WO2017120990A1 - 一种净尺寸复杂形状透明陶瓷件的制备工艺 - Google Patents

一种净尺寸复杂形状透明陶瓷件的制备工艺 Download PDF

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WO2017120990A1
WO2017120990A1 PCT/CN2016/073023 CN2016073023W WO2017120990A1 WO 2017120990 A1 WO2017120990 A1 WO 2017120990A1 CN 2016073023 W CN2016073023 W CN 2016073023W WO 2017120990 A1 WO2017120990 A1 WO 2017120990A1
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ceramic
degreasing
preparing
peg
net
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刘伟
伍海东
周茂鹏
伍尚华
黄家威
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广东工业大学
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/9646—Optical properties
    • C04B2235/9653—Translucent or transparent ceramics other than alumina

Definitions

  • the invention relates to the technical field of high-performance transparent ceramics preparation, in particular to a preparation process of a transparent ceramic piece with a net size and complex shape.
  • This application is based on the Chinese invention patent of application number 2016100255955 and application date January 13, 2016.
  • oxide transparent ceramics such as Y 2 O 3 (yttria), MgO (magnesium oxide), BeO (yttria), CaO (calcium oxide), ThO 2 (yttria), MgAl 2 O 4 (magnesium aluminum) Spinel), (Pb, La) (Zr, Ti) O (lead zirconate titanate) and the like have been successively introduced.
  • yttrium-aluminum garnet such as Nd:YAG
  • a batch of non-oxide transparent ceramics have also been developed, such as AlON transparent ceramics, AlN (aluminum nitride) transparent ceramics, SiAlON (Sialon) transparent ceramics.
  • transparent ceramics are often subjected to conventional molding methods such as dry pressing, grouting, and isostatic pressing.
  • the ceramic dry press molding has high efficiency, there is a phenomenon of density difference and uneven microstructure, and it is difficult to form a profiled part.
  • ceramic injection molding can form shaped products, the molded body is prone to density unevenness and composition segregation, and there are problems such as low dimensional accuracy and reduced product reliability.
  • Cold isostatic pressing can obtain a high-density and high-uniformity molded body, but it is difficult to form a ceramic component having a complicated shape, and the molding efficiency is low and many steps requiring manual operation are required.
  • These conventional molding methods are not suitable for the preparation of high-performance, high-reliability transparent ceramic parts of precise, complex shapes.
  • the object of the present invention is to provide a process for preparing a transparent ceramic part of a net size complex shape, which is suitable for preparing a net size, high precision, high density, high uniformity, high performance and complexity. Shaped transparent ceramic pieces.
  • a preparation process for a transparent ceramic piece of a net size complex shape comprising the following steps:
  • Discharge plasma sintering is performed by a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the above step (1) prepared by the injection molding method to obtain the ceramic body specifically includes:
  • a high-purity nano-ceramic powder having a purity of 99.9% or higher is used as a raw material, and a micro-sintering aid is introduced by a magnetic stirrer in a chemical precipitation manner to obtain a ceramic composite powder containing a sintering aid;
  • the surface modifier is combined with the ceramic composite powder for ball milling pretreatment, and a layer of nanometer thickness is formed on the surface of the ceramic composite powder, and the surface modified ceramic powder is obtained after drying;
  • the organic binder and the surface-modified ceramic powder are made into an injection suspension
  • the ceramic powder is cerium oxide, magnesium oxide, cerium oxide, calcium oxide, cerium oxide, magnesium aluminum spinel, lead zirconate titanate ceramic or aaron ceramic, aluminum nitride ceramic, sialon ceramic with a purity greater than 99.9%. ;
  • the sintering aid is one or more of magnesium oxide, cerium oxide, cerium oxide, and the total amount of the sintering aid is 0.1 to 1% by weight of the total amount of the ceramic powder;
  • the surface modifier is any one of stearic acid, oleic acid, dodecyl stearic acid, and citric acid, and the total amount of the surface modifier accounts for 0.1 to 3 wt% of the total amount of the ceramic composite powder. ;
  • the surface-modified ceramic powder accounts for 80% to 90% by weight of the injection-molded mixture
  • the organic binder accounts for 10 to 20% by weight of the injection-molded mixture. %.
  • the ceramic composite powder containing the sintering aid is obtained by chemically precipitating a small amount of sintering aid by a magnetic stirrer, specifically using a metal ion nitrate or chloride, and adjusting the pH of the slurry to 9.2 to 11.4 using ammonia water. Metal ions are deposited in the form of chemical precipitation onto the surface of the ceramic powder particles;
  • the ball mill uses an alumina ceramic ball mill jar, the grinding ball is a high-purity transparent alumina grinding ball, the ball milling medium is alcohol, the ceramic powder, the alcohol, the grinding ball have a mass ratio of 1:1:2, the rotation speed is 80 rpm to 240 rpm, and the ball mill The time is 3 to 12 hours.
  • the above step (1.2) is compounded by PEG/PVB system, and the binder system composition is: 22 wt% PVB + 33 wt% PEG 4000 + 33 wt% PEG 600 + 9 wt% SA + 2.5% DBP, plus 0.5 wt% Phenothiazine as an antioxidant;
  • the skeleton binder PVB was added to the two-roller mixer. After the PVB was completely in a molten state and the temperature of the double rolls was raised to 170 ° C, the double rolls were started, and then phenothiazine, PEG 4000, PEG 600 and SA were added respectively, and the mixture was mixed. For 45 min, DBP was added 5 min before the end of the mixing to inhibit the plasticization.
  • Another preferred method of the above step (1.2) is to feed the PEG/PMMA system, and the binder system is composed of:
  • the framework binder PMMA was added to the two-roller mixer. After the PMMA was completely in a molten state and the temperature of the two rolls rose to 170 ° C, the two rolls were started, and then phenothiazine, PEG 4000, PEG 600 and SA were added respectively, and the mixture was mixed. For 45 min, DBP was added 5 min before the end of the mixing to inhibit the plasticization.
  • the ceramic body is degreased by a two-step degreasing method of water extraction debinding and thermal degreasing to obtain a mature body. Specifically, the water-soluble binder in the component is removed by water extraction and degreased, and then passed through heat. Degreasing removes the water insoluble binder in the body.
  • the above water extraction degreasing is specifically: the ceramic body is placed in a water bath for water extraction and degreasing, the temperature is 40-60 ° C, and the degreasing time is 8-20 h;
  • the thermal degreasing is specifically: the body after water degreasing is air-dried at 80-100 ° C for 12-24 hours, placed in a muffle furnace, and the temperature is raised to 450-500 ° C for 2 to 3 hours to obtain a mature billet, and the heating rate is increased. It is 2 to 4 ° C / min.
  • the above step (3) is specifically: placing the mature blank in the graphite crucible, and placing the graphite crucible covered with the graphite cap into the discharge plasma sintering apparatus for sintering, and the upper and lower indenters of the discharge plasma sintering apparatus apply pressure to the graphite crucible to fix Graphite crucible.
  • the sintering temperature of the discharge plasma sintering is 1300 to 1600 ° C
  • the heating rate is 10 to 100 ° C / min
  • the holding time is 5 to 20 min.
  • the preparation process of the net size complex shape transparent ceramic piece of the invention comprises the following steps: (1) preparing a ceramic body by an injection molding method; (2) using a two-step degreasing method of water extraction debinding and thermal degreasing to the ceramic body Degreasing to obtain a mature billet; (3) performing discharge plasma sintering by means of a discharge plasma sintering apparatus without directly pressing the cooked billet, and annealing and polishing to obtain a transparent ceramic member.
  • the preparation process of the transparent size transparent ceramic piece is suitable for preparing transparent ceramic parts with net size, high precision, high density, high uniformity, high performance and complex shape structure.
  • FIG. 1 is a schematic view showing the use state of a discharge plasma sintering apparatus and a graphite crucible used in a preparation process of a transparent ceramic member of a net size complicated shape.
  • Example 2 is a schematic view showing the structure of a transparent alumina bracket prepared in Example 6 of the present invention.
  • FIG. 3 is a schematic view showing the SEM surface topography of the transparent alumina bracket of FIG. 2.
  • Graphite crucible 100 graphite cap 200, graphite gasket 300, cooked billet 400, and upper and lower indenter 500.
  • a preparation process of a transparent ceramic piece of a net size complex shape is carried out by the following three steps.
  • a ceramic body is prepared by an injection molding method.
  • Step (1) preparing the ceramic body by the injection molding method specifically comprises:
  • a high-purity nano-ceramic powder is used as a raw material, and a micro-sintering aid is introduced by a magnetic stirrer in a chemical precipitation manner to obtain a ceramic composite powder containing a sintering aid.
  • High-purity nanoceramic powder refers to a powder having a purity greater than 99.9%.
  • the ceramic powder is cerium oxide, magnesium oxide, cerium oxide, calcium oxide, cerium oxide, magnesium aluminum spinel, lead zirconate titanate ceramics having a purity greater than 99.9% or aaron ceramics, aluminum nitride ceramics, and sialon ceramics.
  • the sintering aid is one or more of magnesium oxide, cerium oxide and cerium oxide, and the total amount of the sintering aid accounts for 0.1 to 1% by weight of the total amount of the ceramic powder.
  • the surface modifier is combined with the ceramic composite powder for ball milling pretreatment, and a layer of nanometer thickness coating layer is formed on the surface of the ceramic composite powder, and the surface modified ceramic powder is obtained after drying.
  • the surface modifier is any one of stearic acid, oleic acid, dodecyl stearic acid, and citric acid, and the total amount of the surface modifier accounts for 0.1 to 3 wt% of the total amount of the ceramic composite powder.
  • the organic binder and the surface-modified ceramic powder are made into an injection suspension.
  • the surface-modified ceramic powder accounts for 80% to 90% by weight of the injection-molded mixture
  • the organic binder accounts for 10 to 20% by weight of the injection-molded mixture.
  • the injection molded mixture refers to a mixture of an organic binder and a surface-modified ceramic powder.
  • the mixing is carried out by PEG/PVB system, and the binder system is composed of:
  • the skeleton binder PVB was added to the two-roller mixer. After the PVB was completely in a molten state and the temperature of the double rolls was raised to 170 ° C, the double rolls were started, and then phenothiazine, PEG 4000, PEG 600 and SA were added respectively, and the mixture was mixed. For 45 min, DBP was added 5 min before the end of the mixing to inhibit the plasticization.
  • Injection molding to obtain a ceramic body of a desired shape. Injection molding is performed on an injection molding machine to obtain a ceramic body of a complicated shape. According to different feeding systems and the need to inject different shapes of the blank, the injection parameters, such as injection pressure, injection speed, barrel temperature, storage position, etc., are appropriately adjusted to obtain a perfect injection body.
  • the ceramic body is degreased by a two-step degreasing method using water extraction degreasing combined with thermal degreasing to obtain a mature billet, specifically: the water-soluble binder in the component is first removed by water extraction and degreased, and then thermally degreased. The water-insoluble binder in the body is removed.
  • the water extraction degreasing is specifically: the ceramic body is placed in a water bath for water extraction and degreasing, the temperature is 40-60 ° C, and the degreasing time is 8-20 h.
  • the thermal degreasing is specifically: the body after degreasing of water is air-dried at 80 to 100 ° C for 12 to 24 hours, and then placed in an oven at 80 to 100 ° C for 4 to 6 hours to obtain a mature billet.
  • Discharge plasma sintering is performed by a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the discharge plasma sintering equipment can be realized by high-strength graphite crucible without directly pressing the mature billet.
  • the high-strength graphite crucible means that the strength of the graphite crucible can withstand the pressure exerted on the graphite crucible by the upper and lower indenters of the discharge plasma sintering equipment.
  • the pressure is usually 10 MPa.
  • the mature preform 400 is placed in a high-strength graphite crucible 100, and the graphite crucible 100 covered with the graphite cap 200 is placed in a discharge plasma sintering apparatus for sintering, and the upper and lower indenters 500 of the discharge plasma sintering apparatus are shown.
  • Pressure is applied to the graphite crucible 100 to fix the graphite crucible without pressurizing the sample, and the pulse current and the plasma are thereby heated and sintered to the mature billet 400 as a sample.
  • the high-strength graphite crucible is placed in a discharge plasma sintering apparatus for sintering, thereby applying pressure to the sample during the sintering process, and eliminating the damage of the pressure to the precision ceramic component.
  • the sintering temperature of the spark plasma sintering is 1300 to 1600 ° C, the heating rate is 10 to 100 ° C / min, and the holding time is 5 to 20 min. After sintering, the ceramic part of the desired complex shape is obtained.
  • the discharge plasma sintering apparatus performs the discharge plasma sintering so as not to directly pressurize the cooked billet, and is not limited to the graphite crucible of the present embodiment, and may be carried out by other means.
  • the preparation process of the transparent ceramic piece with a complex size and shape is carried out by controlling the process of each step, preparing a ceramic body of complex shape by injection molding, and degreasing the ceramic body by a two-step degreasing method of water extraction degreasing combined with thermal degreasing.
  • the mature billet is subjected to spark plasma sintering by means of a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the prepared transparent ceramic member has the characteristics of net size, high precision, high density, high uniformity, and good performance, and solves the problem of preparing transparent ceramic parts with complicated shapes.
  • the invention discloses a preparation process of a transparent ceramic piece of a net size complex shape, and other features are the same as those of the first embodiment, except that the technical feature is as follows: a micro-sintering aid is introduced by a magnetic stirrer in a chemical precipitation manner to obtain a sintering aid.
  • the ceramic composite powder of the agent may be a nitrate or chloride of a metal ion, and the pH of the slurry is adjusted to 9.2 to 11.4 using ammonia water so that the metal ions are deposited on the surface of the ceramic powder particles in the form of chemical precipitation.
  • the method has the characteristics of good sintering aid performance and convenient preparation.
  • the invention discloses a preparation process of a transparent ceramic piece of a net size complex shape, and other features are the same as those of the first embodiment, except that the technical feature is as follows: a micro-sintering aid is introduced by a magnetic stirrer in a chemical precipitation manner to obtain a sintering aid.
  • the ceramic composite powder of the agent may be a nitrate or a chloride of magnesium ions, and the pH of the slurry is adjusted to 9.2 to 11.4 using ammonia water, so that Mg 2+ is deposited as a chemical precipitate on the surface of the ceramic powder particles.
  • the method has the characteristics of good sintering aid performance and convenient preparation.
  • the invention discloses a preparation process of a transparent ceramic piece of a net size complex shape, and other features are the same as those of the embodiment 1 or 2 or 3.
  • the technical feature is as follows: the ball mill adopts an alumina ceramic ball mill jar, and the grinding ball is high-purity and transparent.
  • Alumina grinding balls, ball milling medium is alcohol, ceramic powder, alcohol, grinding ball, the mass ratio is 1:1:2, the rotation speed is 80 rpm to 240 rpm, and the ball milling time is 3 to 12 hours.
  • the ball milling process has the characteristics of ball milling effect and uniform particle size of the powder, and is convenient for preparing high-performance transparent ceramic parts.
  • a preparation process of a transparent ceramic piece of a net size complex shape is the same as those of Embodiment 1 or 2 or 3, except that it also has the following technical features:
  • Step (1.2) mixing is carried out by PEG/PMMA system, and the binder system is composed of:
  • the skeleton binder PVB was added to the two-roller mixer. After the PVB was completely in a molten state and the temperature of the double rolls was raised to 170 ° C, the double rolls were started, and then phenothiazine, PEG 4000, PEG 600 and SA were added respectively, and the mixture was mixed. For 45 min, DBP was added 5 min before the end of the mixing to inhibit the plasticization.
  • the preparation process of the transparent ceramic piece with a complex size and shape is carried out by controlling the process of each step, preparing a ceramic body of complex shape by injection molding, and degreasing the ceramic body by a two-step degreasing method of water extraction degreasing combined with thermal degreasing.
  • the mature billet is subjected to spark plasma sintering by means of a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the prepared transparent ceramic member has the characteristics of net size, high precision, high density, high uniformity, and good performance, and solves the problem of preparing transparent ceramic parts with complicated shapes.
  • a preparation process of a transparent ceramic piece of a net size complex shape using ⁇ -Al 2 O 3 having an average particle diameter of 100 nm and a purity of 99.99%, and introducing MgO, Y 2 O 3 as a sintering aid at a content of 0.5 wt% 1 wt% of SA was introduced as a surfactant.
  • Alcohol was used as a ball milling medium, and a self-made transparent alumina grinding ball was ball-milled at a rotation speed of 80 rpm. After ball milling for 4 hours, the surface-modified ceramic powder was obtained.
  • the PEG/PVB system was prepared by the method of (1.2) in Inventive Example 1, and then the transparent alumina ceramic bracket blank was obtained by injection molding on an injection molding machine.
  • the injection molding parameters were: the temperature from the barrel to the gate was 160. -165-170-175 ° C, the mold temperature is 45 ° C.
  • the blank obtained by injection molding was placed in a water bath to dissolve and remove the water-soluble binder.
  • the temperature of the water was 50 ° C, and the degreasing time was 8 h.
  • the degreased body after water extraction was air dried in an oven at 90 ° C for 15 h.
  • the dried body was placed in a muffle furnace and subjected to two-step thermal degreasing.
  • the heating rate was 5 ° C/min and the temperature was raised to 500 ° C, and the temperature was kept for 5 hours.
  • the hot degreased green body is placed in a high-strength graphite crucible, and the graphite crucible graphite crucible is placed in a spark plasma sintering apparatus for sintering, the heating rate is 100 ° C / min, the sintering temperature is 1450 ° C, and the holding time is After 5 min, and then cooled with the furnace, a transparent alumina ceramic bracket was obtained, as shown in FIG.
  • the alumina ceramic bracket prepared by the preparation method of the present invention has a density of 3.97 g/cm 3 , a flexural strength of 600 ⁇ 35 MPa, and a Vickers hardness of 19 GPa.
  • the SEM microstructure is dense and uniform, and the average grain size is about -200 nm without obvious pores and impurities, as shown in FIG.
  • the preparation process of the transparent ceramic piece with a complex size and shape is carried out by controlling the process of each step, preparing a ceramic body of complex shape by injection molding, and degreasing the ceramic body by a two-step degreasing method of water extraction degreasing combined with thermal degreasing.
  • the mature billet is subjected to spark plasma sintering by means of a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the prepared transparent ceramic member has the characteristics of net size, high precision, high density, high uniformity, and good performance, and solves the problem of preparing transparent ceramic parts with complicated shapes.
  • the invention discloses a preparation process of a transparent ceramic piece of a net size complex shape, which adopts ⁇ -Al 2 O 3 having an average particle diameter of 100 nm and a purity of 99.99%, and introduces MgO, Y 2 O 3 as a sintering aid at a content of 1 wt%. 3 wt% of SA was introduced as a surfactant. Alcohol was used as a ball milling medium, and a self-made transparent alumina grinding ball was ball-milled at a rotation speed of 200 rpm. After ball milling for 3 hours, the surface-modified ceramic powder was obtained.
  • the mixed PEG/PMMA system was prepared by the method of (1.2) of Inventive Example 5, and then the transparent alumina ceramic bracket blank was obtained by injection molding on an injection molding machine, and the injection molding parameters were: temperature from the barrel to the gate. The temperature was 158-165-172-178 ° C and the temperature of the mold was 49 ° C.
  • the blank obtained by injection molding was placed in a water bath to dissolve and remove the water-soluble binder.
  • the temperature of the water was 52 ° C, and the degreasing time was 6 h.
  • the degreased body after water extraction was air dried in an oven at 100 ° C for 13 h.
  • the dried body was placed in a muffle furnace and subjected to two-step thermal degreasing.
  • the heating rate was 5 ° C/min and the temperature was raised to 500 ° C, and the temperature was kept for 5 hours.
  • the hot degreased green body is placed in a high-strength graphite crucible, and the graphite crucible graphite crucible is placed in a spark plasma sintering apparatus for sintering, the heating rate is 100 ° C / min, the sintering temperature is 1450 ° C, and the holding time is 5.6 min, then cooled with the furnace to obtain a transparent alumina ceramic bracket.
  • the alumina ceramic bracket prepared by the preparation method of the present invention has a density of 3.99 g/cm 3 , a flexural strength of 610 ⁇ 35 MPa, and a Vickers hardness of 19.2 GPa.
  • the SEM microstructure is dense and uniform, and the average grain size is about 150-200 nm, and there are no obvious pores and impurities.
  • the preparation process of the transparent ceramic piece of the net size complex shape through the control of the process of each step,
  • the ceramic body of complex shape is prepared by injection molding, and the ceramic body is degreased by a two-step degreasing method of water extraction degreasing combined with thermal degreasing to obtain a mature billet, and the discharge plasma is discharged by a discharge plasma sintering apparatus without directly pressing the cooked billet. Sintering, after annealing and polishing to obtain transparent ceramic parts.
  • the prepared transparent ceramic member has the characteristics of net size, high precision, high density, high uniformity, and good performance, and solves the problem of preparing transparent ceramic parts with complicated shapes.
  • Alcohol was used as a ball milling medium, and a self-made transparent alumina grinding ball was ball-milled at a rotation speed of 200 rpm. After ball milling for 3 hours, the surface-modified ceramic powder was obtained.
  • the PEG/PVB system was prepared by the method of (1.2) in Inventive Example 1, and then the transparent cerium oxide ceramic body was injection-molded on an injection molding machine.
  • the injection molding parameters were: the temperature from the barrel to the gate was 160-163. -172-178 ° C, the mold temperature is 59 ° C.
  • the injection-molded body was placed in a water bath to dissolve and remove the water-soluble binder.
  • the temperature of the water was 60 ° C and the degreasing time was 12 h.
  • the degreased body after water extraction was air dried in an oven at 90 ° C for 15 h.
  • the dried green body was placed in a muffle furnace, and subjected to two-step thermal degreasing.
  • the heating rate was raised to 600 ° C at a heating rate of 5 ° C / min, and the temperature was maintained for 4.5 hours.
  • the hot degreased green body is placed in a high-strength graphite crucible, and the graphite crucible graphite crucible is placed in a spark plasma sintering apparatus for sintering, the heating rate is 100 ° C / min, the sintering temperature is 1450 ° C, and the holding time is 5 min, and then cooled with the furnace to obtain a transparent cerium oxide ceramic.
  • the cerium oxide ceramic prepared by the preparation method of the present invention has a density of 4.12 g/cm 3 , a flexural strength of 620 ⁇ 35 MPa, and a Vickers hardness of 18.9 GPa.
  • the SEM microstructure is dense and uniform, and the average grain size is about 80-200 nm, and there are no obvious pores and impurities.
  • the preparation process of the transparent ceramic piece with a complex size and shape is suitable for preparing a transparent ceramic piece with a net size, high precision, high density and high uniformity, and has good performance, and solves the problem of preparing a transparent ceramic piece with a complicated shape.
  • a preparation process of a transparent ceramic piece of a net size complex shape is carried out by the following steps.
  • a ceramic body is prepared by an injection molding method.
  • Step (1) preparing the ceramic body by the injection molding method specifically comprises:
  • a ceramic composite powder containing a sintering aid was obtained by chemically precipitating nickel oxide powder having a purity of 99.9% as a raw material by introducing 0.5 wt% of magnesium oxide as a auxiliaries by means of a magnetic stirrer. Specifically, magnesium chloride is used, and the pH of the slurry is adjusted to 9.2 to 11.4 using ammonia water so that Mg 2+ is deposited as a chemical precipitate onto the surface of the ceramic powder particles.
  • the surface modifier is combined with the ceramic composite powder for ball milling pretreatment, and a layer of nanometer thickness coating layer is formed on the surface of the ceramic composite powder, and the surface modified ceramic powder is obtained after drying.
  • the surface modifier is oleic acid, and the total amount of the surface modifier accounts for 0.8% by weight of the total amount of the ceramic composite powder.
  • the organic binder and the surface-modified ceramic powder are made into an injection suspension.
  • the surface-modified ceramic powder accounts for 85% by weight of the injection-molded mixture
  • the organic binder accounts for 15% by weight of the injection-molded mixture.
  • the mixing was carried out using a PEG/PVB system.
  • Injection molding to obtain a ceramic body of a desired shape. Injection molding is performed on an injection molding machine to obtain a ceramic body of a complicated shape. Adjust the injection parameters, such as injection pressure, injection speed, barrel temperature, storage position, etc., to obtain a good injection blank.
  • the ceramic body is degreased by a two-step degreasing method using water extraction degreasing combined with thermal degreasing to obtain a mature billet, specifically: the water-soluble binder in the component is first removed by water extraction and degreased, and then thermally degreased. The water-insoluble binder in the body is removed.
  • the water extraction degreasing is specifically: the ceramic body is placed in a water bath for water extraction and degreasing, the temperature is 60 ° C, and the degreasing time is 15 h.
  • the thermal degreasing is specifically: the body after degreasing of water is air-dried at 90 ° C for 20 h, and then placed in an oven and thermally degreased at 100 ° C for 4 h to obtain a mature billet.
  • Discharge plasma sintering is performed by a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the discharge plasma sintering equipment can be realized by high-strength graphite crucible without directly pressing the mature billet.
  • the sintering temperature of the spark plasma sintering is 1500 ° C
  • the heating rate is 40 ° C / min
  • the holding time is 10 min. After sintering, the ceramic part of the desired complex shape is obtained.
  • the preparation process of the transparent ceramic piece with a complex size and shape is carried out by controlling the process of each step, preparing a ceramic body of complex shape by injection molding, and degreasing the ceramic body by a two-step degreasing method of water extraction degreasing combined with thermal degreasing.
  • the mature billet is subjected to spark plasma sintering by means of a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the prepared transparent ceramic parts have the characteristics of net size, high precision, high density, high uniformity, and performance. Good, solves the problem of preparing transparent ceramic parts of complex shapes.
  • a preparation process of a transparent ceramic piece of a net size complex shape is carried out by the following steps.
  • a ceramic body is prepared by an injection molding method.
  • Step (1) preparing the ceramic body by the injection molding method specifically comprises:
  • a ceramic composite powder containing a sintering aid was obtained by chemically precipitating a 0.3% by weight of cerium oxide as a auxiliaries by a magnetic stirrer using a cerium oxide nanoceramic powder having a purity of 99.9% as a raw material.
  • the surface modifier is combined with the ceramic composite powder for ball milling pretreatment, and a layer of nanometer thickness coating layer is formed on the surface of the ceramic composite powder, and the surface modified ceramic powder is obtained after drying.
  • the surface modifier is oleic acid, and the total amount of the surface modifier accounts for 0.6% by weight of the total amount of the ceramic composite powder.
  • the organic binder and the surface-modified ceramic powder are made into an injection suspension.
  • the surface-modified ceramic powder accounts for 90% by weight of the injection-molded mixture
  • the organic binder accounts for 16% by weight of the injection-molded mixture.
  • the mixing was carried out using a PEG/PMMA system.
  • Injection molding to obtain a ceramic body of a desired shape. Injection molding is performed on an injection molding machine to obtain a ceramic body of a complicated shape. Adjust the injection parameters, such as injection pressure, injection speed, barrel temperature, storage position, etc., to obtain a good injection blank.
  • the ceramic body is degreased by a two-step degreasing method using water extraction degreasing combined with thermal degreasing to obtain a mature billet, specifically: the water-soluble binder in the component is first removed by water extraction and degreased, and then thermally degreased. The water-insoluble binder in the body is removed.
  • the water extraction degreasing is specifically: the ceramic body is placed in a water bath for water extraction and degreasing, the temperature is 80 ° C, and the degreasing time is 10 h.
  • the thermal degreasing is specifically: the body after water degreasing is air-dried at 100 ° C for 20 h, and then placed in an oven and thermally degreased at 70 ° C for 6 h to obtain a mature billet.
  • Discharge plasma sintering is performed by a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the discharge plasma sintering equipment can be realized by high-strength graphite crucible without directly pressing the mature billet.
  • the sintering temperature of the spark plasma sintering is 1580 ° C, the heating rate is 60 ° C / min, and the holding time is 12 min. After sintering, the ceramic part of the desired complex shape is obtained.
  • the preparation process of the transparent ceramic piece with a complex size and shape is carried out by controlling the process of each step, preparing a ceramic body of complex shape by injection molding, and degreasing the ceramic body by a two-step degreasing method of water extraction degreasing combined with thermal degreasing.
  • the mature billet is subjected to spark plasma sintering by means of a discharge plasma sintering apparatus without directly pressing the cooked billet, and after annealing and polishing, a transparent ceramic member is obtained.
  • the prepared transparent ceramic member has the characteristics of net size, high precision, high density, high uniformity, and good performance, and solves the problem of preparing transparent ceramic parts with complicated shapes.

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Abstract

一种净尺寸复杂形状透明陶瓷件的制备工艺，该工艺包括：1）以注射成型方法制备得到陶瓷坯体；2）采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯；3）通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。该净尺寸复杂形状透明陶瓷件的制备工艺适合制备净尺寸、高精度、高密度、高均匀性、高性能、复杂形状部件的透明陶瓷件。

Description

一种净尺寸复杂形状透明陶瓷件的制备工艺 技术领域
本发明涉及高性能透明陶瓷制备技术领域，特别涉及一种净尺寸复杂形状透明陶瓷件的制备工艺。本申请是以申请号2016100255955、申请日2016年1月13日的中国发明专利为基础的。
背景技术
很长时期以来，人们认为陶瓷是不透明的。但自1962年美国GE公司的R.L.Coble首次报导成功地制备了半透明Al2O3陶瓷(商品名称为Lucalox)从而一举打破了人们的传统观念，也为陶瓷材料开辟了新的应用领域。
此后，其它氧化物透明陶瓷，如Y2O3(氧化钇)、MgO(氧化镁)、BeO(氧化铍)、CaO(氧化钙)、ThO2(氧化钍)、MgAl2O4(镁铝尖晶石)、(Pb、La)(Zr、Ti)O(锆钛酸铅)等相继问世。随后，可作为新一代固体激光材料的掺杂钇铝石榴石(如Nd:YAG)透明陶瓷也被制备出来，并得到广泛的研究和应用。近十余年来，一批非氧化物透明陶瓷也得到相继开发，如AlON(阿隆)透明陶瓷、AlN(氮化铝)透明陶瓷、SiAlON(赛隆)透明陶瓷等。
目前透明陶瓷多采用传统的成型方法，如干压、注浆、等静压成型。陶瓷干压成型虽然效率较高，但存在密度差异、显微结构不均匀的现象，同时不易成型异形部件。陶瓷注浆成型虽可成型异形产品，但成型坯体易产生密度不均和成分偏析，存在成型尺寸精度低和产品可靠性下降等问题。冷等静压成型可得到高密度和高均匀性的成型坯体，但难以成型形状复杂的陶瓷零部件，且成型效率低和需要手工操作的工序较多。这些传统成型方法不适用于制备精密、复杂形状的高性能、高可靠性的透明陶瓷件。
因此，针对现有技术不足，提供一种净尺寸复杂形状透明陶瓷件的制备工艺以克服现有技术不足甚为必要。
发明内容
本发明的目的在于避免现有技术的不足之处而提供一种净尺寸复杂形状透明陶瓷件的制备工艺，该制备工艺适合制备净尺寸、高精度、高密度、高均匀性、高性能、复杂形状的透明陶瓷件。
本发明的上述目的通过如下技术手段实现。
提供一种净尺寸复杂形状透明陶瓷件的制备工艺，包括如下步骤：
(1)以注射成型方法制备得到陶瓷坯体；
(2)采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯；
(3)通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。
上述步骤(1)以注射成型方法制备得到陶瓷坯体具体包括：
(1.1)陶瓷粉体表面改性
以纯度大于等于99.9％的高纯纳米陶瓷粉体作为原料，以化学沉淀的方式通过磁力搅拌器引入微量烧结助剂得到含有烧结助剂的陶瓷复合粉体；
之后将表面改性剂与陶瓷复合粉体一起进行球磨预处理，在陶瓷复合粉体表面形成一层几个纳米厚度的包覆层，烘干后得到表面改性化陶瓷粉体；
(1.2)混炼
将有机粘结剂与表面改性化陶瓷粉体制成注射悬浮体；
(1.3)注射成型得到需要形状的陶瓷坯体。
上述陶瓷粉体为纯度大于99.9％的氧化钇、氧化镁、氧化铍、氧化钙、氧化钍、镁铝尖晶石、锆钛酸铅陶瓷或者为阿隆陶瓷、氮化铝陶瓷、赛隆陶瓷；
所述烧结助剂为氧化镁、氧化钇、氧化镧中的一种或者多种，所述烧结助剂的总量占所述陶瓷粉体总量的0.1～1wt％；
所述表面改性剂为硬脂酸、油酸、十二羟基硬脂酸、柠檬酸中的任意一种，表面改性剂的总量占所述陶瓷复合粉体总量的0.1～3wt％；
在所述注射成型的混合料中，表面改性化陶瓷粉体占注射成型的混合料的重量百分比为80％～90％，有机粘结剂占注射成型的混合料的重量百分比为10～20％。
上述的净尺寸复杂形状透明陶瓷件的制备工艺，
以化学沉淀的方式通过磁力搅拌器引入微量烧结助剂得到含有烧结助剂的陶瓷复合粉体具体是采用金属离子的硝酸盐或者氯化物，使用氨水调节浆料的pH值至9.2～11.4，使得金属离子以化学沉淀的形式沉积到陶瓷粉体颗粒的表面；
球磨采用氧化铝陶瓷球磨罐，磨球为高纯透明氧化铝磨球，球磨介质为酒精，陶瓷粉、酒精、磨球三者的质量比为1：1：2，转速为80rpm～240rpm，球磨时间为3～12h。
优选的，上述步骤(1.2)混炼采用PEG/PVB体系喂料，粘结剂体系组成为：22wt％PVB+33wt％PEG4000+33wt％PEG600+9wt％SA+2.5％DBP，另外加0.5wt％的酚噻嗪作抗氧剂；
首先在双辊混炼机中加入骨架粘结剂PVB，待PVB完全呈现熔融态且双辊温度升至170℃后启动双辊，然后分别加入吩噻嗪、PEG4000、PEG600和SA，混炼总共持续45min,在混炼结束前5min加入DBP以抑制达到增塑的目的。
另一优选的，上述步骤(1.2)混炼采用PEG/PMMA体系喂料，粘结剂体系组成为：
20wt％PMMA+30wt％PEG4000+35wt％PEG600+12wt％SA+2.5％DBP，另外加0.5wt％的酚噻嗪作抗氧剂；
首先在双辊混炼机中加入骨架粘结剂PMMA，待PMMA完全呈现熔融态且双辊温度升至170℃后启动双辊，然后分别加入吩噻嗪、PEG4000、PEG600和SA，混炼总共持续45min，在混炼结束前5min加入DBP以抑制达到增塑的目的。
上述步骤(2)采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯具体是：先通过水萃取脱脂将组分中的水溶性粘结剂脱除，再通过热脱脂除去坯体中的非水溶性粘结剂。
上述水萃取脱脂具体是：将陶瓷坯体置于水浴锅中进行水萃取脱脂，温度为40～60℃，脱脂时间为8～20h；
所述热脱脂具体是：水脱脂后的坯体于80～100℃下空气干燥12～24h后，放入马弗炉中将温度升至450～500℃保温2～3h得到熟坯，升温速率为2～4℃/min。
上述步骤(3)具体是：将熟坯置于石墨坩埚，将盖有石墨盖的石墨坩埚整体放入放电等离子烧结设备中进行烧结，放电等离子烧结设备的上下压头对石墨坩埚施加压力以固定石墨坩埚。
上述步骤(3)中放电等离子烧结的烧结温度为1300～1600℃,升温速率为10～100℃/min，保温时间为5～20min。
本发明的净尺寸复杂形状透明陶瓷件的制备工艺，包括如下步骤：(1)以注射成型方法制备得到陶瓷坯体；(2)采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯；(3)通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。该净尺寸复杂形状透明陶瓷件的制备工艺适合制备净尺寸、高精度、高密度、高均匀性、高性能、复杂形状结构的透明陶瓷件。
附图说明
利用附图对本发明作进一步的说明，但附图中的内容不构成对本发明的任何限制。
图1是本发明一种净尺寸复杂形状透明陶瓷件的制备工艺中所采用的放电等离子烧结设备与石墨坩埚的使用状态示意图。
图2是本发明实施例6所制备的透明氧化铝托槽的结构示意图。
图3是图2的透明氧化铝托槽的SEM表面形貌示意图。
在图1中，包括：
石墨坩埚100、石墨盖200、石墨垫片300、熟坯400、上下压头500。
具体实施方式
结合以下实施例对本发明作进一步描述。
实施例1。
一种净尺寸复杂形状透明陶瓷件的制备工艺，通过如下三个步骤进行。
(1)以注射成型方法制备得到陶瓷坯体。
步骤(1)以注射成型方法制备得到陶瓷坯体具体包括：
(1.1)陶瓷粉体表面改性
以高纯纳米陶瓷粉体作为原料，以化学沉淀的方式通过磁力搅拌器引入微量烧结助剂得到含有烧结助剂的陶瓷复合粉体。高纯纳米陶瓷粉体是指纯度大于99.9％的粉体。陶瓷粉体为纯度大于99.9％的氧化钇、氧化镁、氧化铍、氧化钙、氧化钍、镁铝尖晶石、锆钛酸铅陶瓷或者为阿隆陶瓷、氮化铝陶瓷、赛隆陶瓷。烧结助剂为氧化镁、氧化钇、氧化镧中的一种或者多种，烧结助剂的总量占陶瓷粉体总量的0.1～1wt％。
之后将表面改性剂与陶瓷复合粉体一起进行球磨预处理，在陶瓷复合粉体表面形成一层几个纳米厚度的包覆层，烘干后得到表面改性化陶瓷粉体。表面改性剂为硬脂酸、油酸、十二羟基硬脂酸、柠檬酸中的任意一种，表面改性剂的总量占陶瓷复合粉体总量的0.1～3wt％。
(1.2)混炼
将有机粘结剂与表面改性化陶瓷粉体制成注射悬浮体。在注射成型的混合料中，表面改性化陶瓷粉体占注射成型的混合料的重量百分比为80％～90％，有机粘结剂占注射成型的混合料的重量百分比为10～20％。注射成型的混合料是指有机粘结剂与表面改性化陶瓷粉体的混合料。
混炼采用PEG/PVB体系喂料，粘结剂体系组成为：
22wt％PVB+33wt％PEG4000+33wt％PEG600+9wt％SA+2.5％DBP，另外加0.5wt％的酚噻嗪作抗氧剂。
首先在双辊混炼机中加入骨架粘结剂PVB，待PVB完全呈现熔融态且双辊温度升至170℃后启动双辊，然后分别加入吩噻嗪、PEG4000、PEG600和SA，混炼总共持续45min,在混炼结束前5min加入DBP以抑制达到增塑的目的。
(1.3)注射成型得到需要形状的陶瓷坯体。在注射成型机上注射成型得到复杂形状的陶瓷坯体。根据不同的喂料体系和需要注射不同形状的坯体，适当调节注射参数，如注射压力、注射速度、料筒温度、储料位置等，以得到完好的注射坯体。
(2)采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，具体是：先通过水萃取脱脂将组分中的水溶性粘结剂脱除，再通过热脱脂除去坯体中的非水溶性粘结剂。
水萃取脱脂具体是：将陶瓷坯体置于水浴锅中进行水萃取脱脂，温度为40～60℃，脱脂时间为8～20h。
热脱脂具体是：水脱脂后的坯体于80～100℃下空气干燥12～24h后，放入烘箱中在80～100℃下热脱脂4～6h得到熟坯。
(3)通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。
放电等离子烧结设备以不对熟坯直接加压的方式可以通过高强度石墨坩埚实现，高强度的石墨坩埚是指石墨坩埚的强度能够承受放电等离子烧结设备的上下压头对石墨坩埚施加的压力，这个压力通常是10MPa。如图1所示，将熟坯400置于高强度的石墨坩埚100内，将盖有石墨盖200的石墨坩埚100整体放入放电等离子烧结设备中进行烧结，放电等离子烧结设备的上下压头500对石墨坩埚100施加压力将石墨坩埚固定而不对样品加压，脉冲电流与等离子体从而对作为样品的熟坯400实现加热烧结。通过高强度石墨坩埚放入放电等离子体烧结设备中进行烧结，实现在烧结过程中对样品施加压力，消除压力对精密陶瓷部件的破坏。
放电等离子烧结的烧结温度为1300～1600℃,升温速率为10～100℃/min，保温时间为5～20min。烧结后得到所需的复杂形状的陶瓷件。
需要说明的是，放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结不局限于本实施例的石墨坩埚，还可以通过其它方式进行。
该净尺寸复杂形状透明陶瓷件的制备工艺，通过对各个步骤工艺的控制，采用注射成型制备复杂形状的陶瓷坯体，采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。所制备的透明陶瓷件具备净尺寸、高精度、高密度、高均匀性的特点，且性能良好，解决了制备复杂形状的透明陶瓷件的难题。
实施例2。
一种净尺寸复杂形状透明陶瓷件的制备工艺，其它特征与实施例1相同，不同之处在于，还具有如下技术特征：以化学沉淀的方式通过磁力搅拌器引入微量烧结助剂得到含有烧结助剂的陶瓷复合粉体可以采用金属离子的硝酸盐或者氯化物，使用氨水调节浆料的pH值至9.2～11.4，使得金属离子以化学沉淀的形式沉积到陶瓷粉体颗粒的表面。该方式具有烧结助剂性能良好，制备方便的特点。
实施例3。
一种净尺寸复杂形状透明陶瓷件的制备工艺，其它特征与实施例1相同，不同之处在于，还具有如下技术特征：以化学沉淀的方式通过磁力搅拌器引 入微量烧结助剂得到含有烧结助剂的陶瓷复合粉体可以采用镁离子的硝酸盐或者氯化物，使用氨水调节浆料的pH值至9.2～11.4，使得Mg2+以化学沉淀的形式沉积到陶瓷粉体颗粒的表面。该方式具有烧结助剂性能良好，制备方便的特点。
实施例4。
一种净尺寸复杂形状透明陶瓷件的制备工艺，其它特征与实施例1或2或3相同，不同之处在于，还具有如下技术特征：球磨采用氧化铝陶瓷球磨罐，磨球为高纯透明氧化铝磨球，球磨介质为酒精，陶瓷粉、酒精、磨球三者的质量比为1：1：2，转速为80rpm～240rpm，球磨时间为3～12h。该球磨工艺具有球磨效果、粉料粒度均匀的特点，便于制备高性能的透明陶瓷件。
实施例5。
一种净尺寸复杂形状透明陶瓷件的制备工艺，其它特征与实施例1或2或3相同，不同之处在于，还具有如下技术特征：
步骤(1.2)混炼采用PEG/PMMA体系喂料，粘结剂体系组成为：
22wt％PVB+33wt％PEG4000+33wt％PEG600+9wt％SA+2.5％DBP，另外加0.5wt％的酚噻嗪作抗氧剂；
首先在双辊混炼机中加入骨架粘结剂PVB，待PVB完全呈现熔融态且双辊温度升至170℃后启动双辊，然后分别加入吩噻嗪、PEG4000、PEG600和SA，混炼总共持续45min,在混炼结束前5min加入DBP以抑制达到增塑的目的。
该净尺寸复杂形状透明陶瓷件的制备工艺，通过对各个步骤工艺的控制，采用注射成型制备复杂形状的陶瓷坯体，采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。所制备的透明陶瓷件具备净尺寸、高精度、高密度、高均匀性的特点，且性能良好，解决了制备复杂形状的透明陶瓷件的难题。
实施例6。
一种净尺寸复杂形状透明陶瓷件的制备工艺，采用平均粒径为100nm、纯度为99.99％的α-Al2O3，将MgO，Y2O3作为烧结助剂以0.5wt％的含量引入，1wt％的SA作为表面活性剂引入。采用酒精为球磨介质，自制透明氧化铝磨球进行球磨，转速为80rpm，球磨4h后取出烘干得到表面改性化陶瓷粉 体。
采用发明实施例1中(1.2)方法配制PEG/PVB体系喂料，之后在注射成型机上注射成型得到透明氧化铝陶瓷托槽坯体，注射成型参数为：从料筒到浇口的温度为160-165-170-175℃，模温机温度为45℃。
将注射成型得到的坯体放入水浴锅中，溶解脱除水溶性粘结剂，水的温度为50℃，脱脂时间为8h。水萃取脱脂后的坯体在90℃烘箱中空气干燥15h。
将干燥后的坯体放入马弗炉内，进行二步热脱脂，升温速率为5℃/min升温至500℃，保温5h。将热脱脂之后的坯体置于高强度石墨坩埚中，将该有石墨盖的石墨坩埚置于放电等离子烧结设备中进行烧结，升温速率为100℃/min，烧结温度为1450℃，保温时间为5min，然后随炉冷却，得到透明氧化铝陶瓷托槽，如图2所示。
本发明的制备方法所制备的氧化铝陶瓷托槽的密度为3.97g/cm3，抗弯强度为600±35Mpa，维氏硬度为19Gpa。其SEM显微结构致密且均匀，平均晶粒尺寸约为～200nm，无明显气孔与杂质，如图3所示。
该净尺寸复杂形状透明陶瓷件的制备工艺，通过对各个步骤工艺的控制，采用注射成型制备复杂形状的陶瓷坯体，采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。所制备的透明陶瓷件具备净尺寸、高精度、高密度、高均匀性的特点，且性能良好，解决了制备复杂形状的透明陶瓷件的难题。
实施例7。
一种净尺寸复杂形状透明陶瓷件的制备工艺，采用平均粒径为100nm、纯度为99.99％的α-Al2O3，将MgO，Y2O3作为烧结助剂以1wt％的含量引入，3wt％的SA作为表面活性剂引入。采用酒精为球磨介质，自制透明氧化铝磨球进行球磨，转速为200rpm，球磨3h后取出烘干得到表面改性化陶瓷粉体。
采用发明实施例5中(1.2)的方法配制混PEG/PMMA体系喂料，之后在注射成型机上注射成型得到透明氧化铝陶瓷托槽坯体，注射成型参数为：从料筒到浇口的温度为158-165-172-178℃，模温机温度为49℃。
将注射成型得到的坯体放入水浴锅中，溶解脱除水溶性粘结剂，水的温度为52℃，脱脂时间为6h。水萃取脱脂后的坯体在100℃烘箱中空气干燥13h。
将干燥后的坯体放入马弗炉内，进行二步热脱脂，升温速率为5℃/min升温至500℃，保温5h。将热脱脂之后的坯体置于高强度石墨坩埚中，将该有石墨盖的石墨坩埚置于放电等离子烧结设备中进行烧结，升温速率为100℃/min，烧结温度为1450℃，保温时间为5.6min，然后随炉冷却，得到透明氧化铝陶瓷托槽。
本发明的制备方法所制备的氧化铝陶瓷托槽的密度为3.99g/cm3，抗弯强度为610±35Mpa，维氏硬度为19.2Gpa。其SEM显微结构致密且均匀，平均晶粒尺寸约为150～200nm，无明显气孔与杂质。
该净尺寸复杂形状透明陶瓷件的制备工艺，通过对各个步骤工艺的控制， 采用注射成型制备复杂形状的陶瓷坯体，采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。所制备的透明陶瓷件具备净尺寸、高精度、高密度、高均匀性的特点，且性能良好，解决了制备复杂形状的透明陶瓷件的难题。
实施例8。
一种净尺寸复杂形状透明陶瓷件的制备工艺，采用平均粒径为100nm、纯度为99.99％的氧化铍，将MgO，La2O3作为烧结助剂以0.1wt％的含量引入，2wt％的SA作为表面活性剂引入。采用酒精为球磨介质，自制透明氧化铝磨球进行球磨，转速为200rpm，球磨3h后取出烘干得到表面改性化陶瓷粉体。
采用发明实施例1中(1.2)方法配制PEG/PVB体系喂料，之后在注射成型机上注射成型得到透明氧化铍陶瓷坯体，注射成型参数为：从料筒到浇口的温度为160-163-172-178℃，模温机温度为59℃。
将注射成型得到的坯体放入水浴锅中，溶解脱除水溶性粘结剂，水的温度为60℃，脱脂时间为12h。水萃取脱脂后的坯体在90℃烘箱中空气干燥15h。
将干燥后的坯体放入马弗炉内，进行二步热脱脂，升温速率为5℃/min升温至600℃，保温4.5h。将热脱脂之后的坯体置于高强度石墨坩埚中，将该有石墨盖的石墨坩埚置于放电等离子烧结设备中进行烧结，升温速率为100℃/min，烧结温度为1450℃，保温时间为5min，然后随炉冷却，得到透明氧化铍陶瓷。
本发明的制备方法所制备的氧化铍陶瓷的密度为4.12g/cm3，抗弯强度为620±35Mpa，维氏硬度为18.9Gpa。其SEM显微结构致密且均匀，平均晶粒尺寸约为80～200nm，无明显气孔与杂质。
该净尺寸复杂形状透明陶瓷件的制备工艺，适合于制备净尺寸、高精度、高密度、高均匀性的透明陶瓷件，且性能良好，解决了制备复杂形状的透明陶瓷件的难题。
实施例9。
一种净尺寸复杂形状透明陶瓷件的制备工艺，通过如下步骤进行。
(1)以注射成型方法制备得到陶瓷坯体。
步骤(1)以注射成型方法制备得到陶瓷坯体具体包括：
(1.1)陶瓷粉体表面改性
以纯度99.9％的氧化钇纳米陶瓷粉体作为原料，以化学沉淀的方式通过磁力搅拌器引入0.5wt％的氧化镁作为结助剂得到含有烧结助剂的陶瓷复合粉体。具体是采用镁的氯化物、使用氨水调节浆料的pH值至9.2～11.4，使得 Mg2+以化学沉淀的形式沉积到陶瓷粉体颗粒的表面。
之后将表面改性剂与陶瓷复合粉体一起进行球磨预处理，在陶瓷复合粉体表面形成一层几个纳米厚度的包覆层，烘干后得到表面改性化陶瓷粉体。表面改性剂为油酸，表面改性剂的总量占陶瓷复合粉体总量的0.8wt％。
(1.2)混炼
将有机粘结剂与表面改性化陶瓷粉体制成注射悬浮体。在注射成型的混合料中，表面改性化陶瓷粉体占注射成型的混合料的重量百分比为85％，有机粘结剂占注射成型的混合料的重量百分比为15％。混炼采用PEG/PVB体系喂料。
(1.3)注射成型得到需要形状的陶瓷坯体。在注射成型机上注射成型得到复杂形状的陶瓷坯体。调节注射参数，如注射压力、注射速度、料筒温度、储料位置等，得到完好的注射坯体。
(2)采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，具体是：先通过水萃取脱脂将组分中的水溶性粘结剂脱除，再通过热脱脂除去坯体中的非水溶性粘结剂。
水萃取脱脂具体是：将陶瓷坯体置于水浴锅中进行水萃取脱脂，温度为60℃，脱脂时间为15h。
热脱脂具体是：水脱脂后的坯体于90℃下空气干燥20h后，放入烘箱中在100℃下热脱脂4h得到熟坯。
(3)通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。
放电等离子烧结设备以不对熟坯直接加压的方式可以通过高强度石墨坩埚实现，放电等离子烧结的烧结温度为1500℃,升温速率为40℃/min，保温时间为10min。烧结后得到所需的复杂形状的陶瓷件。
该净尺寸复杂形状透明陶瓷件的制备工艺，通过对各个步骤工艺的控制，采用注射成型制备复杂形状的陶瓷坯体，采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。所制备的透明陶瓷件具备净尺寸、高精度、高密度、高均匀性的特点，且性能 良好，解决了制备复杂形状的透明陶瓷件的难题。
实施例11。
一种净尺寸复杂形状透明陶瓷件的制备工艺，通过如下步骤进行。
(1)以注射成型方法制备得到陶瓷坯体。
步骤(1)以注射成型方法制备得到陶瓷坯体具体包括：
(1.1)陶瓷粉体表面改性
以纯度99.9％的氧化钍纳米陶瓷粉体作为原料，以化学沉淀的方式通过磁力搅拌器引入0.3wt％的氧化镧作为结助剂得到含有烧结助剂的陶瓷复合粉体。
之后将表面改性剂与陶瓷复合粉体一起进行球磨预处理，在陶瓷复合粉体表面形成一层几个纳米厚度的包覆层，烘干后得到表面改性化陶瓷粉体。表面改性剂为油酸，表面改性剂的总量占陶瓷复合粉体总量的0.6wt％。
(1.2)混炼
将有机粘结剂与表面改性化陶瓷粉体制成注射悬浮体。在注射成型的混合料中，表面改性化陶瓷粉体占注射成型的混合料的重量百分比为90％，有机粘结剂占注射成型的混合料的重量百分比为16％。混炼采用PEG/PMMA体系喂料。
(1.3)注射成型得到需要形状的陶瓷坯体。在注射成型机上注射成型得到复杂形状的陶瓷坯体。调节注射参数，如注射压力、注射速度、料筒温度、储料位置等，得到完好的注射坯体。
(2)采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，具体是：先通过水萃取脱脂将组分中的水溶性粘结剂脱除，再通过热脱脂除去坯体中的非水溶性粘结剂。
水萃取脱脂具体是：将陶瓷坯体置于水浴锅中进行水萃取脱脂，温度为80℃，脱脂时间为10h。
热脱脂具体是：水脱脂后的坯体于100℃下空气干燥20h后，放入烘箱中在70℃下热脱脂6h得到熟坯。
(3)通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。
放电等离子烧结设备以不对熟坯直接加压的方式可以通过高强度石墨坩埚实现，放电等离子烧结的烧结温度为1580℃,升温速率为60℃/min，保温时间为12min。烧结后得到所需的复杂形状的陶瓷件。
该净尺寸复杂形状透明陶瓷件的制备工艺，通过对各个步骤工艺的控制，采用注射成型制备复杂形状的陶瓷坯体，采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯，通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。所制备的透明陶瓷件具备净尺寸、高精度、高密度、高均匀性的特点，且性能良好，解决了制备复杂形状的透明陶瓷件的难题。
最后应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于，包括如下步骤：
    (1)以注射成型方法制备得到陶瓷坯体；
    (2)采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯；
    (3)通过放电等离子烧结设备以不对熟坯直接加压的方式进行放电等离子烧结，经过退火抛光后得到透明陶瓷件。
  2. 根据权利要求1所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于，所述步骤(1)以注射成型方法制备得到陶瓷坯体具体包括：
    (1.1)陶瓷粉体表面改性
    以纯度大于等于99.9％的高纯纳米陶瓷粉体作为原料，以化学沉淀的方式通过磁力搅拌器引入微量烧结助剂得到含有烧结助剂的陶瓷复合粉体；
    之后将表面改性剂与陶瓷复合粉体一起进行球磨预处理，在陶瓷复合粉体表面形成一层几个纳米厚度的包覆层，烘干后得到表面改性化陶瓷粉体；
    (1.2)混炼
    将有机粘结剂与表面改性化陶瓷粉体制成注射悬浮体；
    (1.3)注射成型得到需要形状的陶瓷坯体。
  3. 根据权利要求2所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于：
    所述陶瓷粉体为纯度大于99.9％的氧化钇、氧化镁、氧化铍、氧化钙、氧化钍、镁铝尖晶石、锆钛酸铅陶瓷或者为阿隆陶瓷、氮化铝陶瓷、赛隆陶瓷；
    所述烧结助剂为氧化镁、氧化钇、氧化镧中的一种或者多种，所述烧结助剂的总量占所述陶瓷粉体总量的0.1～1wt％；
    所述表面改性剂为硬脂酸、油酸、十二羟基硬脂酸、柠檬酸中的任意一种，表面改性剂的总量占所述陶瓷复合粉体总量的0.1～3wt％；
    在所述注射成型的混合料中，表面改性化陶瓷粉体占注射成型的混合料的重量百分比为80％～90％，有机粘结剂占注射成型的混合料的重量百分比为10～20％。
  4. 根据权利要求3所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于：
    以化学沉淀的方式通过磁力搅拌器引入微量烧结助剂得到含有烧结助剂的陶瓷复合粉体具体是采用金属离子的硝酸盐或者氯化物，使用氨水调节浆料的pH值至9.2～11.4，使得金属离子以化学沉淀的形式沉积到陶瓷粉体颗粒的表面；
    球磨采用氧化铝陶瓷球磨罐，磨球为高纯透明氧化铝磨球，球磨介质为酒精，陶瓷粉、酒精、磨球三者的质量比为1：1：2，转速为80rpm～240rpm，球磨时间为3～12h。
  5. 根据权利要求2所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于：
    所述步骤(1.2)混炼采用PEG/PVB体系喂料，粘结剂体系组成为：22wt％PVB+33wt％PEG4000+33wt％PEG600+9wt％SA+2.5％DBP，另外加0.5wt％的酚噻嗪作抗氧剂；
    首先在双辊混炼机中加入骨架粘结剂PVB，待PVB完全呈现熔融态且双辊温度升至170℃后启动双辊，然后分别加入吩噻嗪、PEG4000、PEG600和SA，混炼总共持续45min,在混炼结束前5min加入DBP以抑制达到增塑的目的。
  6. 根据权利要求2所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于：
    所述步骤(1.2)混炼采用PEG/PMMA体系喂料，粘结剂体系组成为：20wt％PMMA+30wt％PEG4000+35wt％PEG600+12wt％SA+2.5％DBP，另外加0.5wt％的酚噻嗪作抗氧剂；
    首先在双辊混炼机中加入骨架粘结剂PMMA，待PMMA完全呈现熔融态且双辊温度升至170℃后启动双辊，然后分别加入吩噻嗪、PEG4000、PEG600和SA，混炼总共持续45min，在混炼结束前5min加入DBP以抑制达到增塑的目的。
  7. 根据权利要求1至6任意一项所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于：
    所述步骤(2)采用水萃取脱脂结合热脱脂的二步脱脂法对陶瓷坯体进行脱脂得到熟坯具体是：先通过水萃取脱脂将组分中的水溶性粘结剂脱除，再通过热脱脂除去坯体中的非水溶性粘结剂。
  8. 根据权利要求7所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于：
    所述水萃取脱脂具体是：将陶瓷坯体置于水浴锅中进行水萃取脱脂，温度为40～60℃，脱脂时间为8～20h；
    所述热脱脂具体是：水脱脂后的坯体于80～100℃下空气干燥12～24h后，放入马弗炉中将温度升至450～500℃保温2～3h得到熟坯，升温速率为2～4℃/min。
  9. 根据权利要求1所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于：
    所述步骤(3)具体是：将熟坯置于石墨坩埚，将盖有石墨盖的石墨坩埚整体放入放电等离子烧结设备中进行烧结，放电等离子烧结设备的上下压头对石墨坩埚施加压力以固定石墨坩埚。
  10. 根据权利要求5所述的净尺寸复杂形状透明陶瓷件的制备工艺，其特征在于：
    所述步骤(3)中放电等离子烧结的烧结温度为1300～1600℃,升温速率为10～100℃/min，保温时间为5～20min。
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Publication number Priority date Publication date Assignee Title
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1569731A (zh) * 2004-04-23 2005-01-26 清华大学 一种Li－Si－Ni－0基高介电常数陶瓷材料及其合成方法
CN1709823A (zh) * 2005-06-21 2005-12-21 清华大学深圳研究生院 制备透明MgAlON陶瓷的方法及透明MgAlON陶瓷
CN101643360A (zh) * 2009-09-02 2010-02-10 清华大学 一种注射成型制造齿状异形陶瓷部件的方法
CN101691086A (zh) * 2009-10-29 2010-04-07 哈尔滨工业大学 打印头陶瓷基板的粉末微注射成型方法
CN102515720A (zh) * 2011-12-08 2012-06-27 西安交通大学 一种透明氧化铝陶瓷的制备方法
CN103833373A (zh) * 2014-01-02 2014-06-04 佛山市东方智柏纳米材料科技有限公司 一种纳米超细陶瓷的环保生产方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412148A (zh) * 2002-12-06 2003-04-23 王国梁 透明氧化铝陶瓷制品及其制造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1569731A (zh) * 2004-04-23 2005-01-26 清华大学 一种Li－Si－Ni－0基高介电常数陶瓷材料及其合成方法
CN1709823A (zh) * 2005-06-21 2005-12-21 清华大学深圳研究生院 制备透明MgAlON陶瓷的方法及透明MgAlON陶瓷
CN101643360A (zh) * 2009-09-02 2010-02-10 清华大学 一种注射成型制造齿状异形陶瓷部件的方法
CN101691086A (zh) * 2009-10-29 2010-04-07 哈尔滨工业大学 打印头陶瓷基板的粉末微注射成型方法
CN102515720A (zh) * 2011-12-08 2012-06-27 西安交通大学 一种透明氧化铝陶瓷的制备方法
CN103833373A (zh) * 2014-01-02 2014-06-04 佛山市东方智柏纳米材料科技有限公司 一种纳米超细陶瓷的环保生产方法

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CN115108817A (zh) * 2022-06-17 2022-09-27 无锡畾田陶瓷科技有限公司 一种环保耐磨陶砖及其制备工艺
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