WO2017092012A1 - 一种层状陶瓷的制备方法 - Google Patents

一种层状陶瓷的制备方法 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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Prior art keywords
slurry
layer
preparing
layered ceramic
green body
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PCT/CN2015/096353
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English (en)
French (fr)
Inventor
伍尚华
伍海东
周茂鹏
刘伟
吴子薇
程利霞
李强
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Guangdong University of Technology
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Guangdong University of Technology
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Priority to PCT/CN2015/096353 priority Critical patent/WO2017092012A1/zh
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Anticipated expiration legal-status Critical
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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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Abstract

一种层状陶瓷的制备方法，包括：由陶瓷粉体、树脂、分散剂和表面活性剂制成浆料，相邻两层结构对应的浆料的成分不同；将浆料置于光固化面成型设备中，通过光固化面成型法使浆料逐层固化，形成具有n层结构的坯体；坯体经过干燥步骤、脱脂步骤和烧结步骤，制得层状陶瓷。该制备方法可以制造出微米级厚度的层状陶瓷。

Description

一种层状陶瓷的制备方法
技术领域
本 发明涉及陶瓷制备技术领域 ，尤其涉及一种层状陶瓷的制备方法 。
背景技术
层状陶瓷复合材料借助仿生学的思想进行陶瓷材料的结构设计，层状陶瓷主要由高模量和低模量两种陶瓷材料叠层而成。目前层状陶瓷复合材料的成型工艺主要包括：（ 1 ）预制层片叠放成型，基体层和夹层材料均为预制片，按次序依次叠放进行压制成形；（ 2 ）干粉分层敷放压制成型，基体层和夹层材料均为干粉，依次敷放在模具中进行压制形成；（ 3 ）基片涂覆夹层材料浆液后层压成型，基体为预制片，夹层材料为料浆，涂覆后叠放压制。现有的成型工艺一般都要先经过预压成片状，但是这种片状成型工艺较为复杂而且一般要经过热压烧结等，增加了制造成本。同时传统的热压或流延方法主要用于制备毫米级厚度的层状陶瓷材料，无法制备微米级厚度的层状陶瓷材料。因此，急需寻找一种简便且可制备微米级厚度的层状陶瓷材料的方法。
光固化成型技术中的 DLP 成型（ Digital Light Procession ），可以实现快速、精密制造复杂形状的陶瓷部件，其原理如图 1 所示。基于 DLP 的增材制造技术采用了更为先进的数字微镜装置（ Digital Micromirror Device ， DMD ），从而使该层图像直接投影到整个区域中，直接面成型。因此，这种方法能大大提高成型速率，其 xy 面的精度只取决于 DMD 装置的分辨率与成型件的大小。
发明内容
本发明针对现有的层状陶瓷的制备方法局限在毫米级厚度，且制备过程复杂、成本高等问题，提供一种简便且可制备微米级厚度的层状陶瓷的方法。
为实现上述目的，本发明采用以下技术方案。
所述层状陶瓷具有 n 层结构，层状 陶瓷的制备方法 包括以下步骤：
S1 制备浆料：按以下质量百分比称取各组分并混合均匀，由此分别制得用于形成层状陶瓷中各层结构的浆料，用于形成第 n 层结构的浆料称为第 n 浆料；
第 n 浆料中各组分的组成如下：陶瓷粉体与树脂的体积之和为 V ，所述陶瓷粉体的体积为 0.2V-0.45V ；分散剂的质量为陶瓷粉体的质量的 0.1-5% ，表面活性剂的质量为陶瓷粉体的质量的 0.1-5% ；且相邻两层结构对应的浆料的成分不同。
优选的，所述制备浆料步骤中：首先将陶瓷粉体、分散剂和乙醇混合均匀，然后烘干得到分散粉体；接着将分散粉体、树脂和表面活性剂混合均匀，得到初浆料；将初浆料置于 负压环境下并搅拌 20-120min 以除去气泡，制得浆料。
更优选的，以上所述球磨中所用的球磨介质为氧化铝或者氧化锆，球磨介质形状为球状或柱状，球磨介质直径为 3mm 或 5mm 或 10mm ，料球比为 2:1 或 3:1 或 6:1 。
优选的， 所述陶瓷粉体为氧化锆、氧化铝和 TiCN 中的至少一种。 更优选的， 所述陶瓷粉体的粒径为 0.1-8 μ m ；所述陶瓷粉体具有双峰分布结构（即陶瓷粉体粒径分布较宽）或由两种粒径的粉体复配而得。
优选的，所述树脂为可在波长为 365-405nm 的光下固化的树脂。更优选的，所述树脂为丙烯酸树脂。
优选的，所述分散剂为六偏磷酸钠、聚丙烯酸钠、聚丙烯酸铵和 PVP （聚乙烯吡咯烷酮）中的至少一种。
优选的，所述表面活性剂为硬脂酸或偶联剂。
S2 成型：将第 1 浆料置于光固化面成型设备中，通过光固化面成型法使第 1 浆料固化，形成第一层坯体；将第 2 浆料置于第一层坯体上，通过光固化面成型法使第二浆料固化，形成第二层坯体；重复上述步骤使浆料逐层光固化，形成具有 n 层结构的坯体。
优选的，所述光固化面成型设备是数字光处理器投影仪。
优选的，通过光固化面成型法制得坯体后，用紫外灯照射坯体 10-14h ，以加固坯体。
然后，坯体依次经过干燥步骤、脱脂步骤和烧结步骤的加工，制得层状陶瓷。
优选的，所述干燥步骤是：将坯体置于 25-60 ℃下干燥 5-12h 。
优选的，所述脱脂步骤是：先对坯体进行真空脱脂或气氛保护脱脂处理，再对坯体进行空气脱脂处理。
采用真空排胶或气氛保护排胶可降低坯体中有机物的裂解速率，从而减少坯体出现开裂、起泡等缺陷。通过空气排胶可除去坯体中因真空排胶或气氛保护排胶而残留的碳。
更优选的，所述真空脱脂或气氛保护脱脂的条件是：将坯体置于负压的排胶炉内或惰性气体 /N2 保护的排胶炉内，以 1-5 ℃ /min 的速率升温至 300-650 ℃并保温 2-4h ，且升温过程中每隔 50-150 ℃保温 20-60min ；接着，坯体在负压的排胶炉内或惰性气体 /N2 保护的排胶炉内冷却至室温。进一步优选的，所述负压的排胶炉是指排胶炉内的真空度 大于或等于 0.09MPa 。
更优选的，所述空气脱脂的条件是：将坯体置于空气气氛的排胶炉中，以 5-8 ℃ /min 的速率升温至 300-1100 ℃并保温 0.5-3h ；然后坯体随炉冷却至室温。
优选的，所述烧结步骤的条件是：将坯体置于烧结炉中，以 3-10 ℃ /min 的速率升温至 1350-1650 ℃ 并保温 1-4h ，然后随炉冷却，制得层状陶瓷。
更优选的，所述烧结炉为硅钼棒发热体的烧结炉或石墨电极烧结炉。
与现有技术相比，本发明的有益效果是： 本发明通过 优化浆料的组分及配比，使浆料适用于 DLP 光固化面成型法制作层状陶瓷的坯体，不仅成型效率高，还可使坯体中陶瓷颗粒分散均匀，坯体的形状尺寸精度高；再通过控制脱脂及烧结步骤中的工艺参数，使制造过程中坯体不变形、不开裂，可以制造出微米级厚度的层状陶瓷，且致密均匀，表面光洁度好，精度高，性能优异，所制备的陶瓷产品的可靠性高。本发明采用真空 / 气氛保护脱脂与空气脱脂相结合的二步脱脂法，不仅可显著提高脱脂效率，使脱脂时间由现有方法的 48-60h 以上缩短至 8-20h ；还 可减少坯体因一步脱脂升温速率过快或坯体中的有机物裂解速率过快而导致的变形、开裂、起泡等缺陷，而真空 / 气氛保护脱脂后结合空气排胶，则可排出坯体中因真空 / 气氛保护脱脂而残留的碳。
附图说明
图 1 为光固化面成型设备的工作原理示意图 。
具体实施方式
为了更充分的理解本发明的技术内容，下面结合具体实施例对本发明的技术方案作进一步介绍和说明。
实施例 1
本实施例提供一种具有 3 层结构的层状陶瓷的制备方法，具体步骤如下：
（ 1 ）制备浆料
按以下方法分别制备第 1 浆料、第 2 浆料、第 3 浆料：首先将陶瓷粉体、分散剂和乙醇置于行星球磨机（在其它实施方案中也可以是辊式球磨机）中球磨 8h ，使各组分混合均匀；然后将所得混合物置于 60 ℃下烘干，得到分散粉体。然后将分散粉体、树脂和表面活性于球磨机中球磨 16h 使各组分混合均匀，得到初浆料。接着将初浆料置于负压环境下并搅拌 30min 以除去气泡，制得浆料。（球磨中所用的球磨介质为氧化铝，球磨介质的形状为球状，球磨介质直径为 3mm ，料球比为 2:1 。）
第 1 浆料的组成： 100mL 树脂（丙烯酸树脂）， 42.9mL 陶瓷粉体（ 206g ， 50wt%Al2O3 与 50wt%ZrO2 ，粒径为 0.1-8 μ m ）， 1.5g 分散剂（ PVP ）， 3g 表面改性剂 （硬脂酸） 。
第 2 浆料的组成： 100mL 树脂（丙烯酸树脂）， 42.9mL 陶瓷粉体（ 248.6g ， 10wt%Al2O3 与 90wt%ZrO2 ，粒径为 0.1-8 μ m ）， 1.8g 分散剂（ PVP ）， 3.6g 表面改性剂 （硬脂酸） 。
第 3 浆料的组成： 100mL 树脂（丙烯酸树脂）， 42.9mL 陶瓷粉体（ 236.8g ， 20wt%Al2O3 与 80wt%ZrO2 ，粒径为 0.1-8 μ m ）， 1.7g 分散剂（ PVP ）， 3.5g 表面改性剂 （硬脂酸） 。
（ 2 ）成型
光固化面成型设备为数字光处理器投影仪（设置波长为 405nm ），将第 1 浆料置于光固化面成型设备中，通过光固化面成型法使第 1 浆料固化，形成厚度为 50 μ m 的第一层坯体；然后将第 2 浆料置于第一层坯体上，通过光固化面成型法使第二浆料固化，形成厚度为 50 μ m 的第二层坯体；接着将第 3 浆料置于第二层坯体上，通过光固化面成型法使第三浆料固化，形成厚度为 50 μ m 的第三层坯体。第一层坯体、第二层坯体与第三层坯体构成完整的坯体。
然后将坯体表面未固化的浆料清洗干净，并将清理后的胚体放在紫光灯下照射 12h ，以增加胚体的强度。
（ 3 ）干燥
将坯体置于 25 ℃下干燥 12h 。
（ 4 ）脱脂
先对坯体进行气氛保护脱脂：将坯体置于流动的 N2 或 Ar 的气氛炉内，以 2 ℃ /min 的速率升温至 600 ℃并保温 2h ，且升温过程中每隔 50 ℃保温 20min ；然后坯体随排胶炉冷却至室温。
再对坯体进行空气脱脂：将坯体置于空气气氛的排胶炉中，以 8 ℃ /min 的速率升温至 1100 ℃并保温 30min ；接着坯体随炉冷却至室温。
（ 5 ）烧结
将坯体置于 空气气氛下烧结 ，以 8℃/min 的速率升温至 1450℃ 并保温 3h ，制得层状陶瓷。
本实施例所制备的层状陶瓷的性能较佳， 密度为 5.2g/cm3 ，维氏硬度为 14.1GPa ，抗弯强度为 1200MPa ，断裂韧性为 11.75MPa·m1/2 。
实施例 2
本实施例提供一种具有 3 层结构的层状陶瓷的制备方法，具体步骤如下：
（ 1 ）制备浆料
按以下方法分别制备第 1 浆料、第 2 浆料、第 3 浆料：首先将陶瓷粉体、分散剂和乙醇置于行星球磨机中球磨 8h ，使各组分混合均匀；然后将所得混合物置于 60 ℃下烘干，得到分散粉体。然后将分散粉体、树脂和表面活性剂置于球磨机中球磨 16h 使各组分混合均匀，得到初浆料。接着将初浆料置于负压环境下并搅拌 60min 以除去气泡，制得浆料。（球磨中所用的球磨介质为氧化锆，球磨介质的形状为柱状，球磨介质直径为 5mm ，料球比为 2:1 。）
第 1 浆料的组成： 100mL 树脂（丙烯酸树脂）， 66.7mL 陶瓷粉体（ 367.5g ， 20wt%Al2O3 与 80wt%ZrO2 ，粒径为 0.1-8 μ m ）， 3g 分散剂（ PVP ）， 7 g 表面改性剂（硬脂酸）。
第 2 浆料的组成： 100mL 树脂（丙烯酸树脂）， 66.7mL 陶瓷粉体（ 396.2g ， 5wt%Al2O3 与 95wt%ZrO2 ，粒径为 0.1-8 μ m ）， 3.20g 分散剂（ PVP ）， 7.5 g 表面改性剂（硬脂酸）。
第 3 浆料的组成： 100mL 树脂（丙烯酸树脂）， 66.7mL 陶瓷粉体（ 350.2 g ， 30wt%Al2O3 与 70wt%ZrO2 ，粒径为 0.1-8 μ m ）， 2.86g 分散剂（ PVP ）， 6.6 g 表面改性剂（硬脂酸）。
（ 2 ）成型
光固化面成型设备为数字光处理器投影仪（设置波长为 405nm ），将第 1 浆料置于光固化面成型设备中，通过光固化面成型法使第 1 浆料固化，形成厚度为 50 μ m 的第一层坯体；然后将第 2 浆料置于第一层坯体上，通过光固化面成型法使第二浆料固化，形成厚度为 50 μ m 的第二层坯体；接着将第 3 浆料置于第二层坯体上，通过光固化面成型法使第三浆料固化，形成厚度为 50 μ m 的第三层坯体。第一层坯体、第二层坯体与第三层坯体构成完整的坯体。
然后将坯体表面未固化的浆料清洗干净，并将清理后的胚体放在紫光灯下照射 10h ，以增加胚体的强度。
（ 3 ）干燥
将坯体置于 60 ℃的烘箱中干燥 5h 。
（ 4 ）脱脂
先对坯体进行气氛保护脱脂：将坯体置于流动的 N2 或 Ar 的气氛炉内，以 1 ℃ /min 的速率升温至 600 ℃并保温 3h ，且升温过程中每隔 50 ℃保温 30min ；然后坯体随排胶炉冷却至室温。
再对坯体进行空气脱脂：将坯体置于空气气氛的排胶炉中，以 5 ℃ /min 的速率升温至 1100 ℃并保温 1h ；接着坯体随炉冷却至室温。
（ 5 ）烧结
将坯体置于 空气气氛下 ，以 10℃/min 的速率升温至 1200℃ ，然后再以 5 ℃ /min 的速率升温至 1550℃ 并保温 3h ，制得层状陶瓷。
本实施例所制备的层状陶瓷的性能较佳， 密度为 5.7g/cm3 ，维氏硬度为 13.5GPa ，抗弯强度为 1350MPa ，断裂韧性为 15.7MPa·m1/2 。
实施例 3
本实施例提供一种具有 3 层结构的层状陶瓷的制备方法，具体步骤如下：
（ 1 ）制备浆料
按以下方法分别制备第 1 浆料、第 2 浆料、第 3 浆料：首先将陶瓷粉体、分散剂和乙醇置于辊式球磨机中球磨 8h ，使各组分混合均匀；然后将所得混合物置于 60 ℃下烘干，得到分散粉体。然后将分散粉体、树脂和表面活性剂置于球磨机中球磨 24h 使各组分混合均匀，得到初浆料。接着将初浆料置于负压环境下并搅拌 20min 以除去气泡，制得浆料。（球磨中所用的球磨介质为氧化锆，球磨介质的形状为柱状，球磨介质直径为 10mm ，料球比为 6:1 。）
第 1 浆料的组成： 100mL 树脂（丙烯酸树脂）， 53.8mL 陶瓷粉体（ 206g ， 50wt%Al2O3 与 50wt%ZrO2 ，粒径为 0.1-8 μ m ）， 1.5g 分散剂（聚丙烯酸铵）， 2.58g 表面改性剂（硬脂酸）。
第 2 浆料的组成： 100mL 树脂（丙烯酸树脂）， 53.8mL 陶瓷粉体（ 248.6g ， 10wt%Al2O3 与 90wt%ZrO2 ，粒径为 0.1-8 μ m ）， 1.8g 分散剂（聚丙烯酸铵）， 3.11g 表面改性剂（硬脂酸）。
第 3 浆料的组成： 100mL 树脂（丙烯酸树脂）， 53.8mL 陶瓷粉体（ 236.8g ， 20wt%Al2O3 与 80wt%ZrO2 ，粒径为 0.1-8 μ m ）， 1.7g 分散剂（聚丙烯酸铵）， 2.96g 表面改性剂（硬脂酸）。
（ 2 ）成型
光固化面成型设备为数字光处理器投影仪（设置波长为 405nm ），将第 1 浆料置于光固化面成型设备中，通过光固化面成型法使第 1 浆料固化，形成厚度为 60 μ m 的第一层坯体；然后将第 2 浆料置于第一层坯体上，通过光固化面成型法使第二浆料固化，形成厚度为 60 μ m 的第二层坯体；接着将第 3 浆料置于第二层坯体上，通过光固化面成型法使第三浆料固化，形成厚度为 60 μ m 的第三层坯体。第一层坯体、第二层坯体与第三层坯体构成完整的坯体。
然后将坯体表面未固化的浆料清洗干净，并将清理后的胚体放在紫光灯下照射 14h ，以增加胚体的强度。
（ 3 ）干燥
将坯体置于 40 ℃的烘箱中干燥 8h 。
（ 4 ）脱脂
先对坯体进行真空脱脂：将坯体置于真空度 ≥ 0.09MPa 的排胶炉内，以 5 ℃ /min 的速率升温至 600 ℃并保温 2h ，且升温过程中每隔 150 ℃保温 20min ；保持排胶炉的真空度，坯体随排胶炉冷却至室温。
再对坯体进行空气脱脂：将坯体置于空气气氛的排胶炉中，以 5 ℃ /min 的速率升温至 1000 ℃并保温 3h ；接着坯体随炉冷却至室温。
（ 5 ）烧结
将坯体置于 空气气氛的 硅钼棒发热体烧结炉 中 ，以 10℃/min 的速率升温至 1450℃ 并保温 3h ，制得层状陶瓷。
本实施例所制备的层状陶瓷的性能较佳， 密度为 5.1g/cm3 ，维氏硬度为 13.8GPa ，抗弯强度为 1030MPa ，断裂韧性为 10.5MPa·m1/2 。
实施例 4
本实施例提供一种具有 3 层结构的层状陶瓷的制备方法，具体步骤如下：
（ 1 ）制备浆料
按以下方法分别制备第 1 浆料、第 2 浆料、第 3 浆料：首先将陶瓷粉体、分散剂和乙醇置于辊式球磨机中球磨 8h ，使各组分混合均匀；然后将所得混合物置于 60 ℃下烘干，得到分散粉体。然后将分散粉体、树脂和表面活性剂置于球磨机中球磨 24h 使各组分混合均匀，得到初浆料。接着将初浆料置于负压环境下并搅拌 20min 以除去气泡，制得浆料。（球磨中所用的球磨介质为氧化锆，球磨介质的形状为柱状，球磨介质直径为 10mm ，料球比为 6:1 。）
第 1 浆料的组成： 100mL 树脂（丙烯酸树脂）， 53.8mL 陶瓷粉体（ 350.2g ， 30wt%Al2O3 与 70wt%ZrO2 ，粒径为 0.1-8 μ m ）， 10.6g 分散剂（聚丙烯酸铵）， 10.6g 表面改性剂（硬脂酸）。
第 2 浆料的组成： 100mL 树脂（丙烯酸树脂）， 53.8mL 陶瓷粉体（ 396.2 g ， 5wt%Al2O3 与 95wt%ZrO2 ，粒径为 0.1-8 μ m ）， 10.6g 分散剂（聚丙烯酸铵）， 10.6g 表面改性剂（硬脂酸）。
第 3 浆料的组成： 100mL 树脂（丙烯酸树脂）， 53.8mL 陶瓷粉体（ 350.2g ， 30wt%Al2O3 与 70wt%ZrO2 ，粒径为 0.1-8 μ m ）， 10.6g 分散剂（聚丙烯酸铵）， 10.6g 表面改性剂（硬脂酸）。
（ 2 ）成型
光固化面成型设备为数字光处理器投影仪（设置波长为 405nm ），将第 1 浆料置于光固化面成型设备中，通过光固化面成型法使第 1 浆料固化，形成厚度为 60 μ m 的第一层坯体；然后将第 2 浆料置于第一层坯体上，通过光固化面成型法使第二浆料固化，形成厚度为 60 μ m 的第二层坯体；接着将第 3 浆料置于第二层坯体上，通过光固化面成型法使第三浆料固化，形成厚度为 60 μ m 的第三层坯体。第一层坯体、第二层坯体与第三层坯体构成完整的坯体。
然后将坯体表面未固化的浆料清洗干净，并将清理后的胚体放在紫光灯下照射 14h ，以增加胚体的强度。
（ 3 ）干燥
将坯体置于 40 ℃的烘箱中干燥 8h 。
（ 4 ）脱脂
先对坯体进行真空脱脂：将坯体置于真空度 ≥ 0.09MPa 的排胶炉内，以 5 ℃ /min 的速率升温至 1100 ℃并保温 2h ，且升温过程中每隔 150 ℃保温 20min ；保持排胶炉的真空度，坯体随排胶炉冷却至室温。
再对坯体进行空气脱脂：将坯体置于空气气氛的排胶炉中，以 5 ℃ /min 的速率升温至 300 ℃并保温 3h ；接着坯体随炉冷却至室温。
（ 5 ）烧结
将坯体置于 空气气氛的 硅钼棒发热体烧结炉 中 ，以 10℃/min 的速率升温至 1450℃ 并保温 3h ，制得层状陶瓷。
本实施例所制备的层状陶瓷的性能较佳， 密度为 5.35g/cm3 ，维氏硬度为 13.9GPa ，抗弯强度为 1270MPa ，断裂韧性为 13.55MPa·m1/2 。
实施例 5
（ 1 ）制备浆料
按以下方法分别制备第 1 浆料、第 2 浆料、第 3 浆料：首先将陶瓷粉体、分散剂和乙醇置于行星球磨机中球磨 8h ，使各组分混合均匀；然后将所得混合物置于 60 ℃下烘干，得到分散粉体。然后将分散粉体、树脂和表面活性剂置于球磨机中球磨 3h 使各组分混合均匀，得到初浆料。接着将初浆料置于负压环境下并搅拌 120min 以除去气泡，制得浆料。（球磨中所用的球磨介质为氧化锆，球磨介质的形状为柱状，球磨介质直径为 5mm ，料球比为 2:1 。）
第 1 浆料的组成： 100mL 树脂（丙烯酸树脂）， 25mL 陶瓷粉体（ 99.5g ， Al2O3 ，粒径为 0.1-8 μ m ，双峰分布结构）， 1.2g 分散剂（六偏磷酸钠）， 1 g 表面改性剂（油酸）。
第 2 浆料的组成： 100mL 树脂（丙烯酸树脂）， 25mL 陶瓷粉体（ 99.5g ， Al2O3 ，粒径为 0.1-8 μ m ，双峰分布结构）， 0.8g 分散剂（六偏磷酸钠）， 0.5 g 表面改性剂（油酸）。
第 3 浆料的组成： 100mL 树脂（丙烯酸树脂）， 25mL 陶瓷粉体（ 99.5g ， Al2O3 ，粒径为 0.1-8 μ m ，双峰分布结构）， 0.5g 分散剂（六偏磷酸钠）， 0.8 g 表面改性剂（油酸）。
（ 2 ）成型
光固化面成型设备为数字光处理器投影仪（设置波长为 405nm ），将第 1 浆料置于光固化面成型设备中，通过光固化面成型法使第 1 浆料固化，形成厚度为 60 μ m 的第一层坯体；然后将第 2 浆料置于第一层坯体上，通过光固化面成型法使第二浆料固化，形成厚度为 60 μ m 的第二层坯体；接着将第 3 浆料置于第二层坯体上，通过光固化面成型法使第三浆料固化，形成厚度为 60 μ m 的第三层坯体。第一层坯体、第二层坯体与第三层坯体构成完整的坯体。
然后将坯体表面未固化的浆料清洗干净，并将清理后的胚体放在紫光灯下照射 14h ，以增加胚体的强度。
（ 3 ）干燥
将坯体置于 40 ℃的烘箱中干燥 8h 。
（ 4 ）脱脂
先对坯体进行真空脱脂：将坯体置于真空度 ≥ 0.09MPa 的排胶炉内，以 1 ℃ /min 的速率升温至 300 ℃并保温 4h ，且升温过程中每隔 70 ℃保温 60min ；保持排胶炉的真空度，坯体随排胶炉冷却至室温。
再对坯体进行空气脱脂：将坯体置于空气气氛的排胶炉中，以 7 ℃ /min 的速率升温至 700 ℃并保温 2.5h ；接着坯体随炉冷却至室温。
（ 5 ）烧结
将坯体置于 空气气氛的 硅钼棒发热体烧结炉 中 ，以 5℃/min 的速率升温至 1350℃ 并保温 4h ，制得层状陶瓷。
本实施例所制备的层状陶瓷的性能较佳， 密度为 3.80g/cm3 ，维氏硬度为 14.1 GPa ，抗弯强度为 320MPa ，断裂韧性为 3.2MPa·m1/2 。
实施例 6
（ 1 ）制备浆料
按以下方法分别制备第 1 浆料、第 2 浆料、第 3 浆料：首先将陶瓷粉体、分散剂和乙醇置于行星球磨机中球磨 8h ，使各组分混合均匀；然后将所得混合物置于 60 ℃下烘干，得到分散粉体。然后将分散粉体、树脂和表面活性剂置于球磨机中球磨 10h 使各组分混合均匀，得到初浆料。接着将初浆料置于负压环境下并搅拌 80min 以除去气泡，制得浆料。（球磨中所用的球磨介质为氧化锆，球磨介质的形状为柱状，球磨介质直径为 5mm ，料球比为 2:1 。）
第 1 浆料的组成： 100mL 树脂（丙烯酸树脂）， 81.8mL 陶瓷粉体（ 365g ， 50wt%Al2O3 与 50wt% TiCN ，粒径为 0.1-8 μ m ）， 2.19g 分散剂（聚丙烯酸钠）， 3.65 g 表面改性剂（硬脂酸）。
第 2 浆料的组成： 100mL 树脂（丙烯酸树脂）， 81.8mL 陶瓷粉体（ 404 g ， 10wt%Al2O3 与 90wt% TiCN ，粒径为 0.1-8 μ m ）， 2.42 g 分散剂（聚丙烯酸钠）， 4.04 g 表面改性剂（硬脂酸）。
第 3 浆料的组成： 100mL 树脂（丙烯酸树脂）， 81.8mL 陶瓷粉体（ 393 g ， 20wt%Al2O3 与 80wt% TiCN ，粒径为 0.1-8 μ m ）， 2.35 g 分散剂（聚丙烯酸钠）， 3.93 g 表面改性剂（硬脂酸）。
（ 2 ）成型
光固化面成型设备为数字光处理器投影仪（设置波长为 405nm ），将第 1 浆料置于光固化面成型设备中，通过光固化面成型法使第 1 浆料固化，形成厚度为 60 μ m 的第一层坯体；然后将第 2 浆料置于第一层坯体上，通过光固化面成型法使第二浆料固化，形成厚度为 60 μ m 的第二层坯体；接着将第 3 浆料置于第二层坯体上，通过光固化面成型法使第三浆料固化，形成厚度为 60 μ m 的第三层坯体。第一层坯体、第二层坯体与第三层坯体构成完整的坯体。
然后将坯体表面未固化的浆料清洗干净，并将清理后的胚体放在紫光灯下照射 14h ，以增加胚体的强度。
（ 3 ）干燥
将坯体置于 40 ℃的烘箱中干燥 8h 。
（ 4 ）脱脂
先对坯体进行真空脱脂：将坯体置于真空度 ≥ 0.09MPa 的排胶炉内，以 3 ℃ /min 的速率升温至 700 ℃并保温 3h ，且升温过程中每隔 100 ℃保温 50min ；保持排胶炉的真空度，坯体随排胶炉冷却至室温。
再对坯体进行空气脱脂：将坯体置于空气气氛的排胶炉中，以 8 ℃ /min 的速率升温至 800 ℃并保温 2h ；接着坯体随炉冷却至室温。
（ 5 ）烧结
将坯体置于 真空下石墨电极 发热体烧结炉 中 ，以 10℃/min 的速率升温至 1550℃ 并保温 1h ，制得层状陶瓷。
本实施例所制备的层状陶瓷的性能较佳， 密度为 4.7g/cm3 ，维氏硬度为 16.5GPa ，抗弯强度为 1500MPa ，断裂韧性为 9.2MPa·m1/2 。
在其它实施方案中，所述陶瓷粉体还可以是氧化锆、氧化铝和 TiCN 中的至少一种；陶瓷粉体的粒径还可以在 0.1-8 μ m 的范围内；陶瓷粉体除了具有双峰分布结构（即陶瓷粉体粒径分布较宽）外，还可以由两种粒径的粉体复配而得。
在其它实施方案中，所述树脂还可以是可在波长为 365-405nm 的光下固化的其它树脂。
在其它实施方案中，分散剂还可以是六偏磷酸钠、聚丙烯酸钠、聚丙烯酸铵和 PVP （聚乙烯吡咯烷酮）中的至少一种；表面活性剂还可以是其它偶联剂或硬脂酸。
以上所述仅以实施例来进一步说明本发明的技术内容，以便于读者更容易理解，但不代表本发明的实施方式仅限于此，任何依本发明所做的技术延伸或再创造，均受本发明的保护。

Claims (10)

  1. 一种层状陶瓷的制备方法，所述层状陶瓷具有n层结构，其特征在于，所述制备方法包括以下步骤：
    S1制备浆料：按以下质量百分比称取各组分并混合均匀，由此分别制得用于形成层状陶瓷中各层结构的浆料，用于形成第n层结构的浆料称为第n浆料；
    第n浆料中各组分的组成如下：陶瓷粉体与树脂的体积之和为V，所述陶瓷粉体的体积为0.2V-0.45V；分散剂的质量为陶瓷粉体的质量的0.1-5%，表面活性剂的质量为陶瓷粉体的质量的0.1-5%；且相邻两层结构对应的浆料的成分不同；
    S2成型：将第1浆料置于光固化面成型设备中，通过光固化面成型法使第1浆料固化，形成第一层坯体；将第2浆料置于第一层坯体上，通过光固化面成型法使第二浆料固化，形成第二层坯体；重复上述步骤使浆料逐层光固化，形成具有n层结构的坯体；
    然后，坯体依次经过干燥步骤、脱脂步骤和烧结步骤，制得层状陶瓷。
  2. 根据权利要求1所述一种层状陶瓷的制备方法，其特征在于，所述成型步骤中，光固化面成型设备是数字光处理器投影仪。
  3. 根据权利要求2所述一种层状陶瓷的制备方法，其特征在于，所述成型步骤中，通过光固化面成型法制得坯体后，用紫外灯照射坯体10-14h。
  4. 根据权利要求1所述一种层状陶瓷的制备方法，其特征在于，所述干燥步骤是：将坯体置于25-60℃下干燥5-12h。
  5. 根据权利要求1所述一种层状陶瓷的制备方法，其特征在于，所述脱脂步骤是：先对坯体进行真空脱脂或气氛保护脱脂处理，再对坯体进行空气脱脂处理。
  6. 根据权利要求5所述一种层状陶瓷的制备方法，其特征在于，所述真空脱脂或气氛保护脱脂的条件是：将坯体置于负压的排胶炉内或惰性气体/N2保护的排胶炉内，以1-5℃/min的速率升温至300-650℃并保温2-4h，且升温过程中每隔50-150℃保温20-60min；接着，坯体在负压的排胶炉内或惰性气体/N2保护的排胶炉内冷却至室温。
  7. 根据权利要求5所述一种层状陶瓷的制备方法，其特征在于，所述空气脱脂的条件是：将坯体置于空气气氛的排胶炉中，以5-8℃/min的速率升温至300-1100℃并保温0.5-3h；然后坯体随炉冷却至室温。
  8. 根据权利要求1所述一种层状陶瓷的制备方法，其特征在于，所述烧结步骤是：将坯体置于烧结炉中，以3-10℃/min的速率升温至1350-1650℃并保温1-4h，然后随炉冷却，制得层状陶瓷。
  9. 根据权利要求1所述一种层状陶瓷的制备方法，其特征在于，所述制备浆料步骤中：首先将陶瓷粉体、分散剂和乙醇混合均匀，然后烘干得到分散粉体；接着将分散粉体、树脂和表面活性剂混合均匀，得到初浆料；将初浆料置于负压环境下并搅拌20-120min以除去气泡，制得浆料。
  10. 根据权利要求1所述一种层状陶瓷的制备方法，其特征在于，所述陶瓷粉体为氧化锆、氧化铝和TiCN中的至少一种。
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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
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CN117623766A (zh) * 2022-08-11 2024-03-01 比亚迪股份有限公司 一种多色陶瓷坯体及其制备方法和应用
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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
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WO2025189502A1 (zh) * 2024-03-14 2025-09-18 中国科学院金属研究所 一种增材-等材协同制备双层壁冷陶瓷型芯的方法
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