Search

KR-20260063077-A - Method for manufacturing ceramic molded articles with improved mechanical properties using photocuring 3D printing

KR20260063077AKR 20260063077 AKR20260063077 AKR 20260063077AKR-20260063077-A

Abstract

The present invention relates to a method for manufacturing a ceramic molded article with improved mechanical properties using photocuring 3D printing. By pressurizing a laminate obtained by photocuring 3D printing with cold isostatic pressing to improve the density of the laminate, and then sintering the laminate, the effect of significantly improving strength and hardness while ensuring dimensional stability is achieved.

Inventors

  • 박주석
  • 이민호
  • 김진우
  • 이재승
  • 임근안

Assignees

  • 한국세라믹기술원

Dates

Publication Date
20260507
Application Date
20241030

Claims (10)

  1. Step of obtaining a ceramic additive by photocuring 3D printing (Step 1); A step of pressurizing the laminate obtained in Step 1 using cold isostatic pressing (CIP) (Step 2); and A step of sintering the pressurized laminate obtained in Step 2 (Step 3); comprising Method for manufacturing a ceramic molded article with improved mechanical properties using photocuring 3D printing .
  2. In paragraph 1, A manufacturing method in which the laminate obtained in Step 1 above is placed in a vacuum vinyl or rubber tube, vacuum-packed, and subjected to pressure treatment by cold hydrostatic molding.
  3. In paragraph 1, A ceramic slurry composition was used for the photocuring 3D printing in Step 1 above, and A method of manufacturing in which the ceramic slurry composition comprises one or more ceramic powders selected from the group consisting of zirconia, yttria, alumina, magnesia, silica, silicon nitride, mullite, and cordierite.
  4. In paragraph 3, A method of manufacturing the above ceramic slurry composition further comprising a dispersant, a photoinitiator, and a monomer.
  5. In paragraph 4, The above dispersant is an unsaturated polycarboxylic acid polymer and polysiloxane copolymer solution (Model: DISPERBYK-W 940, Manufacturer: BYK), an acidic group-containing polyacrylic acid copolymer solution (Model: DISPERBYK-110, Manufacturer: BYK), a polyacrylic acid copolymer solution (Model: DISPERBYK-163, Manufacturer: BYK), a polyacrylic acid ester solution (Model: DISPERBYK-154, Manufacturer: BYK), an acidic group-containing polyether solution (Model: DISPERBYK-180, Manufacturer: BYK), a nonionic group-containing polyether solution (Model: DISPERBYK-P 104, Manufacturer: BYK), a polyacrylic acid ester solution (Model: DISPERBYK-1640, Manufacturer: BYK), a polyether-modified polydimethylsiloxane solution (Model: DISPERBYK-333, Manufacturer: BYK), One or more selected from the group consisting of styrene maleic anhydride copolymer solution (model name: DISPERBYK-2000, manufacturer: BYK), phosphated polyurethane solution (model name: DISPERBYK-2001, manufacturer: BYK), polyvinylpyrrolidone (PVP), and ammonium salt solution of acrylic acid (model name: Dispex A40, manufacturer: BASF), and The above photoinitiator is one or more selected from the group consisting of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), phenylphosphine oxide (PPO), 2-hydroxy-2-methylpropiophenone (Darocur 1173), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure 819), benzoin methyl ether, camphorquinone, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (BAPO). The above monomers are 1,6-Hexanediol diacrylate (HDDA), Polyethylene Glycol Diacrylate (PEGDA), Trimethylolpropane Triacrylate (TMPTA), Isobornyl Acrylate, Ethoxylated Trimethylolpropane Triacrylate (ETMPTA), Bisphenol A Ethoxylate Diacrylate, Hydroxyethyl Methacrylate (HEMA), Urethane Dimethacrylate (UDA), Glycidyl Methacrylate (GMA), and Methyl Methacrylate. A manufacturing method comprising one or more selected from the group consisting of methacrylate, MMA.
  6. In paragraph 1, A manufacturing method in which the photocuring 3D printing of step 1 above uses a digital light processing (DLP) method or a stereolithography apparatus (SLA) method.
  7. In paragraph 6, A manufacturing method in which the photocuring 3D printing of Step 1 above uses a DLP (Digital Light Processing) 3D printer.
  8. In paragraph 1, A manufacturing method in which the pressurization treatment by cold isostatic pressing (CIP) in step 2 above is performed at 50-300 MPa for 5-60 seconds.
  9. In paragraph 8, A manufacturing method in which the pressurization treatment by cold isostatic pressing (CIP) in step 2 above is applied at 190-210 MPa for 9-11 seconds.
  10. In paragraph 1, A manufacturing method in which the sintering treatment of step 3 above is performed at 1300-1600℃ for 10-20 hours.

Description

Method for manufacturing ceramic molded articles with improved mechanical properties using photocuring 3D printing The present invention relates to a method for manufacturing a ceramic molded article with improved mechanical properties using photocuring 3D printing. The technical feature of the invention is that by pressurizing a laminate obtained by photocuring 3D printing with cold isostatic pressing to improve the density of the laminate, and then sintering the laminate, dimensional stability is ensured while strength and hardness are significantly improved. Ceramic products have been produced through manufacturing processes such as injection molding, tape casting, and die pressing, and are applied in various fields due to their excellent thermal and mechanical properties. In particular, in advanced ceramic material application fields such as aerospace, bio, and energy, geometric design and structural complexity of the ceramics are required to achieve high product performance. However, conventional ceramic product manufacturing processes have technical limitations due to low productivity and high production costs resulting from the use of molds. Therefore, 3D printing technology, which can produce products with complex shapes without using molds, has recently been proposed. In various 3D printing technologies, ceramic products are generally manufactured using powder or slurry. Methods using powder include Selective Laser Sintering (SLS) and Selective Laser Melting (SLM). These powder-based methods consume a significant amount of energy because they utilize an energy source, such as a laser beam, to melt the binder coated on the ceramic or ceramic particles, thereby selectively bonding the particles. Furthermore, this equipment is very expensive because it must be equipped with features to prevent shrinkage and deformation that occur during the additive manufacturing process. Methods using ceramic slurries as raw materials include the Material Extrusion (ME) method, which produces a green body by layering materials extruded through a nozzle using a thermoplastic resin and mixed with ceramics to form a slurry, and Digital Light Processing (DLP) and Stereolithography Apparatus (SLA) methods, which create a three-dimensional shape by selectively irradiating a photocurable slurry with light. Additionally, there is a composite 3D printing method of photopolymerization material extrusion in which materials are layered by extruding a photocurable slurry through a nozzle and then cured by irradiating with light. Among 3D printing technologies utilizing ceramic slurries, DLP and SLA printing methods offer high precision and can be widely used to create complex geometric structures. The ceramic slurries used consist of ceramic particles, a photocurable resin containing initiators and other additives, and a dispersant. However, in DLP and SLA printing, volume shrinkage occurs as monomers form cross-linked polymers, and cracking and warping may occur during the sintering process required to obtain dense ceramics. Due to these issues, the accurate realization of complex dimensions is impossible. In general ceramic product manufacturing processes, the solid content of the ceramic must be as high as possible to obtain green bodies and sintered bodies with high dimensional stability. However, for application in DLP and SLA processes, it is necessary to use a ceramic slurry with appropriate fluidity and viscosity. This is because it is closely related to preventing particle aggregation and ensuring uniform coating of the slurry on the laminated surface. Accordingly, while devising a method to ensure dimensional stability without cracks or warping during the sintering process and to improve mechanical properties such as strength and hardness while using a slurry composition with a ceramic solid content generally used in the field of ceramic printing technology, the inventor confirmed that by pressurizing a laminate obtained by 3D printing with cold isostatic pressing to increase the density of the laminate and then sintering it, dimensional stability is ensured and strength and hardness are significantly improved, and thus completed the present invention. The present invention will be explained in more detail below through the following examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited by the following examples. <Preparation Example 1> Preparation of a ceramic slurry composition for ceramic 3D printing Ingredient nameContent (Based on 100 parts by weight of the composition)Ceramic powder 1Zirconia45-70 parts by weightCeramic powder 2Itria1-10 parts by weightDispersantDISPERBYK-20010.3-5 parts by weightPhotoinitiatorTPO0.05-10 parts by weightMonomer 1HDDA1-10 parts by weightMonomer 2PEGDA1-10 parts by weight Phosphated Polyurethane Solution (Model Name: DISPERBYK-2001, Manufacturer: BYK) Diphenyl(2,4,6-trimethylbenzoyl)phosphine