WO2017092012A1 - Procédé de préparation de céramiques en couches - Google Patents

Procédé de préparation de céramiques en couches Download PDF

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Publication number
WO2017092012A1
WO2017092012A1 PCT/CN2015/096353 CN2015096353W WO2017092012A1 WO 2017092012 A1 WO2017092012 A1 WO 2017092012A1 CN 2015096353 W CN2015096353 W CN 2015096353W WO 2017092012 A1 WO2017092012 A1 WO 2017092012A1
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WIPO (PCT)
Prior art keywords
slurry
layer
preparing
layered ceramic
green body
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PCT/CN2015/096353
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English (en)
Chinese (zh)
Inventor
伍尚华
伍海东
周茂鹏
刘伟
吴子薇
程利霞
李强
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广东工业大学
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Priority to PCT/CN2015/096353 priority Critical patent/WO2017092012A1/fr
Publication of WO2017092012A1 publication Critical patent/WO2017092012A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • C04B35/119—Composites with zirconium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites

Definitions

  • the present invention relates to the field of ceramic preparation technology, and in particular to a method for preparing a layered ceramic.
  • the layered ceramic composite material is designed by the idea of bionics.
  • the layered ceramic is mainly composed of two kinds of ceramic materials of high modulus and low modulus.
  • the forming process of layered ceramic composites mainly includes: (1 The prefabricated layer is stacked and formed, and the base layer and the interlayer material are prefabricated sheets, which are sequentially stacked in order for press forming; (2) The dry powder is layered and put into compression molding, and the base layer and the interlayer material are dry powders, which are sequentially placed in a mold for pressing formation; (3) The substrate is coated with a slurry of the interlayer material and then laminated, the substrate is a pre-formed sheet, the interlayer material is a slurry, and the coating is stacked and pressed.
  • the existing molding process generally has to be pre-compressed into a sheet shape, but the sheet molding process is complicated and generally subjected to hot press sintering, etc., which increases the manufacturing cost.
  • the conventional hot pressing or casting method is mainly used for preparing a layered ceramic material having a thickness of a millimeter, and it is impossible to prepare a layered ceramic material having a micron thickness. Therefore, there is an urgent need for a method for preparing a layered ceramic material which is simple and capable of producing micron-thickness.
  • DLP molding in photocuring technology Digital Light Procession
  • DMD Digital Micromirror Device
  • the invention aims at a method for preparing a layered ceramic in the prior art, which is limited to a millimeter-thickness, and has a complicated preparation process and high cost, and provides a method for preparing a layered ceramic which is simple and can prepare a micron-thickness.
  • the present invention adopts the following technical solutions.
  • the layered ceramic has an n-layer structure, and the method for preparing the layered ceramic comprises the following steps:
  • each component is weighed and mixed uniformly according to the following mass percentage, thereby separately preparing a slurry for forming each layer structure in the layered ceramic, and the slurry for forming the n-th layer structure is called nth Slurry
  • each component in the nth slurry is as follows: the sum of the volume of the ceramic powder and the resin is V, and the volume of the ceramic powder is 0.2V-0.45V; the mass of the dispersant is 0.1-5% of the mass of the ceramic powder, and the mass of the surfactant is 0.1-5% of the mass of the ceramic powder. And the composition of the slurry corresponding to the adjacent two-layer structure is different.
  • the ceramic powder, the dispersing agent and the ethanol are uniformly mixed, and then dried to obtain a dispersed powder; then the dispersed powder, the resin and the surfactant are uniformly mixed to obtain a primary slurry. Place the initial slurry The slurry was obtained by stirring under a negative pressure for 20-120 min to remove bubbles.
  • the ball milling medium used in the above ball milling is alumina or zirconia
  • the shape of the ball milling medium is spherical or columnar
  • the diameter of the ball milling medium is 3mm or 5mm or 10mm
  • the ball ratio is 2:1 or 3:1 or 6:1.
  • the ceramic powder is at least one of zirconia, alumina and TiCN. More preferably, the particle size of the ceramic powder is 0.1-8 ⁇ m; the ceramic powder has a bimodal distribution structure (that is, the ceramic powder has a wide particle size distribution) or is obtained by compounding powders of two particle sizes.
  • the resin is at a wavelength of 365-405 nm
  • the resin cured under the light More preferably, the resin is an acrylic resin.
  • the dispersing agent is sodium hexametaphosphate, sodium polyacrylate, ammonium polyacrylate and PVP At least one of (polyvinylpyrrolidone).
  • the surfactant is stearic acid or a coupling agent.
  • the first slurry is placed in a photocuring surface forming apparatus, and the first curing method is used to form the first slurry.
  • the slurry is solidified to form a first layer of the green body;
  • the second slurry is placed on the first layer of the green body, and the second slurry is solidified by photocuring surface forming to form a second layer of the green body;
  • Material layer-by-layer light curing, forming with n A blank of layer structure.
  • the photocuring surface forming apparatus is a digital light processor projector.
  • the body is obtained by a photocuring surface forming method
  • the body is irradiated with an ultraviolet lamp for 10-14 hours to reinforce the body.
  • the green body is sequentially subjected to a drying step, a degreasing step, and a sintering step to obtain a layered ceramic.
  • the drying step is: drying the green body at 25-60 ° C for 5-12 h.
  • the degreasing step is: first performing vacuum degreasing or atmosphere protection degreasing treatment on the green body, and then performing air degreasing treatment on the green body.
  • vacuum debinding or atmosphere protection debinding can reduce the rate of cracking of organic matter in the green body, thereby reducing defects such as cracking and foaming of the green body.
  • the carbon remaining in the body due to vacuum debinding or atmosphere protection debinding can be removed by air debinding.
  • the vacuum degreasing or atmosphere protection degreasing condition is: placing the blank in a vacuum debinding furnace or an inert gas / N 2 -protected debinding furnace at a rate of 1-5 ° C / min Warm up to 300-650 °C and keep 2-4h, and keep warm every 50-150 °C for 20-60min; then, the blank is in the vacuum oven or inert gas / N 2 protection Cool to room temperature.
  • the negative pressure debinding furnace means that the degree of vacuum in the debinding furnace is greater than or equal to 0.09 MPa.
  • the air degreasing condition is: placing the blank in a debinding furnace in an air atmosphere, and heating to a rate of 5-8 ° C /min to 300-1100 °C and keep warm for 0.5-3h; then the body is cooled to room temperature with the furnace.
  • the sintering step is carried out by placing the green body in a sintering furnace and raising the temperature to a rate of 3-10 ° C /min to 1350-1650 °C and 1-4h, then cooled with the furnace to produce layered ceramics.
  • the sintering furnace is a sintering furnace or a graphite electrode sintering furnace of a silicon molybdenum rod heating element.
  • the present invention makes the slurry suitable for DLP by optimizing the composition and ratio of the slurry.
  • the photo-curing surface forming method produces the layered ceramic body, which not only has high molding efficiency, but also can disperse the ceramic particles in the green body uniformly, and the shape and dimensional precision of the green body is high; and then control the process parameters in the degreasing and sintering steps to make During the manufacturing process, the green body is not deformed or cracked, and a layered ceramic having a micron-thickness thickness can be manufactured, and the compactness is uniform, the surface smoothness is good, the precision is high, the performance is excellent, and the prepared ceramic product has high reliability.
  • the invention uses vacuum / Two-step degreasing method combining atmospheric degreasing and air degreasing, not only can significantly improve the degreasing efficiency, but also shorten the degreasing time from 48-60h to 8-20h of the existing method; It can reduce the defects such as deformation, cracking and foaming caused by the excessive degreasing rate of the blank or the excessive cracking rate of the organic matter in the green body, and the vacuum/atmosphere protection after degreasing combined with air debinding can discharge the blank Medium vacuum / The atmosphere protects the residual carbon from degreasing.
  • Figure 1 is a schematic diagram of the working principle of the photocuring surface forming equipment.
  • This embodiment provides a method for preparing a layered ceramic having a three-layer structure, and the specific steps are as follows:
  • the ceramic powder, dispersant and ethanol are first ball milled in a planetary ball mill (in other embodiments, also in a roller ball mill) for 8 h to uniformly mix the components; then the resulting mixture is placed in 60 Drying at ° C to obtain a dispersed powder. Then, the dispersed powder, the resin and the surface active were ball-milled in a ball mill for 16 hours to uniformly mix the components to obtain a primary slurry. Then place the primary slurry under negative pressure and stir for 30 minutes. In order to remove bubbles, a slurry was obtained.
  • the ball milling medium used in the ball milling is alumina, the shape of the ball milling medium is spherical, the diameter of the ball milling medium is 3 mm, and the ratio of the ball to the ball is 2:1.
  • the first slurry composition 100mL resin (acrylic resin), 42.9mL ceramic powder (206g, 50wt% Al 2 O 3 and 50wt% ZrO 2, a particle size of 0.1-8 ⁇ m), 1.5g dispersing agent (PVP ), 3g surface modifier (stearic acid).
  • resin acrylic resin
  • ceramic powder 206g, 50wt% Al 2 O 3 and 50wt% ZrO 2, a particle size of 0.1-8 ⁇ m
  • PVP dispersing agent
  • surface modifier stearic acid
  • Composition of the second slurry 100 mL of resin (acrylic resin), 42.9 mL of ceramic powder (248.6 g, 10 wt% of Al 2 O 3 and 90 wt% of ZrO 2 , particle size of 0.1-8 ⁇ m), 1.8 g of dispersant ( PVP), 3.6g surface modifier (stearic acid).
  • resin acrylic resin
  • ceramic powder 248.6 g, 10 wt% of Al 2 O 3 and 90 wt% of ZrO 2 , particle size of 0.1-8 ⁇ m
  • PVP dispersant
  • surface modifier stearic acid
  • Composition of the third slurry 100 mL resin (acrylic resin), 42.9 mL ceramic powder (236.8 g, 20 wt% Al 2 O 3 and 80 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 1.7 g dispersant ( PVP), 3.5g surface modifier (stearic acid).
  • the light curing surface forming equipment is a digital light processor projector (set wavelength is 405nm), which will be the first
  • the slurry is placed in a photocuring surface forming apparatus, and the first slurry is solidified by photocuring surface forming to form a first layer of the green body having a thickness of 50 ⁇ m;
  • the slurry is placed on the first layer of the green body, and the second slurry is solidified by photocuring surface forming to form a second layer of the green body having a thickness of 50 ⁇ m;
  • the slurry was placed on the second layer of the green body, and the third slurry was solidified by photocuring surface forming to form a third layer of the green body having a thickness of 50 ⁇ m.
  • the first layer of the body, the second layer of the body and the third layer of the body constitute a complete body.
  • the uncured slurry on the surface of the blank is cleaned, and the cleaned embryo body is irradiated under a violet light for 12 hours. To increase the strength of the embryo body.
  • the green body was dried at 25 ° C for 12 h.
  • the body is degreased by atmosphere protection: the body is placed in a flowing N 2 or Ar atmosphere furnace, heated to 600 ° C at 2 ° C /min and kept for 2 h, and kept at 50 ° C for 20 min during the heating process. The body is then cooled to room temperature with the degreaser.
  • the body is then degreased by air: the body is placed in a degassing furnace in an air atmosphere and heated to 1100 at a rate of 8 °C / min. °C and keep warm for 30min; then the body is cooled to room temperature with the furnace.
  • the green body was sintered in an air atmosphere, and the temperature was raised to 1450 ° C at a rate of 8 ° C / min and kept for 3 h. , layered ceramics are produced.
  • the layered ceramic prepared in this example has better properties, a density of 5.2 g/cm 3 , a Vickers hardness of 14.1 GPa, a flexural strength of 1200 MPa, and a fracture toughness of 11.75 MPa ⁇ m 1/2 .
  • This embodiment provides a method for preparing a layered ceramic having a three-layer structure, and the specific steps are as follows:
  • the ceramic powder, dispersant and ethanol were ball milled in a planetary ball mill for 8 h to mix the components uniformly; then the mixture was placed in 60 Drying at ° C to obtain a dispersed powder. Then, the dispersed powder, the resin and the surfactant were ball-milled in a ball mill for 16 hours to uniformly mix the components to obtain a primary slurry. Then place the primary slurry under negative pressure and stir for 60 minutes. In order to remove bubbles, a slurry was obtained.
  • the ball milling medium used in ball milling is zirconia.
  • the shape of the ball milling media is columnar.
  • the diameter of the ball milling media is 5 mm and the ratio of the ball to ball is 2:1.
  • Composition of the first slurry 100 mL resin (acrylic resin), 66.7 mL ceramic powder (367.5 g, 20 wt% Al 2 O 3 and 80 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 3 g dispersant (PVP) ), 7 g surface modifier (stearic acid).
  • resin acrylic resin
  • ceramic powder 367.5 g, 20 wt% Al 2 O 3 and 80 wt% ZrO 2 , particle size 0.1-8 ⁇ m
  • PVP dispersant
  • 7 g surface modifier stearic acid
  • Composition of the second slurry 100 mL resin (acrylic resin), 66.7 mL ceramic powder (396.2 g, 5 wt% Al 2 O 3 and 95 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 3.20 g dispersant ( PVP), 7.5 g surface modifier (stearic acid).
  • Composition of the third slurry 100 mL resin (acrylic resin), 66.7 mL ceramic powder (350.2 g, 30 wt% Al 2 O 3 and 70 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 2.86 g dispersant ( PVP), 6.6 g surface modifier (stearic acid).
  • the light curing surface forming equipment is a digital light processor projector (set wavelength is 405nm), which will be the first
  • the slurry is placed in a photocuring surface forming apparatus, and the first slurry is solidified by photocuring surface forming to form a first layer of the green body having a thickness of 50 ⁇ m;
  • the slurry is placed on the first layer of the green body, and the second slurry is solidified by photocuring surface forming to form a second layer of the green body having a thickness of 50 ⁇ m;
  • the slurry was placed on the second layer of the green body, and the third slurry was solidified by photocuring surface forming to form a third layer of the green body having a thickness of 50 ⁇ m.
  • the first layer of the body, the second layer of the body and the third layer of the body constitute a complete body.
  • the uncured slurry on the surface of the blank is cleaned, and the cleaned embryo body is placed under a violet light for 10 hours. To increase the strength of the embryo body.
  • the body was dried in an oven at 60 ° C for 5 h.
  • the body is degreased by atmosphere protection: the body is placed in a flowing N 2 or Ar atmosphere furnace, heated to 600 ° C at a rate of 1 ° C / min and kept for 3 h, and kept at 50 ° C for 30 min during the heating process. The body is then cooled to room temperature with the degreaser.
  • the body is then degreased by air: the body is placed in a debinding oven in an air atmosphere and heated to 1100 at a rate of 5 °C / min. °C and keep warm for 1h; then the body is cooled to room temperature with the furnace.
  • the layered ceramic prepared in this example has a good density, a density of 5.7 g/cm 3 , a Vickers hardness of 13.5 GPa, a flexural strength of 1350 MPa, and a fracture toughness of 15.7 MPa ⁇ m 1/2 .
  • This embodiment provides a method for preparing a layered ceramic having a three-layer structure, and the specific steps are as follows:
  • the ceramic powder, dispersant and ethanol were ball milled in a roller mill for 8 h to mix the components uniformly; then the mixture was placed in 60 Drying at ° C to obtain a dispersed powder. Then, the dispersed powder, the resin and the surfactant were ball-milled in a ball mill for 24 hours to uniformly mix the components to obtain a primary slurry. Then place the primary slurry under negative pressure and stir for 20 minutes. In order to remove bubbles, a slurry was obtained.
  • the ball milling medium used in ball milling is zirconia, the shape of the ball milling medium is columnar, the diameter of the ball milling medium is 10 mm, and the ratio of the ball to the ball is 6:1.
  • Composition of the first slurry 100 mL resin (acrylic resin), 53.8 mL ceramic powder (206 g, 50 wt% Al 2 O 3 and 50 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 1.5 g dispersant (polymerized) Ammonium acrylate), 2.58 g of surface modifier (stearic acid).
  • Composition of the second slurry 100 mL resin (acrylic resin), 53.8 mL ceramic powder (248.6 g, 10 wt% Al 2 O 3 and 90 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 1.8 g dispersant ( Ammonium polyacrylate), 3.11g surface modifier (stearic acid).
  • Composition of the third slurry 100 mL of resin (acrylic resin), 53.8 mL of ceramic powder (236.8 g, 20 wt% of Al 2 O 3 and 80 wt% of ZrO 2 , particle size of 0.1-8 ⁇ m), 1.7 g of dispersant ( Ammonium polyacrylate), 2.96 g of surface modifier (stearic acid).
  • the light curing surface forming equipment is a digital light processor projector (set wavelength is 405nm), which will be the first
  • the slurry is placed in a photocuring surface forming apparatus, and the first slurry is solidified by photocuring surface forming to form a first layer of the green body having a thickness of 60 ⁇ m;
  • the slurry is placed on the first layer of the green body, and the second slurry is solidified by photocuring surface forming to form a second layer of the green body having a thickness of 60 ⁇ m;
  • the slurry was placed on the second layer of the green body, and the third slurry was solidified by photocuring surface forming to form a third layer of the green body having a thickness of 60 ⁇ m.
  • the first layer of the body, the second layer of the body and the third layer of the body constitute a complete body.
  • the uncured slurry of the blank surface is cleaned, and the cleaned embryo body is irradiated under a violet light for 14 hours. To increase the strength of the embryo body.
  • the body was dried in an oven at 40 ° C for 8 h.
  • Vacuum degreasing the blank first: place the blank in a rubber oven with a vacuum of ⁇ 0.09 MPa at 5 °C / min The rate is raised to 600 °C and kept for 2 hours, and the temperature is maintained at 150 °C for 20 minutes during the heating process; the vacuum of the rubberizing furnace is maintained, and the body is cooled to room temperature with the rubberizing furnace.
  • the body is then degreased by air: the body is placed in a debinding furnace in an air atmosphere and heated to 1000 at a rate of 5 °C / min. °C and keep warm for 3h; then the body is cooled to room temperature with the furnace.
  • the blank is placed in a silicon-molybdenum rod heating element sintering furnace in an air atmosphere, and is heated to 1450 ° C at a rate of 10 ° C / min and insulated. 3h, layered ceramics were produced.
  • the layered ceramic prepared in this example has a good density of 5.1 g/cm 3 , a Vickers hardness of 13.8 GPa, a flexural strength of 1030 MPa, and a fracture toughness of 10.5 MPa ⁇ m 1/2 .
  • This embodiment provides a method for preparing a layered ceramic having a three-layer structure, and the specific steps are as follows:
  • the ceramic powder, dispersant and ethanol were ball milled in a roller mill for 8 h to mix the components uniformly; then the mixture was placed in 60 Drying at ° C to obtain a dispersed powder. Then, the dispersed powder, the resin and the surfactant were ball-milled in a ball mill for 24 hours to uniformly mix the components to obtain a primary slurry. Then place the primary slurry under negative pressure and stir for 20 minutes. In order to remove bubbles, a slurry was obtained.
  • the ball milling medium used in ball milling is zirconia, the shape of the ball milling medium is columnar, the diameter of the ball milling medium is 10 mm, and the ratio of the ball to the ball is 6:1.
  • Composition of the first slurry 100 mL resin (acrylic resin), 53.8 mL ceramic powder (350.2 g, 30 wt% Al 2 O 3 and 70 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 10.6 g dispersant ( Ammonium polyacrylate), 10.6 g of surface modifier (stearic acid).
  • Composition of the second slurry 100 mL resin (acrylic resin), 53.8 mL ceramic powder (396.2 g, 5 wt% Al 2 O 3 and 95 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 10.6 g dispersant ( Ammonium polyacrylate), 10.6 g of surface modifier (stearic acid).
  • Composition of the third slurry 100 mL resin (acrylic resin), 53.8 mL ceramic powder (350.2 g, 30 wt% Al 2 O 3 and 70 wt% ZrO 2 , particle size 0.1-8 ⁇ m), 10.6 g dispersant ( Ammonium polyacrylate), 10.6 g of surface modifier (stearic acid).
  • the light curing surface forming equipment is a digital light processor projector (set wavelength is 405nm), which will be the first
  • the slurry is placed in a photocuring surface forming apparatus, and the first slurry is solidified by photocuring surface forming to form a first layer of the green body having a thickness of 60 ⁇ m;
  • the slurry is placed on the first layer of the green body, and the second slurry is solidified by photocuring surface forming to form a second layer of the green body having a thickness of 60 ⁇ m;
  • the slurry was placed on the second layer of the green body, and the third slurry was solidified by photocuring surface forming to form a third layer of the green body having a thickness of 60 ⁇ m.
  • the first layer of the body, the second layer of the body and the third layer of the body constitute a complete body.
  • the uncured slurry of the blank surface is cleaned, and the cleaned embryo body is irradiated under a violet light for 14 hours. To increase the strength of the embryo body.
  • the body was dried in an oven at 40 ° C for 8 h.
  • Vacuum degreasing the blank first: place the blank in a rubber oven with a vacuum of ⁇ 0.09 MPa at 5 °C / min The rate is raised to 1100 °C and kept for 2 hours, and the temperature is maintained at 150 °C for 20 minutes during the heating process; the vacuum of the rubberizing furnace is maintained, and the body is cooled to room temperature with the rubberizing furnace.
  • the body is then degreased by air: the body is placed in a degassing furnace in an air atmosphere and heated to 300 at a rate of 5 °C / min. °C and keep warm for 3h; then the body is cooled to room temperature with the furnace.
  • the blank is placed in a silicon-molybdenum rod heating element sintering furnace in an air atmosphere, and is heated to 1450 ° C at a rate of 10 ° C / min and insulated. 3h, layered ceramics were produced.
  • the layered ceramic prepared in this example has a good density of 5.35 g/cm 3 , a Vickers hardness of 13.9 GPa, a flexural strength of 1270 MPa, and a fracture toughness of 13.55 MPa ⁇ m 1/2 .
  • the ceramic powder, dispersant and ethanol were ball milled in a planetary ball mill for 8 h to mix the components uniformly; then the mixture was placed in 60 Drying at ° C to obtain a dispersed powder. Then, the dispersed powder, the resin and the surfactant were ball-milled in a ball mill for 3 hours to uniformly mix the components to obtain a primary slurry. Then place the primary slurry under negative pressure and stir for 120 minutes. In order to remove bubbles, a slurry was obtained.
  • the ball milling medium used in ball milling is zirconia.
  • the shape of the ball milling media is columnar.
  • the diameter of the ball milling media is 5 mm and the ratio of the ball to ball is 2:1.
  • Composition of the first slurry 100mL resin (acrylic resin), 25mL ceramic powder (99.5g, Al 2 O 3 , particle size 0.1-8 ⁇ m, bimodal distribution structure), 1.2g dispersant (hexamethylene phosphate) Sodium), 1 g surface modifier (oleic acid).
  • composition of the second slurry 100mL resin (acrylic resin), 25mL ceramic powder (99.5g, Al 2 O 3 , particle size 0.1-8 ⁇ m, bimodal distribution structure), 0.8g dispersant (hexamethylene phosphate) Sodium), 0.5 g surface modifier (oleic acid).
  • Composition of the third slurry 100mL resin (acrylic resin), 25mL ceramic powder (99.5g, Al 2 O 3 , particle size 0.1-8 ⁇ m, bimodal distribution structure), 0.5g dispersant (hexamethylene phosphate) Sodium), 0.8 g surface modifier (oleic acid).
  • the light curing surface forming equipment is a digital light processor projector (set wavelength is 405nm), which will be the first
  • the slurry is placed in a photocuring surface forming apparatus, and the first slurry is solidified by photocuring surface forming to form a first layer of the green body having a thickness of 60 ⁇ m;
  • the slurry is placed on the first layer of the green body, and the second slurry is solidified by photocuring surface forming to form a second layer of the green body having a thickness of 60 ⁇ m;
  • the slurry was placed on the second layer of the green body, and the third slurry was solidified by photocuring surface forming to form a third layer of the green body having a thickness of 60 ⁇ m.
  • the first layer of the body, the second layer of the body and the third layer of the body constitute a complete body.
  • the uncured slurry of the blank surface is cleaned, and the cleaned embryo body is irradiated under a violet light for 14 hours. To increase the strength of the embryo body.
  • the body was dried in an oven at 40 ° C for 8 h.
  • First vacuum degrease the blank place the blank in a rubber oven with a vacuum of ⁇ 0.09 MPa at 1 °C / min The rate is raised to 300 ° C and kept for 4 h, and the temperature is maintained at 70 ° C for 60 min during the heating process; the vacuum of the debinding furnace is maintained, and the body is cooled to room temperature with the debinding furnace.
  • the body is then degreased by air: the body is placed in a degassing furnace in an air atmosphere and heated to 700 at a rate of 7 ° C / min. °C and keep warm for 2.5h; then the body is cooled to room temperature with the furnace.
  • the blank is placed in a silicon-molybdenum rod heating element sintering furnace in an air atmosphere, and is heated to 1350 ° C at a rate of 5 ° C / min and insulated. 4h, layered ceramics were produced.
  • the layered ceramic prepared in this example has a good density, a density of 3.80 g/cm 3 , a Vickers hardness of 14.1 GPa, a flexural strength of 320 MPa, and a fracture toughness of 3.2 MPa ⁇ m 1/2 .
  • the ceramic powder, dispersant and ethanol were ball milled in a planetary ball mill for 8 h to mix the components uniformly; then the mixture was placed in 60 Drying at ° C to obtain a dispersed powder. Then, the dispersed powder, the resin and the surfactant were ball-milled in a ball mill for 10 hours to uniformly mix the components to obtain a primary slurry. Then place the primary slurry under negative pressure and stir for 80 minutes. In order to remove bubbles, a slurry was obtained.
  • the ball milling medium used in ball milling is zirconia.
  • the shape of the ball milling media is columnar.
  • the diameter of the ball milling media is 5 mm and the ratio of the ball to ball is 2:1.
  • the first slurry composition 100mL resin (acrylic resin), 81.8mL ceramic powder (365g, 50wt% Al 2 O 3 and 50wt% TiCN, a particle size of 0.1-8 ⁇ m), 2.19g dispersing agent (polyacrylic acid Sodium), 3.65 g surface modifier (stearic acid).
  • Composition of the second slurry 100 mL resin (acrylic resin), 81.8 mL ceramic powder (404 g, 10 wt% Al 2 O 3 and 90 wt% TiCN, particle size 0.1-8 ⁇ m), 2.42 g dispersant (poly Sodium acrylate), 4.04 g surface modifier (stearic acid).
  • Composition of the third slurry 100 mL resin (acrylic resin), 81.8 mL ceramic powder (393 g, 20 wt% Al 2 O 3 and 80 wt% TiCN, particle size 0.1-8 ⁇ m), 2.35 g dispersant (polymerized) Sodium acrylate), 3.93 g surface modifier (stearic acid).
  • the light curing surface forming equipment is a digital light processor projector (set wavelength is 405nm), which will be the first
  • the slurry is placed in a photocuring surface forming apparatus, and the first slurry is solidified by photocuring surface forming to form a first layer of the green body having a thickness of 60 ⁇ m;
  • the slurry is placed on the first layer of the green body, and the second slurry is solidified by photocuring surface forming to form a second layer of the green body having a thickness of 60 ⁇ m;
  • the slurry was placed on the second layer of the green body, and the third slurry was solidified by photocuring surface forming to form a third layer of the green body having a thickness of 60 ⁇ m.
  • the first layer of the body, the second layer of the body and the third layer of the body constitute a complete body.
  • the uncured slurry of the blank surface is cleaned, and the cleaned embryo body is irradiated under a violet light for 14 hours. To increase the strength of the embryo body.
  • the body was dried in an oven at 40 ° C for 8 h.
  • First vacuum degrease the blank place the blank in a rubber oven with a vacuum of ⁇ 0.09 MPa at 3 °C / min The rate is raised to 700 °C and kept for 3 hours, and the temperature is kept at 100 °C for 50 min during the heating process; the vacuum of the debinding furnace is maintained, and the body is cooled to room temperature with the debinding furnace.
  • the body is then degreased by air: the body is placed in a degassing furnace in an air atmosphere and heated to 800 at a rate of 8 °C / min. °C and keep warm for 2h; then the body is cooled to room temperature with the furnace.
  • the blank is placed in a graphite electrode heating element sintering furnace under vacuum, and is heated to 1550 ° C at a rate of 10 ° C / min and kept warm 1h, layered ceramics were produced.
  • the layered ceramic prepared in this example has better properties, a density of 4.7 g/cm 3 , a Vickers hardness of 16.5 GPa, a flexural strength of 1500 MPa, and a fracture toughness of 9.2 MPa ⁇ m 1/2 .
  • the ceramic powder may also be at least one of zirconia, alumina, and TiCN; the particle size of the ceramic powder may also be In the range of 0.1-8 ⁇ m; in addition to the bimodal distribution structure (that is, the ceramic powder particle size distribution is wide), the ceramic powder can also be obtained by compounding powders of two particle sizes.
  • the resin may also be another resin that is curable at light having a wavelength of from 365 to 405 nm.
  • the dispersing agent may also be sodium hexametaphosphate, sodium polyacrylate, ammonium polyacrylate, and PVP. At least one of (polyvinylpyrrolidone); the surfactant may also be other coupling agents or stearic acid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne un procédé de préparation de céramiques en couches comprenant les étapes consistant à : formuler des suspensions avec une poudre céramique, une résine, un agent de dispersion et un tensioactif, les suspensions correspondantes de deux couches adjacentes étant différentes en termes de composition ; placer les suspensions respectives dans un appareil de stéréolithographie, et durcir chacune des suspensions par un procédé utilisant l'appareil de stéréolithographie pour former une ébauche ayant une structure à n couches ; soumettre l'ébauche à une étape de séchage, une étape de dégraissage et une étape de frittage pour obtenir les céramiques en couches. Le procédé de préparation peut produire des céramiques en couches ayant une épaisseur de l'ordre du micromètre.
PCT/CN2015/096353 2015-12-03 2015-12-03 Procédé de préparation de céramiques en couches WO2017092012A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109665808A (zh) * 2018-12-28 2019-04-23 福建泉州顺美集团有限责任公司 一种环保型多层复合高强度白云陶及其制作工艺
CN112441842A (zh) * 2019-08-27 2021-03-05 南京航空航天大学 一种孔隙率可控的多孔生物陶瓷涂层制备方法
CN114478049A (zh) * 2020-11-13 2022-05-13 西安增材制造国家研究院有限公司 一种高厚度高强度光固化氮化硅陶瓷及其制备方法
CN114770695A (zh) * 2022-04-12 2022-07-22 山东大学 光固化3d打印陶瓷的方法
CN115196976A (zh) * 2022-06-30 2022-10-18 山东工业陶瓷研究设计院有限公司 一种梯度多孔陶瓷及其制备方法
CN116199505A (zh) * 2022-11-18 2023-06-02 中国科学院金属研究所 一种层状界面强化的光固化3d打印陶瓷型芯及制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004179181A (ja) * 2002-11-22 2004-06-24 Kyocera Corp 複合シートの製造方法、並びに積層部品の製造方法
CN1597280A (zh) * 2003-08-19 2005-03-23 日本碍子株式会社 填塞蜂窝状结构体的制造方法、填塞部成型用掩模及制造方法
CN101306950A (zh) * 2008-06-23 2008-11-19 西安交通大学 一种空心叶片陶瓷铸型的光固化直接制造方法
CN101660202A (zh) * 2009-09-15 2010-03-03 西安交通大学 一种光固化直接成型制备陶瓷基三维光子晶体的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004179181A (ja) * 2002-11-22 2004-06-24 Kyocera Corp 複合シートの製造方法、並びに積層部品の製造方法
CN1597280A (zh) * 2003-08-19 2005-03-23 日本碍子株式会社 填塞蜂窝状结构体的制造方法、填塞部成型用掩模及制造方法
CN101306950A (zh) * 2008-06-23 2008-11-19 西安交通大学 一种空心叶片陶瓷铸型的光固化直接制造方法
CN101660202A (zh) * 2009-09-15 2010-03-03 西安交通大学 一种光固化直接成型制备陶瓷基三维光子晶体的方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109665808A (zh) * 2018-12-28 2019-04-23 福建泉州顺美集团有限责任公司 一种环保型多层复合高强度白云陶及其制作工艺
CN109665808B (zh) * 2018-12-28 2023-09-15 福建泉州顺美集团有限责任公司 一种环保型多层复合高强度白云陶及其制作工艺
CN112441842A (zh) * 2019-08-27 2021-03-05 南京航空航天大学 一种孔隙率可控的多孔生物陶瓷涂层制备方法
CN114478049A (zh) * 2020-11-13 2022-05-13 西安增材制造国家研究院有限公司 一种高厚度高强度光固化氮化硅陶瓷及其制备方法
CN114770695A (zh) * 2022-04-12 2022-07-22 山东大学 光固化3d打印陶瓷的方法
CN115196976A (zh) * 2022-06-30 2022-10-18 山东工业陶瓷研究设计院有限公司 一种梯度多孔陶瓷及其制备方法
CN116199505A (zh) * 2022-11-18 2023-06-02 中国科学院金属研究所 一种层状界面强化的光固化3d打印陶瓷型芯及制备方法
CN116199505B (zh) * 2022-11-18 2024-05-03 中国科学院金属研究所 一种层状界面强化的光固化3d打印陶瓷型芯及制备方法

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