphenyl)titanocene (0.4 part by weight) and trimethylbenzoyl-diphenylphosphine oxide (0.1 part by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add Al 2 O 3 powder (25 parts by weight, refractive index nD is 2.5), and then place it in a mixer and stir for 1 min to mix it evenly. Thus, the Al 2 O 3 slurry is prepared.

[0118] (2) Place the Al 2 O 3 slurry in a centrifugal stirrer for degassing treatment to avoid defects during printing.

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

[0120] (4) Take out the formed blank from the printing platform, clean the residual resin with alcohol, and then keep it warm at 40 °C for 0.5 hours to completely dry the blank. Finally, place the blank in a debinding and sintering furnace with an inert atmosphere, raise the temperature to 460 °C at a heating rate of 5 °C / min and keep it warm for 1 hour for debinding, and then continue to raise the temperature to 1200 °C at a heating rate of 10 °C / min for sintering for 2 hours to obtain Al 2 O 3 Ceramic porous sintered plate device.

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

[0122] Preparation of WC-Co cemented carbide drill bit in Comparative Example 3

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

[0124] (1) Prepare WC-Co slurry. Mix PEGDA (3.5 parts by weight) and PUA (2.1 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant SP-1344 (0.1 part by weight), photoinitiator bis(2,6-difluoro-3-pyrrolophenyl)titanocene (0.7 part by weight) and 2,4-diethylthiazole ketone (0.5 part by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add WC-Co powder (31 parts by weight, refractive index nD is 2.4), and then place it in a mixer and stir for 1 min to mix it evenly. Thus, the WC-Co slurry is prepared.

[0125] (2) Place the WC-Co slurry in a centrifugal stirrer for degassing treatment to avoid defects during printing.

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

[0127] (4) Take out the formed green body from the printing platform, clean its residual resin with alcohol, and then keep it at a temperature of 40 °C for 0.5 hours to completely dry the green body. Finally, place the green body in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 430 °C at a heating rate of 3 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1400 °C at a heating rate of 5 °C / min for sintering for 1 hour to obtain a WC-Co cemented carbide drill bit device.

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

[0129] Comparative Example 4. Preparation of WC-Co Cemented Carbide Drill Bit

[0130] In this example, the preparation process was basically the same as that of Example 9, except that the photoinitiator was modified to a thermal initiator azobisisobutyronitrile. The preparation process was as follows:

[0131] (1) Prepare WC-Co slurry. Mix PEGDA (3.5 parts by weight) and PUA (2.1 parts by weight), disperse them under a high-speed disperser for 5 min, then add a dispersant SP-1344 (0.1 part by weight) and azobisisobutyronitrile (1.2 parts by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add WC-Co powder (31 parts by weight, refractive index nD is 2.4), and then place it in a mixer and stir for 1 min to mix evenly. Thus, the WC-Co slurry is prepared.

[0132] (2) Place the WC-Co slurry in a centrifugal stirrer for degassing treatment to avoid defects during printing.

[0133] (3) Add the slurry to a near-infrared light-curing additive manufacturing device to quickly print a WC-Co drill bit green body. Among them, the energy density of the near-infrared light source is 5 W / cm 2 , the wavelength is 980 nm, the maximum single-layer printing thickness is about 1.0 mm, and the forming speed is 360 mm / h.

[0134] (4) Take out the formed green body from the printing platform, clean its residual resin with alcohol, and then keep it at a temperature of 40 °C for 0.5 hours to completely dry the green body. Finally, place the green body in a debinding and sintering furnace under an inert atmosphere, raise the temperature to 430 °C at a heating rate of 3 °C / min and hold for 1 hour for debinding, and then continue to raise the temperature to 1400 °C at a heating rate of 5 °C / min for sintering for 1 hour to obtain a WC-Co cemented carbide drill bit device.

[0135] Compared with Example 9, the maximum single-layer printing thickness of Comparative Example 4 was reduced to 1.0 mm, lower than 1.2 mm of Example 9, and the forming speed was reduced to 360 mm / h, lower than 432 mm / h of Example 9. After the initiator was replaced with a thermal initiator, the temperature of some areas of the sample was too high during the printing process, resulting in the organic system being prone to overreaction under the thermal initiator. Specifically, the actual accuracy was worse than that of Example 9, and there was slight coking in the area where the green body temperature was concentrated.

[0136] Preparation of WC-Co Cemented Carbide Drill Bit in Comparative Example 5

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

[0138] 1) Prepare WC-Co slurry. Mix PEGDA (3.5 parts by weight) and PUA (2.1 parts by weight), disperse them under a high-speed disperser for 5 min, then add dispersant SP-1344 (0.1 part by weight), photoinitiator bis(2,6-difluoro-3-pyrrolophenyl)titanocene (0.7 part by weight) and 2,4-diethylthiazole (0.5 part by weight), and place them in an ultrasonic dissolver for ultrasonic treatment for 15 min to fully dissolve them. Finally, add WC-Co powder (31 parts by weight, refractive index nD is 2.4), and then place it in a mixer and stir for 1 min to mix it evenly. Thus, the WC-Co slurry is prepared.

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

[0140] (3) Add the slurry to a near-infrared light-curing additive manufacturing equipment, and it is impossible to print a green body normally. Its single-layer morphology is as Figure 4 shown, and most of them show a charred black state.

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

[0142] In addition, according to Figure 5 the comparison of the infrared spectra of each slurry before and after near-infrared light curing, it can be seen that there are obvious changes in the characteristic peak of carbon-carbon double bond at 1631 cm -1 . Table 1 shows the changes in the double bond infrared peak area of the slurries in different examples before and after near-infrared light curing. As can be seen from Table 1, there is a conversion of double bonds in the organic system during the curing process, which proves that this process is photo-curing. 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; The first auxiliary agent, the photoinitiator, and the inorganic material powder in the slurry are in the first combination or the second combination: The first combination is: the first auxiliary agent contains both a first auxiliary agent A and a 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); the slurry contains one or two of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and bis 2,6-difluoro-3-pyrrolephenyl titanocene as photoinitiators; and the refractive index of the inorganic material powder in the slurry is in the range of 1.5 to <2.0; The second combination includes: wherein the first auxiliary agent contains both a first auxiliary agent C and a 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-pyrrolphenyl titanocene as photoinitiators; and the refractive index range of the inorganic material powder in the slurry is 2.0~2.

8.

2. The near-infrared light direct curing additive manufacturing slurry according to claim 1, wherein: 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 as described in claim 1, wherein the inorganic material powder includes one or more of Al2O3 powder, SiC powder, Si3N4 powder, ZrO2 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, wherein the particle size D of the inorganic material powder is 50 0.1-50μm.

5. The method for preparing the near-infrared light direct curing additive manufacturing slurry according to any one of claims 1 to 4, comprising: 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.

6. A method for manufacturing a three-dimensional structure product by direct near-infrared light curing, comprising: (1) Obtaining the near-infrared light direct curing additive manufacturing slurry as described in any one of claims 1 to 4; (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 ~15 W / cm 2 .

7. The method for manufacturing a three-dimensional structure product by near-infrared light direct curing according to claim 6, wherein: In the step (1), the near-infrared light direct curing additive manufacturing slurry as described in claim 1 is obtained, wherein the slurry uses the refractive index of the first auxiliary agent, photoinitiator, and inorganic material powder as described in the first combination, and the wavelength of the light source used for curing in the step (3) is 850-<980nm.

8. The method for manufacturing a three-dimensional structure product by near-infrared light direct curing according to claim 6, wherein: In the step (1), the near-infrared light direct curing additive manufacturing slurry as described in claim 1 is obtained, wherein the slurry uses the refractive index of the first auxiliary agent, photoinitiator, and inorganic material powder as described in the second combination, and the wavelength of the light source used for curing in the step (3) is 980-1100nm.

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