WO2022233327A1 - Method for cleaning 3d printing green body of high-yield-stress ceramic material - Google Patents

Method for cleaning 3d printing green body of high-yield-stress ceramic material Download PDF

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Publication number
WO2022233327A1
WO2022233327A1 PCT/CN2022/091250 CN2022091250W WO2022233327A1 WO 2022233327 A1 WO2022233327 A1 WO 2022233327A1 CN 2022091250 W CN2022091250 W CN 2022091250W WO 2022233327 A1 WO2022233327 A1 WO 2022233327A1
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WIPO (PCT)
Prior art keywords
cleaning
ceramic material
yield stress
high yield
stress ceramic
Prior art date
Application number
PCT/CN2022/091250
Other languages
French (fr)
Chinese (zh)
Inventor
邢占文
李文利
刘卫卫
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苏州大学
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Publication of WO2022233327A1 publication Critical patent/WO2022233327A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/22—Apparatus or processes for treating or working the shaped or preshaped articles for cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/02—Cleaning by the force of jets or sprays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
    • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B17/00—Details of, or accessories for, apparatus for shaping the material; Auxiliary measures taken in connection with such shaping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/008—Polymeric surface-active agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention relates to the technical field of additive manufacturing (3D printing), in particular to a cleaning method for a 3D printing blank of a high yield stress ceramic material.
  • Ceramic materials have high strength, high hardness, high wear resistance, excellent high temperature resistance and good biocompatibility, and have been widely used in aerospace, industry, biomedical and other fields. With the rapid development of product iteration and flexible manufacturing, 3D printing has become a new technology that has attracted much attention in recent years. This method is a method based on digital model files, using metal powder, plastic, ceramic powder and photosensitive resin The technology of constructing solid bodies by layer-by-layer printing with other bondable materials. Ceramic materials have the characteristics of high melting point and high thermal shock sensitivity. Selective laser melting directly produces low forming accuracy and is prone to cracks.
  • the present invention proposes a cleaning method for a 3D printing body of a high yield stress ceramic material.
  • the cleaning principle of the present invention for 3D printing of high yield stress ceramic materials is to use the above cleaning solution to destroy the three-dimensional network structure formed in the material, so that the components originally limited in the three-dimensional network structure can flow out and flow freely, and then To achieve the purpose of easy washing and good washing effect, especially, the present invention achieves excellent cleaning effect while maintaining high surface quality.
  • the technical solution of the present invention is as follows: a method for cleaning a 3D printing body of a high yield stress ceramic material, comprising the following steps: using a cleaning solution to spray the 3D printing body of a high yield stress ceramic material to complete the high yield stress 3D printing body Cleaning of the 3D printing body of ceramic material; or adding the 3D printing body of high yield stress ceramic material to the cleaning solution and ultrasonic treatment to complete the cleaning of the 3D printing body of high yield stress ceramic material.
  • a cleaning agent is mixed with a cleaning auxiliary to obtain a cleaning solution;
  • the cleaning agent is isobornyl acrylate (IBOA), N-acryloyl morpholine (ACMO), hydroxyethyl methacrylate (HEMA), One or more combinations of 3-ethyl-3-hydroxymethyl oxetane (EHO);
  • the cleaning aids are Dispers 750W, Dispers 655, Tego 688, one or a combination of Tego 755.
  • the weight of the cleaning aid is 0-3% of the weight of the main cleaning agent, and does not include 0; preferably, the weight of the cleaning aid is 0.4-1.5% of the weight of the main cleaning agent, most preferably 0.6- 0.9%.
  • the present invention utilizes the cleaning liquid, and adopts the method of spraying or ultrasonic for cleaning.
  • the ultrasonic cleaning method the high yield stress ceramic material 3D printing body is placed in the ultrasonic cleaning equipment with the cleaning solution, and then the high yield stress ceramic material 3D printing body is immersed in the cleaning solution, and the ultrasonic wave is turned on for cleaning; spray
  • the high-yield stress ceramic material 3D printed body is placed on the cleaning tank or cleaning table, and a gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying.
  • conventional ultrasonic cleaning machine is used for ultrasonic cleaning; preferably, the power is 200-500W, the frequency is 20-80KHz, and the time is 3-8 minutes; further preferably, the power is 300-450W, the frequency is 30-50KHz, The time is 4 to 6 minutes.
  • conventional gas-liquid mixing spray gun is used for spray cleaning, the 3D printing blank of high yield stress ceramic material is placed on the cleaning table, and the gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying; preferably, the pressure is 0.2-0.8Mpa, time is 1-3 minutes; more preferably, pressure is 0.4-0.6Mpa, time is 1.5-2.5 minutes.
  • the cleaning solution used for the high yield stress ceramic 3D printing material of the present invention is obtained by mixing the cleaning main agent and the cleaning auxiliary.
  • the cleaning solution contacts the high yield stress ceramic material the original space of the ceramic material will be destroyed.
  • the three-dimensional network structure flows out the components originally limited in the three-dimensional network structure, and the cleaning efficiency is high, and the surface of the parts is not damaged.
  • Figure 1 is a flow curve of a high yield stress ceramic material.
  • Figure 2 is a photo of a 3D printed body of a high yield stress ceramic material.
  • FIG. 3 is a diagram showing the effect of spray cleaning of the cleaning solution according to the first embodiment.
  • FIG. 4 is a diagram showing the effect of ultrasonic cleaning of the cleaning solution in the second embodiment.
  • FIG. 5 is a surface effect diagram after the spraying of the first embodiment and the ultrasonic cleaning of the second embodiment.
  • FIG. 6 is a diagram showing the effect of ultrasonic cleaning of the cleaning solution in Comparative Example 1.
  • FIG. 7 is a cleaning effect diagram of the third embodiment.
  • FIG. 8 is a cleaning effect diagram of the fourth embodiment.
  • FIG. 9 is a cleaning effect diagram of the fifth embodiment.
  • FIG. 10 is a cleaning effect diagram of the sixth embodiment.
  • Fig. 11 is a cleaning effect diagram of the seventh embodiment.
  • the cleaning solution is used to spray the 3D printing body of the high yield stress ceramic material to complete the cleaning of the 3D printing body of the high yield stress ceramic material; Cleaning of 3D printed bodies of high yield stress ceramic materials. Cleaning can be done at room temperature, no other steps are required, and the surface quality is good.
  • the composition of the high yield stress ceramic material is (mass fraction): HDDA (1,6-hexanediol acrylate) 12 parts, PPTTA (ethoxylated pentaerythritol tetraacrylate) 2 parts, dispersant Anti-terra U100 0.5 part, DBP (dibutyl phthalate) 3 parts, alumina 82.5 parts, the above components are wetted and dispersed by conventional ball milling to obtain high yield stress (260Pa) ceramic 3D printing material, the rheological curve is shown in Figure 1.
  • Ultrasonic cleaning uses a conventional ultrasonic cleaning machine (JP-020S, Shenzhen Jiemeng Cleaning Equipment Co., Ltd.), and spray cleaning uses a gas-liquid mixed spray gun with cleaning liquid for pressure spraying.
  • the effect judgment is the comparative effect.
  • the uncleaned high-yield stress ceramic material 3D printing body as a control, the cleaned products of each group were observed microscopically.
  • the degree of residual ceramic material on the surface it was divided into a large amount of residual, moderate residual, mild residual, and a small residual. and complete removal; according to the degree of damage to the surface, it is divided into severe damage, moderate damage, minor damage and no damage. It was found in the experiment that the degree of cleaning effect of each group was clearly distinguished, which was further observed through microscope magnification.
  • the weight of the cleaning aid is 0.4-1.5% of the weight of the main cleaning agent, preferably 0.6-0.9%.
  • Example 1 Spray cleaning The 3D printed body of the high yield stress ceramic material is placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; Consists of 10Kg IBOA and 80g Tego 688.
  • Example 2 Ultrasonic cleaning: Put the cleaning liquid into the ultrasonic cleaning equipment, then immerse the high yield stress ceramic material 3D printing body in the cleaning liquid, and turn on the ultrasonic wave for cleaning; the power is 300W, the frequency is 40KHz, and the time is 5 minutes; cleaning; The liquid consisted of 10Kg IBOA and 80g Tego 688.
  • FIG. 3 which is the result of spray cleaning in Example 1, it can be seen that the cleaning method disclosed for the first time in the present invention achieves a very good cleaning effect for the 3D printed body of high yield stress ceramic material, and is completely removed.
  • FIG. 4 which is the result of ultrasonic cleaning in Example 2, it can be seen that the cleaning method disclosed for the first time in the present invention has a good cleaning effect on the 3D printing body of high yield stress ceramic material and can be completely removed.
  • FIG. 5 it is a micrograph of the surface of the spray cleaning in Example 1 and the ultrasonic cleaning in Example 2. It can be seen that the surface of the spray cleaning is not damaged, but the ultrasonic is slightly damaged.
  • Comparative Example 1 Ultrasonic cleaning: put the cleaning solution into the ultrasonic cleaning equipment, then immerse the high yield stress ceramic material 3D printing body into the cleaning solution, and turn on the ultrasonic wave for cleaning; the power is 300W, the frequency is 40KHz, and the time is 5 minutes; cleaning The liquid is composed of 10Kg HDDA/anhydrous ethanol and 180g BYK-111, and the volume ratio of HDDA (1,6-hexanediol acrylate) and anhydrous ethanol is 1:1.
  • Figure 6 which is the result of ultrasonic cleaning in Comparative Example 1, moderate damage occurs, and it can be seen that the change of the formula has a greater impact on the cleaning effect. Using the spray cleaning method of the first embodiment, it still cannot be cleaned, and the surface is moderately damaged.
  • Comparative Example 2 Taking the existing commercially available NW water-based cleaning agent as the cleaning solution, no matter whether the spray of Example 1 or the ultrasound of Example 2 is used, it cannot be cleaned, there is a large amount of residue, and the green body is moderately damaged.
  • Example 3 Spray cleaning The high yield stress ceramic material 3D printing body is placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; Consists of 10Kg IBOA and 80g Tego 755. The cleaning results are shown in Figure 7.
  • Example 4 Ultrasonic cleaning Put the cleaning liquid into the ultrasonic cleaning equipment, then immerse the high yield stress ceramic material 3D printing body in the cleaning liquid, and turn on the ultrasonic wave for cleaning; the power is 300W, the frequency is 40KHz, and the time is 5 minutes; cleaning The liquid consisted of 10Kg IBOA and 80g Dispers 750W. The cleaning results are shown in Figure 8.
  • Example 5 Spray cleaning The 3D printed body of the high-yield stress ceramic material was placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid was used for pressure spraying, the pressure was 0.5Mpa, and the time was 2 minutes; Consists of 10Kg IBOA and 150g Tego 688. The cleaning results are shown in Figure 9, with slight damage.
  • Example 6 Spray cleaning The high yield stress ceramic material 3D printed body is placed on the cleaning tank, and a gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.4Mpa, and the time is 2.5 minutes; Consists of 10Kg IBOA and 80g Tego 688. The cleaning results are shown in Figure 10. The cleaning is complete, and the surface quality is slightly worse than that of Example 1.
  • Example 7 Ultrasonic cleaning: Put the cleaning solution into the ultrasonic cleaning equipment, then immerse the 3D printing body of the high yield stress ceramic material in the cleaning solution, and turn on the ultrasonic wave for cleaning; the power is 400W, the frequency is 30KHz, and the time is 6 minutes; The liquid consisted of 10Kg IBOA and 80g Tego 688. The cleaning results are shown in Figure 11. The cleaning is complete, and the surface quality is slightly worse than that of Example 2.
  • Example 8 Spray cleaning The high yield stress ceramic material 3D printed body is placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.6Mpa, and the time is 1.5 minutes; Consists of 10Kg IBOA and 80g Tego 688.
  • Example 9 Ultrasonic cleaning: Put the cleaning solution into the ultrasonic cleaning equipment, then immerse the high yield stress ceramic material 3D printing body in the cleaning solution, and turn on the ultrasonic wave for cleaning; the power is 200W, the frequency is 60KHz, and the time is 7 minutes; cleaning The liquid consisted of 10Kg IBOA and 80g Tego 688.
  • the high yield stress ceramic 3D printing material of the above example or comparative example is 260Pa.
  • the above formula is routinely changed to obtain a high yield stress ceramic 3D printing material with a yield stress of 950 Pa.
  • 3D printing equipment iAMC150, Suzhou Zhongrui Zhichuang
  • Three-dimensional Technology Co., Ltd. conventional printing, to obtain 3D printing blanks of high yield stress ceramic materials, using the cleaning methods of Example 10 to Example 12, the uncured material can be completely removed, and the surface has no damage or nearly no damage.
  • Example 10 Spray cleaning The high yield stress ceramic material 3D printing body is placed on the cleaning tank, and a gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; Consists of 10Kg IBOA and 80g Tego 688.
  • Example 11 Spray cleaning The 3D printed body of the high yield stress ceramic material is placed on the cleaning tank, and a gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; cleaning; The liquid consisted of 10Kg IBOA and 70g Tego 688.
  • Example 12 Spray cleaning The 3D printed body of the high yield stress ceramic material was placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid was used for pressure spraying, the pressure was 0.6Mpa, and the time was 100 seconds; cleaning The liquid consisted of 10Kg HEMA and 80g Tego 688.
  • the above formula is routinely changed as follows to obtain a high yield stress ceramic 3D printing material with a yield stress of 1620 Pa.
  • 3D printing equipment iAMC150, Suzhou Zhongrui Zhichuang 3D Technology Co., Ltd.
  • conventional printing is used to obtain a high yield stress ceramic material 3D
  • the uncured material can be completely removed, and the surface has no damage or nearly no damage.
  • Example 13 Spray cleaning The high yield stress ceramic material 3D printed body is placed on the cleaning tank, and a gas-liquid mixing spray gun equipped with cleaning liquid is used to carry out pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; cleaning; The liquid consisted of 10Kg ACMO and 80g Dispers 750W.
  • Example 14 Spray cleaning The 3D printed body of the high yield stress ceramic material was placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid was used for pressure spraying, the pressure was 0.5Mpa, and the time was 130 seconds; The liquid consisted of 10Kg IBOA and 80g Tego 688.
  • Example 15 Spray cleaning The 3D printed body of the high yield stress ceramic material was placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid was used for pressure spraying, the pressure was 0.5Mpa, and the time was 110 seconds; The liquid consisted of 10Kg IBOA and 80g Tego 688.
  • the ceramic material 3D printing body is a body obtained by conventional 3D printing with high yield stress ceramic material, which is an existing product; the yield stress of the high yield stress ceramic material is 50-2000Pa.
  • the existing cleaning methods use phase solvents to dissolve the slurry to achieve the purpose of cleaning, and it is necessary to add to reduce the cleaning viscosity.
  • the small molecule solvent mostly anhydrous ethanol
  • this cleaning principle selects the configuration of the cleaning liquid according to the composition of the slurry.
  • high-yield-stress ceramic materials which have obviously different spatial three-dimensional network structures, they cannot be effectively cleaned by the existing compatibility method.
  • the invention creatively discloses a cleaning solution for 3D printing blanks of high-yield-stress ceramic materials.
  • the technical idea is different from slurry cleaning, which realizes the technical effect of good cleaning effect and short cleaning time, and is not limited by the composition of high yield stress materials, and does not require viscosity reducing solvents such as absolute ethanol and isobutyl acetate. Existing technology cannot achieve what is expected.

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Abstract

Disclosed in the present invention is a method for cleaning a 3D printing green body of a high-yield-stress ceramic material. The method comprises the following steps: spraying, by using a cleaning fluid, a 3D printing green body of a high-yield-stress ceramic material, so as to complete the cleaning of the 3D printing green body of the high-yield-stress ceramic material; or adding the 3D printing green body of the high-yield-stress ceramic material to the cleaning fluid, and then performing an ultrasonic treatment, thereby completing the cleaning of the 3D printing green body of the high-yield-stress ceramic material. According to the present invention, the cleaning principle applied to a 3D printing green body of a high-yield-stress ceramic material is to use a cleaning fluid in order to destroy a stereoscopic mesh structure formed in the material, such that a component which is originally limited to be in the stereoscopic mesh structure can freely flow out and flow, thereby achieving the aims of facilitating washing and having a good washing effect. In particular, by means of the present invention, a high surface quality is maintained while achieving an excellent cleaning effect.

Description

一种高屈服应力陶瓷材料3D打印坯体的清洗方法A cleaning method for 3D printing body of high yield stress ceramic material 技术领域technical field
本发明涉及增材制造（3D打印）技术领域，具体涉及一种高屈服应力陶瓷材料3D打印坯体的清洗方法。The invention relates to the technical field of additive manufacturing (3D printing), in particular to a cleaning method for a 3D printing blank of a high yield stress ceramic material.
背景技术Background technique
陶瓷材料具有高强度、高硬度、高耐磨性以及优异的耐高温性能和良好的生物相容性，在航天航空、工业、生物医疗等领域得到了广泛的应用。随着产品迭代以及柔性制造的快速发展，3D打印成为近年来倍受关注的一种新的技术手段，该方法是一种以数字模型文件为基础，运用金属粉末、塑料、陶瓷粉末和光敏树脂等可粘合材料，通过逐层打印的方式来构造实体的技术。陶瓷材料具有高熔点、高热震敏感性的特点，选区激光熔融直接制造成型精度低且易出现裂纹，通常采用间接方法把含有陶瓷粉末和粘结剂的混合物构建形成三维素坯，再经有机物脱除和烧结致密化得到陶瓷零件。高屈服应力为零件添加非接触支撑以保证零件的表面质量，但缺点是零件表面及复杂结构内部的高屈服应力陶瓷材料难以去除，清洗困难，特别是微/多孔复杂结构，现有技术无法提供有效的清洗方案。Ceramic materials have high strength, high hardness, high wear resistance, excellent high temperature resistance and good biocompatibility, and have been widely used in aerospace, industry, biomedical and other fields. With the rapid development of product iteration and flexible manufacturing, 3D printing has become a new technology that has attracted much attention in recent years. This method is a method based on digital model files, using metal powder, plastic, ceramic powder and photosensitive resin The technology of constructing solid bodies by layer-by-layer printing with other bondable materials. Ceramic materials have the characteristics of high melting point and high thermal shock sensitivity. Selective laser melting directly produces low forming accuracy and is prone to cracks. Usually, an indirect method is used to build a mixture containing ceramic powder and a binder to form a three-dimensional green body, and then it is removed by organic matter. Removal and sintering densification results in ceramic parts. The high yield stress adds non-contact support to the parts to ensure the surface quality of the parts, but the disadvantage is that the high yield stress ceramic materials on the surface of the parts and inside the complex structure are difficult to remove and difficult to clean, especially for micro/porous complex structures, which cannot be provided by the existing technology. Effective cleaning program.
技术问题technical problem
为解决上述技术问题，本发明提出了一种高屈服应力陶瓷材料3D打印坯体的清洗方法。本发明用于高屈服应力陶瓷材料3D打印坯体的清洗原理是使用上述清洗液破坏材料中形成的立体网状结构，使原本限制于立体网状结构中的组分能够自由流出和流动，继而达到便于洗涤和洗涤效果好的目的，尤其是，本发明在取得优异清洗效果的同时保持高表面质量。In order to solve the above technical problems, the present invention proposes a cleaning method for a 3D printing body of a high yield stress ceramic material. The cleaning principle of the present invention for 3D printing of high yield stress ceramic materials is to use the above cleaning solution to destroy the three-dimensional network structure formed in the material, so that the components originally limited in the three-dimensional network structure can flow out and flow freely, and then To achieve the purpose of easy washing and good washing effect, especially, the present invention achieves excellent cleaning effect while maintaining high surface quality.
技术解决方案technical solutions
为达到上述目的，本发明的技术方案如下：一种高屈服应力陶瓷材料3D打印坯体的清洗方法，包括如下步骤，利用清洗液喷淋高屈服应力陶瓷材料3D打印坯体，完成高屈服应力陶瓷材料3D打印坯体的清洗；或者将高屈服应力陶瓷材料3D打印坯体加入清洗液中，超声处理，完成高屈服应力陶瓷材料3D打印坯体的清洗。In order to achieve the above purpose, the technical solution of the present invention is as follows: a method for cleaning a 3D printing body of a high yield stress ceramic material, comprising the following steps: using a cleaning solution to spray the 3D printing body of a high yield stress ceramic material to complete the high yield stress 3D printing body Cleaning of the 3D printing body of ceramic material; or adding the 3D printing body of high yield stress ceramic material to the cleaning solution and ultrasonic treatment to complete the cleaning of the 3D printing body of high yield stress ceramic material.
本发明中，将清洗主剂与清洗助剂混合，得到清洗液；清洗主剂为丙烯酸异冰片酯（IBOA）、N-丙烯酰吗啉（ACMO）、甲基丙烯酸羟乙酯（HEMA）、3-乙基-3-羟甲基氧杂环丁烷(EHO)中一种或几种的组合；所述清洗助剂为Dispers 750W、Dispers 655、Tego 688、Tego 755中一种或几种的组合。In the present invention, a cleaning agent is mixed with a cleaning auxiliary to obtain a cleaning solution; the cleaning agent is isobornyl acrylate (IBOA), N-acryloyl morpholine (ACMO), hydroxyethyl methacrylate (HEMA), One or more combinations of 3-ethyl-3-hydroxymethyl oxetane (EHO); the cleaning aids are Dispers 750W, Dispers 655, Tego 688, one or a combination of Tego 755.
本发明清洗液中，清洗助剂的重量为清洗主剂重量的0～3%，且不包括0；优选的，清洗助剂的重量为清洗主剂重量的0.4～1.5%，最优选0.6～0.9%。In the cleaning solution of the present invention, the weight of the cleaning aid is 0-3% of the weight of the main cleaning agent, and does not include 0; preferably, the weight of the cleaning aid is 0.4-1.5% of the weight of the main cleaning agent, most preferably 0.6- 0.9%.
本发明利用清洗液，采用喷淋或者超声的方法进行清洗。具体的，超声清洗方式时，将高屈服应力陶瓷材料3D打印坯体用清洗液置入超声波清洗设备中，再将高屈服应力陶瓷材料3D打印坯体浸入清洗液，开启超声波进行清洗；喷淋清洗方式时，将高屈服应力陶瓷材料3D打印坯体置于清洗槽或清洗台上，采用装有清洗液的气液混合喷枪进行压力喷淋。The present invention utilizes the cleaning liquid, and adopts the method of spraying or ultrasonic for cleaning. Specifically, in the ultrasonic cleaning method, the high yield stress ceramic material 3D printing body is placed in the ultrasonic cleaning equipment with the cleaning solution, and then the high yield stress ceramic material 3D printing body is immersed in the cleaning solution, and the ultrasonic wave is turned on for cleaning; spray In the cleaning method, the high-yield stress ceramic material 3D printed body is placed on the cleaning tank or cleaning table, and a gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying.
本发明中，超声清洗采用常规超声波清洗机；优选的，功率为200～500W、频率为20～80KHz，时间为3～8分钟；进一步优选的，功率为300～450W、频率为30～50KHz，时间为4～6分钟。In the present invention, conventional ultrasonic cleaning machine is used for ultrasonic cleaning; preferably, the power is 200-500W, the frequency is 20-80KHz, and the time is 3-8 minutes; further preferably, the power is 300-450W, the frequency is 30-50KHz, The time is 4 to 6 minutes.
本发明中，喷淋清洗采用常规气液混合喷枪，将高屈服应力陶瓷材料3D打印坯体置入清洗台上，利用装有清洗液的气液混合喷枪进行压力喷淋；优选的，压力为0.2～0.8Mpa、时间为1～3分钟；进一步优选的，压力为0.4～0.6Mpa、时间为1.5～2.5分钟。In the present invention, conventional gas-liquid mixing spray gun is used for spray cleaning, the 3D printing blank of high yield stress ceramic material is placed on the cleaning table, and the gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying; preferably, the pressure is 0.2-0.8Mpa, time is 1-3 minutes; more preferably, pressure is 0.4-0.6Mpa, time is 1.5-2.5 minutes.
有益效果beneficial effect
通过上述技术方案，本发明用于高屈服应力陶瓷3D打印材料的清洗液由清洗主剂与清洗助剂混合得到清洗液，当清洗液与高屈服应力陶瓷材料接触时会破坏原本陶瓷材料的空间立体网状结构，流出原本限制于立体网状结构中的组分，清洗效率高，且不破坏零件表面。Through the above technical solutions, the cleaning solution used for the high yield stress ceramic 3D printing material of the present invention is obtained by mixing the cleaning main agent and the cleaning auxiliary. When the cleaning solution contacts the high yield stress ceramic material, the original space of the ceramic material will be destroyed. The three-dimensional network structure flows out the components originally limited in the three-dimensional network structure, and the cleaning efficiency is high, and the surface of the parts is not damaged.
附图说明Description of drawings
图1为高屈服应力陶瓷材料的流变曲线。Figure 1 is a flow curve of a high yield stress ceramic material.
图2为高屈服应力陶瓷材料3D打印坯体照片。Figure 2 is a photo of a 3D printed body of a high yield stress ceramic material.
图3为实施例一的清洗液喷淋清洗效果图。FIG. 3 is a diagram showing the effect of spray cleaning of the cleaning solution according to the first embodiment.
图4为实施例二的清洗液超声清洗效果图。FIG. 4 is a diagram showing the effect of ultrasonic cleaning of the cleaning solution in the second embodiment.
图5为实施例一的喷淋、实施例二的超声清洗后的表面效果图。FIG. 5 is a surface effect diagram after the spraying of the first embodiment and the ultrasonic cleaning of the second embodiment.
图6为对比例一的清洗液超声清洗效果图。FIG. 6 is a diagram showing the effect of ultrasonic cleaning of the cleaning solution in Comparative Example 1. FIG.
图7为实施例三清洗效果图。FIG. 7 is a cleaning effect diagram of the third embodiment.
图8为实施例四清洗效果图。FIG. 8 is a cleaning effect diagram of the fourth embodiment.
图9为实施例五清洗效果图。FIG. 9 is a cleaning effect diagram of the fifth embodiment.
图10为实施例六清洗效果图。FIG. 10 is a cleaning effect diagram of the sixth embodiment.
图11为实施例七清洗效果图。Fig. 11 is a cleaning effect diagram of the seventh embodiment.
本发明的实施方式Embodiments of the present invention
本发明的清洗液与高屈服应力陶瓷材料接触作用时破坏其空间立体网状结构，使原本限制于立体网状结构中的组分能够流动，从而实现达到高屈服应力陶瓷材料便于从3D打印坯体表面据及内部结构清除的目的。下面将结合本发明实施例对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。When the cleaning solution of the invention contacts the high yield stress ceramic material, its spatial three-dimensional network structure is destroyed, so that the components originally limited in the three-dimensional network structure can flow, so that the high yield stress ceramic material can be easily removed from the 3D printing blank. The purpose of body surface data and internal structure removal. The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
本发明利用清洗液喷淋高屈服应力陶瓷材料3D打印坯体，完成高屈服应力陶瓷材料3D打印坯体的清洗；或者将高屈服应力陶瓷材料3D打印坯体加入清洗液中，超声处理，完成高屈服应力陶瓷材料3D打印坯体的清洗。清洗常温即可完成，无需其他的步骤，即可清洗干净且表面质量好。In the present invention, the cleaning solution is used to spray the 3D printing body of the high yield stress ceramic material to complete the cleaning of the 3D printing body of the high yield stress ceramic material; Cleaning of 3D printed bodies of high yield stress ceramic materials. Cleaning can be done at room temperature, no other steps are required, and the surface quality is good.
下面对本发明的具体实施方式作进一步详细的说明。The specific embodiments of the present invention will be described in further detail below.
高屈服应力陶瓷材料的成分为（质量分数）：HDDA（1,6-己二醇丙烯酸酯）12份，PPTTA（乙氧化季戊四醇四丙烯酸酯）2份，分散剂Anti-terra U100 0.5份，DBP（邻苯二甲酸二丁酯）3份，氧化铝82.5份，以上组分经过常规球磨润湿分散得到高屈服应力（260Pa）陶瓷3D打印材料，流变曲线见图1。The composition of the high yield stress ceramic material is (mass fraction): HDDA (1,6-hexanediol acrylate) 12 parts, PPTTA (ethoxylated pentaerythritol tetraacrylate) 2 parts, dispersant Anti-terra U100 0.5 part, DBP (dibutyl phthalate) 3 parts, alumina 82.5 parts, the above components are wetted and dispersed by conventional ball milling to obtain high yield stress (260Pa) ceramic 3D printing material, the rheological curve is shown in Figure 1.
采用3D打印设备（iAMC150，苏州中瑞智创三维科技股份有限公司），常规打印，得到高屈服应力陶瓷材料3D打印坯体，参见图2，表面存在未固化的高粘度陶瓷材料，多组相同的3D打印坯体进行平行清洗实验，设一组不清洗作为空白组对比，图2任意给出其中十组。Using 3D printing equipment (iAMC150, Suzhou Zhongrui Zhichuang 3D Technology Co., Ltd.), conventional printing, a 3D printing body of high yield stress ceramic material is obtained, see Figure 2, there is uncured high viscosity ceramic material on the surface, and multiple groups are the same The 3D printing blanks were subjected to parallel cleaning experiments, and a group of no cleaning was set as a blank group for comparison, and ten groups of them are arbitrarily given in Figure 2.
超声清洗采用常规超声波清洗机（JP-020S，深圳市洁盟清洗设备有限公司），喷淋清洗利用装有清洗液的气液混合喷枪进行压力喷淋。Ultrasonic cleaning uses a conventional ultrasonic cleaning machine (JP-020S, Shenzhen Jiemeng Cleaning Equipment Co., Ltd.), and spray cleaning uses a gas-liquid mixed spray gun with cleaning liquid for pressure spraying.
效果判断，为对比效果。以未清洗的高屈服应力陶瓷材料3D打印坯体为对照，对各组清洗后的产品进行显微观察，根据表面残留陶瓷材料的程度分为大量残留、中度残留、轻度残留、少许残留以及完全去除；根据表面损伤破坏的程度分为重度损伤、中度损伤、轻微损伤以及无损伤。实验发现，各组清洗效果程度区分明显，进一步通过显微镜放大观察。The effect judgment is the comparative effect. Taking the uncleaned high-yield stress ceramic material 3D printing body as a control, the cleaned products of each group were observed microscopically. According to the degree of residual ceramic material on the surface, it was divided into a large amount of residual, moderate residual, mild residual, and a small residual. and complete removal; according to the degree of damage to the surface, it is divided into severe damage, moderate damage, minor damage and no damage. It was found in the experiment that the degree of cleaning effect of each group was clearly distinguished, which was further observed through microscope magnification.
实施例、对比例中，清洗助剂的重量为清洗主剂重量的0.4～1.5%，优选0.6～0.9%。In the examples and comparative examples, the weight of the cleaning aid is 0.4-1.5% of the weight of the main cleaning agent, preferably 0.6-0.9%.
实施例一 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.5Mpa、时间为2分钟；清洗液由10Kg IBOA与80g Tego 688组成。Example 1 Spray cleaning: The 3D printed body of the high yield stress ceramic material is placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; Consists of 10Kg IBOA and 80g Tego 688.
实施例二 超声清洗：将清洗液置入超声波清洗设备中，再将高屈服应力陶瓷材料3D打印坯体浸入清洗液，开启超声波进行清洗；功率为300W、频率为40KHz，时间为5分钟；清洗液由10Kg IBOA与80g Tego 688组成。Example 2 Ultrasonic cleaning: Put the cleaning liquid into the ultrasonic cleaning equipment, then immerse the high yield stress ceramic material 3D printing body in the cleaning liquid, and turn on the ultrasonic wave for cleaning; the power is 300W, the frequency is 40KHz, and the time is 5 minutes; cleaning; The liquid consisted of 10Kg IBOA and 80g Tego 688.
参见图3，为实施例一喷淋清洗的结果，可以看出，本发明首次公开的清洗方法，针对高屈服应力陶瓷材料3D打印坯体取得非常好的清洗效果，完全去除。参见附图4，为实施例二超声清洗的结果，可以看出，本发明首次公开的清洗方法，针对高屈服应力陶瓷材料3D打印坯体的清洗效果好，完全去除。参见附图5，为实施例一喷淋、实施例二超声清洗的表面显微图，可以看出喷淋清洗表面无损伤，超声则有轻微损伤。Referring to FIG. 3 , which is the result of spray cleaning in Example 1, it can be seen that the cleaning method disclosed for the first time in the present invention achieves a very good cleaning effect for the 3D printed body of high yield stress ceramic material, and is completely removed. Referring to FIG. 4, which is the result of ultrasonic cleaning in Example 2, it can be seen that the cleaning method disclosed for the first time in the present invention has a good cleaning effect on the 3D printing body of high yield stress ceramic material and can be completely removed. Referring to FIG. 5, it is a micrograph of the surface of the spray cleaning in Example 1 and the ultrasonic cleaning in Example 2. It can be seen that the surface of the spray cleaning is not damaged, but the ultrasonic is slightly damaged.
对比例一 超声清洗：将清洗液置入超声波清洗设备中，再将高屈服应力陶瓷材料3D打印坯体浸入清洗液，开启超声波进行清洗；功率为300W、频率为40KHz，时间为5分钟；清洗液由10Kg HDDA /无水乙醇与180g BYK-111组成，HDDA（1,6-己二醇丙烯酸酯）、无水乙醇的体积比为1∶1。参见图6，为对比例一超声清洗的结果，出现中度损伤，可以看出，配方的改变，对清洗效果影响较大。采用实施例一的喷淋清洗方法，依然无法清洗干净，且表面中度损伤。Comparative Example 1 Ultrasonic cleaning: put the cleaning solution into the ultrasonic cleaning equipment, then immerse the high yield stress ceramic material 3D printing body into the cleaning solution, and turn on the ultrasonic wave for cleaning; the power is 300W, the frequency is 40KHz, and the time is 5 minutes; cleaning The liquid is composed of 10Kg HDDA/anhydrous ethanol and 180g BYK-111, and the volume ratio of HDDA (1,6-hexanediol acrylate) and anhydrous ethanol is 1:1. Referring to Figure 6, which is the result of ultrasonic cleaning in Comparative Example 1, moderate damage occurs, and it can be seen that the change of the formula has a greater impact on the cleaning effect. Using the spray cleaning method of the first embodiment, it still cannot be cleaned, and the surface is moderately damaged.
对比例二 ：以现有市售NW水性清洗剂为清洗液，无论采用实施例一的喷淋还是实施例二的超声，都无法清洗，存在大量残留，且中度损伤坯体。Comparative Example 2: Taking the existing commercially available NW water-based cleaning agent as the cleaning solution, no matter whether the spray of Example 1 or the ultrasound of Example 2 is used, it cannot be cleaned, there is a large amount of residue, and the green body is moderately damaged.
实施例三 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.5Mpa、时间为2分钟；清洗液由10Kg IBOA与80g Tego 755组成。清洗结果见图7。Example 3 Spray cleaning: The high yield stress ceramic material 3D printing body is placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; Consists of 10Kg IBOA and 80g Tego 755. The cleaning results are shown in Figure 7.
实施例四 超声清洗：将清洗液置入超声波清洗设备中，再将高屈服应力陶瓷材料3D打印坯体浸入清洗液，开启超声波进行清洗；功率为300W、频率为40KHz，时间为5分钟；清洗液由10Kg IBOA与80g Dispers 750W组成。清洗结果见图8。Example 4 Ultrasonic cleaning: Put the cleaning liquid into the ultrasonic cleaning equipment, then immerse the high yield stress ceramic material 3D printing body in the cleaning liquid, and turn on the ultrasonic wave for cleaning; the power is 300W, the frequency is 40KHz, and the time is 5 minutes; cleaning The liquid consisted of 10Kg IBOA and 80g Dispers 750W. The cleaning results are shown in Figure 8.
实施例五 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.5Mpa、时间为2分钟；清洗液由10Kg IBOA与150g Tego 688组成。清洗结果见图9，出现轻微损伤。Example 5 Spray cleaning: The 3D printed body of the high-yield stress ceramic material was placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid was used for pressure spraying, the pressure was 0.5Mpa, and the time was 2 minutes; Consists of 10Kg IBOA and 150g Tego 688. The cleaning results are shown in Figure 9, with slight damage.
实施例六 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.4Mpa、时间为2.5分钟；清洗液由10Kg IBOA与80g Tego 688组成。清洗结果见图10，清洗完全，表面质量较实施例一略差。Example 6 Spray cleaning: The high yield stress ceramic material 3D printed body is placed on the cleaning tank, and a gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.4Mpa, and the time is 2.5 minutes; Consists of 10Kg IBOA and 80g Tego 688. The cleaning results are shown in Figure 10. The cleaning is complete, and the surface quality is slightly worse than that of Example 1.
实施例七 超声清洗：将清洗液置入超声波清洗设备中，再将高屈服应力陶瓷材料3D打印坯体浸入清洗液，开启超声波进行清洗；功率为400W、频率为30KHz，时间为6分钟；清洗液由10Kg IBOA与80g Tego 688组成。清洗结果见图11，清洗完全，表面质量较实施例二略差。Example 7 Ultrasonic cleaning: Put the cleaning solution into the ultrasonic cleaning equipment, then immerse the 3D printing body of the high yield stress ceramic material in the cleaning solution, and turn on the ultrasonic wave for cleaning; the power is 400W, the frequency is 30KHz, and the time is 6 minutes; The liquid consisted of 10Kg IBOA and 80g Tego 688. The cleaning results are shown in Figure 11. The cleaning is complete, and the surface quality is slightly worse than that of Example 2.
实施例八 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.6Mpa、时间为1.5分钟；清洗液由10Kg IBOA与80g Tego 688组成。Example 8 Spray cleaning: The high yield stress ceramic material 3D printed body is placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.6Mpa, and the time is 1.5 minutes; Consists of 10Kg IBOA and 80g Tego 688.
实施例九 超声清洗：将清洗液置入超声波清洗设备中，再将高屈服应力陶瓷材料3D打印坯体浸入清洗液，开启超声波进行清洗；功率为200W、频率为60KHz，时间为7分钟；清洗液由10Kg IBOA与80g Tego 688组成。Example 9 Ultrasonic cleaning: Put the cleaning solution into the ultrasonic cleaning equipment, then immerse the high yield stress ceramic material 3D printing body in the cleaning solution, and turn on the ultrasonic wave for cleaning; the power is 200W, the frequency is 60KHz, and the time is 7 minutes; cleaning The liquid consisted of 10Kg IBOA and 80g Tego 688.
以上实施例或者对比例的高屈服应力陶瓷3D打印材料为260Pa，以下常规更改上述配方，得到屈服应力为950 Pa的高屈服应力陶瓷3D打印材料，采用3D打印设备（iAMC150，苏州中瑞智创三维科技股份有限公司），常规打印，得到高屈服应力陶瓷材料3D打印坯体，采用实施例十至实施例十二的清洗方式，可以完全去除未固化材料，且表面无损伤或者接近无损伤。The high yield stress ceramic 3D printing material of the above example or comparative example is 260Pa. The above formula is routinely changed to obtain a high yield stress ceramic 3D printing material with a yield stress of 950 Pa. 3D printing equipment (iAMC150, Suzhou Zhongrui Zhichuang) is used. Three-dimensional Technology Co., Ltd.), conventional printing, to obtain 3D printing blanks of high yield stress ceramic materials, using the cleaning methods of Example 10 to Example 12, the uncured material can be completely removed, and the surface has no damage or nearly no damage.
实施例十 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.5Mpa、时间为2分钟；清洗液由10Kg IBOA与80g Tego 688组成。Example 10 Spray cleaning: The high yield stress ceramic material 3D printing body is placed on the cleaning tank, and a gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; Consists of 10Kg IBOA and 80g Tego 688.
实施例十一 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.5Mpa、时间为2分钟；清洗液由10Kg IBOA与70g Tego 688组成。Example 11 Spray cleaning: The 3D printed body of the high yield stress ceramic material is placed on the cleaning tank, and a gas-liquid mixing spray gun equipped with cleaning liquid is used for pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; cleaning; The liquid consisted of 10Kg IBOA and 70g Tego 688.
实施例十二 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.6Mpa、时间为100秒；清洗液由10Kg HEMA与80g Tego 688组成。Example 12 Spray cleaning: The 3D printed body of the high yield stress ceramic material was placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid was used for pressure spraying, the pressure was 0.6Mpa, and the time was 100 seconds; cleaning The liquid consisted of 10Kg HEMA and 80g Tego 688.
以下常规更改上述配方，得到屈服应力为1620 Pa的高屈服应力陶瓷3D打印材料，采用3D打印设备（iAMC150，苏州中瑞智创三维科技股份有限公司），常规打印，得到高屈服应力陶瓷材料3D打印坯体，采用实施例十三至实施例十五的清洗方式，可以完全去除未固化材料，且表面无损伤或者接近无损伤。The above formula is routinely changed as follows to obtain a high yield stress ceramic 3D printing material with a yield stress of 1620 Pa. Using 3D printing equipment (iAMC150, Suzhou Zhongrui Zhichuang 3D Technology Co., Ltd.), conventional printing is used to obtain a high yield stress ceramic material 3D For the printing blank, using the cleaning methods of Embodiment 13 to Embodiment 15, the uncured material can be completely removed, and the surface has no damage or nearly no damage.
实施例十三 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.5Mpa、时间为2分钟；清洗液由10Kg ACMO与80g Dispers 750W组成。Example 13 Spray cleaning: The high yield stress ceramic material 3D printed body is placed on the cleaning tank, and a gas-liquid mixing spray gun equipped with cleaning liquid is used to carry out pressure spraying, the pressure is 0.5Mpa, and the time is 2 minutes; cleaning; The liquid consisted of 10Kg ACMO and 80g Dispers 750W.
实施例十四 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.5Mpa、时间为130秒；清洗液由10Kg IBOA与80g Tego 688组成。Example 14 Spray cleaning: The 3D printed body of the high yield stress ceramic material was placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid was used for pressure spraying, the pressure was 0.5Mpa, and the time was 130 seconds; The liquid consisted of 10Kg IBOA and 80g Tego 688.
实施例十五 喷淋清洗：将高屈服应力陶瓷材料3D打印坯体置于清洗槽上，采用装有清洗液的气液混合喷枪进行压力喷淋，压力为0.5Mpa、时间为110秒；清洗液由10Kg IBOA与80g Tego 688组成。Example 15 Spray cleaning: The 3D printed body of the high yield stress ceramic material was placed on the cleaning tank, and a gas-liquid mixed spray gun equipped with cleaning liquid was used for pressure spraying, the pressure was 0.5Mpa, and the time was 110 seconds; The liquid consisted of 10Kg IBOA and 80g Tego 688.
本发明中，陶瓷材料3D打印坯体为采用高屈服应力陶瓷材料进行常规3D打印得到的坯体，为现有产品；高屈服应力陶瓷材料的屈服应力为50～2000Pa。目前，现有技术存在用于3D打印坯体清洗的技术，但是都是针对浆料或者较低屈服应力陶瓷材料，这与高屈服应力陶瓷材料存在技术区别，即使浆料粘度大，也属于流体，低屈服应力陶瓷材料与高屈服应力陶瓷材料的形态、物理结构、化学性质都不同，尤其是，现有清洗方法都是利用相溶剂溶解浆料，实现清洗的目的，还需要加入降低清洗粘度的小分子溶剂（大都为无水乙醇），这种清洗原理根据浆料的成份选择清洗液的配置。对于高屈服应力陶瓷材料，其具有明显不同的空间立体网状结构，利用现有相溶的方式无法有效的清洗，本发明创造性的公开了高屈服应力陶瓷材料3D打印坯体用清洗液，采用与浆料清洗不同的技术思路，实现了清洗效果好、清洗时间短的技术效果，而且不受高屈服应力材料的组成限制，而且无需无水乙醇、醋酸异丁酯等降粘溶剂，这是现有技术无法实现与预期的。In the present invention, the ceramic material 3D printing body is a body obtained by conventional 3D printing with high yield stress ceramic material, which is an existing product; the yield stress of the high yield stress ceramic material is 50-2000Pa. At present, there are technologies for cleaning 3D printing bodies in the prior art, but they are all aimed at slurry or ceramic materials with low yield stress, which is technically different from ceramic materials with high yield stress. Even if the slurry viscosity is large, it is a fluid , The shape, physical structure and chemical properties of low yield stress ceramic materials and high yield stress ceramic materials are different. In particular, the existing cleaning methods use phase solvents to dissolve the slurry to achieve the purpose of cleaning, and it is necessary to add to reduce the cleaning viscosity. The small molecule solvent (mostly anhydrous ethanol), this cleaning principle selects the configuration of the cleaning liquid according to the composition of the slurry. For high-yield-stress ceramic materials, which have obviously different spatial three-dimensional network structures, they cannot be effectively cleaned by the existing compatibility method. The invention creatively discloses a cleaning solution for 3D printing blanks of high-yield-stress ceramic materials. The technical idea is different from slurry cleaning, which realizes the technical effect of good cleaning effect and short cleaning time, and is not limited by the composition of high yield stress materials, and does not require viscosity reducing solvents such as absolute ethanol and isobutyl acetate. Existing technology cannot achieve what is expected.
以上所述的仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those of ordinary skill in the art, some modifications and improvements can be made without departing from the inventive concept of the present invention, which belong to the present invention. the scope of protection of the invention.

Claims (10)

  1. 一种高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，包括如下步骤，利用清洗液喷淋高屈服应力陶瓷材料3D打印坯体，完成高屈服应力陶瓷材料3D打印坯体的清洗；或者将高屈服应力陶瓷材料3D打印坯体加入清洗液中，超声处理，完成高屈服应力陶瓷材料3D打印坯体的清洗。A method for cleaning a 3D printing body of a high yield stress ceramic material, which is characterized by comprising the steps of: spraying a 3D printing body of a high yield stress ceramic material with a cleaning liquid to complete the cleaning of the 3D printing body of a high yield stress ceramic material ; Or add the high yield stress ceramic material 3D printing body into the cleaning solution and ultrasonically treat it to complete the cleaning of the high yield stress ceramic material 3D printing body.
  2. 根据权利要求1所述高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，将清洗主剂与清洗助剂混合，得到清洗液；所述清洗主剂为丙烯酸异冰片酯、N-丙烯酰吗啉、甲基丙烯酸羟乙酯、3-乙基-3-羟甲基氧杂环丁烷中一种或几种的组合。The method for cleaning a 3D printing body of a high yield stress ceramic material according to claim 1, wherein a cleaning agent is mixed with a cleaning aid to obtain a cleaning solution; the cleaning agent is isobornyl acrylate, N- One or a combination of acryloyl morpholine, hydroxyethyl methacrylate and 3-ethyl-3-hydroxymethyl oxetane.
  3. 根据权利要求1所述高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，所述清洗助剂为Dispers 750W、Dispers 655、Tego 688、Tego 755中一种或几种的组合。The cleaning method of the high yield stress ceramic material 3D printing body according to claim 1, wherein the cleaning aid is one or a combination of Dispers 750W, Dispers 655, Tego 688, and Tego 755.
  4. 根据权利要求1所述高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，高屈服应力陶瓷材料的屈服应力为50～2000Pa。The method for cleaning a 3D printed body of a high-yield-stress ceramic material according to claim 1, wherein the yield stress of the high-yield-stress ceramic material is 50-2000 Pa.
  5. 根据权利要求1所述高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，超声清洗方式时，将高屈服应力陶瓷材料3D打印坯体用清洗液置入超声波清洗设备中，再将高屈服应力陶瓷材料3D打印坯体浸入清洗液，开启超声进行清洗；喷淋清洗方式时，将高屈服应力陶瓷材料3D打印坯体置于清洗槽或清洗台上，采用装有清洗液的气液混合喷枪进行压力喷淋。The method for cleaning a 3D printing body of a high yield stress ceramic material according to claim 1, wherein in the ultrasonic cleaning method, the cleaning solution for the 3D printing body of the high yield stress ceramic material is placed in the ultrasonic cleaning equipment, and then the The 3D printing body of high yield stress ceramic material is immersed in the cleaning solution, and the ultrasonic wave is turned on for cleaning; in the spray cleaning method, the 3D printing body of the high yield stress ceramic material is placed on the cleaning tank or cleaning table, and a gas filled with cleaning solution is used. The liquid mixing spray gun is used for pressure spraying.
  6. 根据权利要求1所述高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，超声清洗时，功率为200～500W、频率为20～80KHz，时间为3～8分钟。The method for cleaning a 3D printing body of a high yield stress ceramic material according to claim 1, characterized in that, during ultrasonic cleaning, the power is 200-500W, the frequency is 20-80KHz, and the time is 3-8 minutes.
  7. 根据权利要求5所述高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，功率为300～450W、频率为30～50KHz，时间为4～6分钟。The method for cleaning a 3D printed body of a high yield stress ceramic material according to claim 5, wherein the power is 300-450W, the frequency is 30-50KHz, and the time is 4-6 minutes.
  8. 根据权利要求1所述高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，喷淋清洗时，压力为0.2～0.8Mpa、时间为1～3分钟。The method for cleaning a 3D printing body of a high yield stress ceramic material according to claim 1, characterized in that, during the spray cleaning, the pressure is 0.2-0.8 Mpa and the time is 1-3 minutes.
  9. 根据权利要求8所述高屈服应力陶瓷材料3D打印坯体的清洗方法，其特征在于，压力为0.4～0.6Mpa、时间为1.5～2.5分钟。The cleaning method for a 3D printing body of a high yield stress ceramic material according to claim 8, wherein the pressure is 0.4-0.6 Mpa and the time is 1.5-2.5 minutes.
  10. 利用权利要求1所述高屈服应力陶瓷材料3D打印坯体的清洗方法得到的清洗高屈服应力陶瓷材料3D打印坯体。The cleaned high yield stress ceramic material 3D printing body obtained by the cleaning method of the high yield stress ceramic material 3D printing body according to claim 1.
PCT/CN2022/091250 2021-05-06 2022-05-06 Method for cleaning 3d printing green body of high-yield-stress ceramic material WO2022233327A1 (en)

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