WO2023095954A1 - Corps fritté en alumine noire et son procédé de fabrication - Google Patents

Corps fritté en alumine noire et son procédé de fabrication Download PDF

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WO2023095954A1
WO2023095954A1 PCT/KR2021/017572 KR2021017572W WO2023095954A1 WO 2023095954 A1 WO2023095954 A1 WO 2023095954A1 KR 2021017572 W KR2021017572 W KR 2021017572W WO 2023095954 A1 WO2023095954 A1 WO 2023095954A1
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alumina
black
black alumina
slurry
granules
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Korean (ko)
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이상진
공헌
오복현
박상진
안유경
이종근
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목포대학교산학협력단
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Definitions

  • the present invention relates to a black alumina sintered body and a manufacturing method thereof.
  • Alumina is a representative ceramic material with excellent mechanical strength, heat resistance, wear resistance and insulation, and has been used in various fields based on chemical resistance and mechanical properties.
  • it is used as a chuck plate for fixing substrates in semiconductor and display manufacturing processes.
  • it has a disadvantage in the photo process because of its high reflectance due to its color close to ivory.
  • secondary light exposure occurs due to the reflection of the light source, which is likely to cause defects in the circuit pattern. Therefore, to prevent the reflection of the light source from the chuck plate, alumina with a black color that can absorb light material development is required.
  • An object of the present invention is to prepare a black alumina sintered body having a low reflectance and a black color by adding a transition metal oxide to alumina.
  • the present invention aims to replace the conventional Japanese black alumina by manufacturing black alumina using domestic alumina raw materials in view of Japan's export regulations and the high unit price of imported alumina.
  • the present invention is a method for preparing a black alumina sintered body having a low reflectance and black color by adding a transition metal oxide to alumina, and is characterized in that a molded body is prepared using black alumina powder or black alumina granules and then sintered.
  • the present invention is a manufacturing method using black alumina powder, comprising: a first step of preparing a mixed powder for preparing black alumina by mixing alumina and an additive; A second step of preparing a black alumina slurry by wet ball milling the mixed powder for preparing black alumina; A third step of drying the black alumina slurry and pulverizing it to obtain a homogenized black alumina powder by sieving with a 240 mesh; And a fourth step of compressing the homogenized black alumina powder to produce a black alumina powder molded body and heat-treating at 1250 to 1400 ° C. for 1 hour to prepare a black alumina sintered body.
  • Method for producing a black alumina sintered body comprising: provides
  • the mixed powder for producing black alumina is characterized in that it includes 65 to 95% by weight of alumina and 5 to 35% by weight of additives, and the additives are titanium dioxide (TiO 2 ), iron (III) oxide (Fe 2 O 3 ), oxide of one oxide or two or more oxides selected from the group consisting of cobalt(III) (Co 2 O 3 ), silicon dioxide (SiO 2 ), manganese oxide (MnO), zirconium oxide (ZrO 2 ), and zinc oxide (ZnO). It is characterized by being a mixture.
  • the black alumina sintered body produced by the manufacturing method using the black alumina powder has a black color, has a reflectance of 6.4 to 9.7% for visible light (380 to 780 nm), a density of 3.45 to 4.0 g/cm 3 , and a hardness of 3.45 to 4.0 g/cm 3 . It is characterized in that 800 to 1250Hv.
  • the present invention is a manufacturing method using black alumina granules, comprising: a first step of preparing an alumina slurry for primary ball milling by mixing an alumina raw material, a solvent, a dispersant, and an additive; A second step of preparing a first black alumina slurry by primary ball milling the alumina slurry for primary ball milling; A third step of preparing a black alumina slurry for secondary ball milling by adding a binder, a plasticizer, and an antifoaming agent to the first black alumina slurry; A fourth step of preparing a second black alumina slurry by secondary ball milling of the black alumina slurry for secondary ball milling; A fifth step of adding a coagulant to the second black alumina slurry and then stirring to prepare a third black alumina slurry; and a sixth step of spray-drying the third black alumina slurry to prepare black alumina granules and compressing
  • the mixed powder for producing black alumina is characterized in that it includes 65 to 95% by weight of alumina and 5 to 35% by weight of additives, and the additives are titanium dioxide (TiO 2 ), iron (III) oxide (Fe 2 O 3 ), oxide of one oxide or two or more oxides selected from the group consisting of cobalt(III) (Co 2 O 3 ), silicon dioxide (SiO 2 ), manganese oxide (MnO), zirconium oxide (ZrO 2 ), and zinc oxide (ZnO). It is characterized by being a mixture.
  • the black alumina granules are spherical and can be controlled in various particle sizes according to spray drying process conditions.
  • the coagulant used in the spraying process is characterized in that the pH of the second black alumina slurry is adjusted to induce partial agglomeration of the alumina powder, and the black alumina granules have an average particle size of 40 to 50 ⁇ m.
  • the coagulant adjusts the pH of the second black alumina slurry to induce partial agglomeration of alumina powder, and the third black alumina slurry prepared by partially coagulating alumina by the coagulant has a viscosity of 350 to 650 cPs.
  • the black alumina sintered body produced by the manufacturing method of the black alumina sintered body using the black alumina granules of the present invention has a black color, has a reflectance for visible light (380 to 780 nm) of 5.5 to 9.7%, and a density of 3.8 to 4.3 g / cm 3 , characterized in that the hardness is 1100 to 1650Hv.
  • the black alumina of the present invention replaces the Japanese alumina raw material and black alumina, which have a high unit price due to Japan's export regulations, and uses domestic alumina raw materials to produce the same or better black alumina, so conventional Japanese alumina raw materials or black alumina There is an effect that can replace .
  • the black alumina manufacturing method of the present invention establishes the ratio between alumina and additives and the sintering temperature for densification so that it can have a black color and low reflectance while maintaining the excellent mechanical properties of conventional alumina.
  • liquid phase sintering is performed due to additives during the sintering process. Therefore, it is possible to densify the material at a temperature lower than 1600 ° C, which is the alumina sintering temperature by conventional solid-state sintering, so there is an economical advantage and a low reflectance of black color, so it can be used in the photo process.
  • Figure 1 shows the microstructure of the domestic alumina raw material and additives of the present invention.
  • FIG. 2 shows hollow alumina granules and spherical alumina granules of the present invention.
  • Figure 3 shows the fracture surface of the hollow alumina granule molded body and the spherical alumina granule molded body of the present invention.
  • Figure 4 shows the fracture surface of the hollow alumina granule sintered body and the spherical alumina granule sintered body of the present invention.
  • Figure 6 shows the microstructure of the sintered body prepared by sintering the black alumina granular shaped body of the present invention at a temperature of 1250 °C.
  • Figure 7 shows the change in sintering density for each sintering temperature for Example 6 series and Example 12 series of the present invention.
  • Figure 8 shows the fracture surface of the black alumina sintered body (sintering temperature 1200 °C) of the present invention.
  • Figure 9 shows the fracture surface of the black alumina sintered body (sintering temperature 1350 °C) of the present invention.
  • Figure 10 shows the change in reflectance according to sintering temperature for the Example 6 series and the Example 12 series of the present invention.
  • Figure 11 shows the color of the black alumina sintered body (sintering temperature 1200 °C) of the present invention.
  • the present invention is a manufacturing method using black alumina powder, comprising: a first step of preparing a mixed powder for preparing black alumina by mixing alumina and an additive; A second step of preparing a black alumina slurry by wet ball milling the mixed powder for preparing black alumina; A third step of drying the black alumina slurry and pulverizing it to obtain a homogenized black alumina powder by sieving with a 240 mesh; And a fourth step of compressing the homogenized black alumina powder to produce a black alumina powder molded body and heat-treating at 1250 to 1400 ° C. for 1 hour to prepare a black alumina sintered body.
  • Method for producing a black alumina sintered body comprising: provides
  • the black alumina sintered body produced by the manufacturing method of the black alumina sintered body using the black alumina granules of the present invention has a black color, has a reflectance for visible light (380 to 780 nm) of 5.5 to 9.7%, and a density of 3.8 to 4.3 g / cm 3 , characterized in that the hardness is 1100 to 1650Hv.
  • the present invention provides a black alumina sintered body prepared using black alumina powder or granules and a method for producing the same.
  • the method for producing a black alumina sintered body using the black alumina powder of the present invention includes a first step of preparing a mixed powder for producing black alumina by mixing alumina and an additive; A second step of preparing a black alumina slurry by wet ball milling the mixed powder for preparing black alumina; A third step of drying the black alumina slurry and pulverizing it to obtain a homogenized black alumina powder by sieving with a 240 mesh; and a fourth step of compressing the homogenized black alumina powder to produce a black alumina powder molded body and heat-treating the black alumina powder at 1250 to 1400° C. for 1 hour to prepare a black alumina sintered body.
  • a method for producing black alumina using the black alumina granules of the present invention includes a first step of preparing an alumina slurry for primary ball milling by mixing an alumina raw material, a solvent, a dispersant, and additives; A second step of preparing a first black alumina slurry by primary ball milling the alumina slurry for primary ball milling; A third step of preparing a black alumina slurry for secondary ball milling by adding a binder, a plasticizer, and an antifoaming agent to the first black alumina slurry;
  • a fourth step of preparing a second black alumina slurry by secondary ball milling of the black alumina slurry for secondary ball milling A fifth step of adding a coagulant to the second black alumina slurry and then stirring to prepare a third black alumina slurry; a sixth step of spray drying the third black alumina slurry to produce black alumina granules; and a seventh step of compressing the black alumina granules to prepare a black alumina powder molded body and heat-treating the black alumina powder at 1250 to 1450° C. for 1 hour to prepare a black alumina sintered body.
  • the black alumina powder and the black alumina granules are the same in that black alumina is produced and homogenized by ball milling after mixing an alumina raw material and additives.
  • the black alumina powder is prepared by drying and sieving the black alumina slurry
  • the black alumina granules are prepared by adding a binder, a plasticizer, and an antifoaming agent to the black alumina slurry, followed by ball milling, and then adding a coagulant. there is.
  • the black alumina powder had a problem in that the molding characteristics and sintering characteristics were deteriorated due to the different particle sizes of the alumina raw materials and additives constituting the black alumina powder, but it was processed homogeneously through ball milling and sieving, so that the molding It is judged that the properties and sintering characteristics are improved.
  • the black alumina granules have a spherical shape and are homogeneously prepared with an average particle size of 40 to 50 ⁇ m, it is considered that the molding characteristics and sintering characteristics are improved compared to conventional hollow alumina granules.
  • the sintered body of the present invention has improved molding characteristics and sintering characteristics by the black alumina powder, black alumina granules, and additives prepared above, even if it is sintered at 1200 to 1450 ° C., which is lower than the conventional alumina sintering temperature of 1600 ° C, it is the same or better. Since an alumina sintered body of excellent quality can be obtained, there is an advantage of reducing production cost by saving energy.
  • the alumina is characterized in that domestically produced isintered alumina is used, and the additives are titanium dioxide (TiO 2 ), iron (III) oxide (Fe 2 O 3 ), cobalt (III) oxide (Co 2 O 3 ), silicon dioxide It is characterized in that it is one oxide selected from the group consisting of (SiO 2 ), manganese oxide (MnO), zirconium oxide (ZrO 2 ), and zinc oxide (ZnO), or a mixture of two or more oxides.
  • the alumina and the additives are mixed at 65 to 95% by weight: 5 to 35% by weight (alumina: additive) to prepare a mixed powder for preparing black alumina, and after adding the same amount of solvent (DI-water) as the mixed powder Ball milling may be performed to produce a black alumina slurry.
  • the alumina and the additives may be mixed at 65 to 75% by weight: 25 to 35% by weight (alumina: additive), and more preferably, the alumina and the additive are 70% by weight: 30% by weight (alumina: Additives) to prepare a mixed powder for preparing black alumina, and after adding the same amount of solvent (DI-water) as the mixed powder, ball milling may be performed to prepare a black alumina slurry.
  • the ball milling may be performed at 55 to 65 cycles/hr and 20 to 28 hours, preferably at 60 cycles/hr and 24 hours.
  • the prepared black alumina slurry is dried, further pulverized, and sieved through a 240 mesh to prepare a homogenized black alumina powder.
  • the homogenized black alumina powder is compressed to prepare a black alumina powder molded body and heat-treated at 1250 to 1400 ° C. for 1 hour to prepare a black alumina sintered body. ), a reflectance of 6.4 to 9.7%, a density of 3.45 to 4.0 g/cm 3 , and a hardness of 800 to 1250 Hv.
  • an alumina slurry for primary ball milling is prepared by mixing an alumina raw material, a solvent, a dispersant, and an additive, and then ball milling is performed to prepare the first black alumina slurry.
  • the alumina raw material is domestically produced iso-sintered alumina, and the additives are titanium dioxide (TiO 2 ), iron (III) oxide (Fe 2 O 3 ), cobalt (III) oxide (Co 2 O 3 ), silicon dioxide (SiO 2 ), It is characterized in that it is one oxide selected from the group consisting of manganese oxide (MnO), zirconium oxide (ZrO 2 ), and zinc oxide (ZnO), or a mixture of two or more oxides.
  • the alumina raw material and additives may be mixed at 65 to 95% by weight: 5 to 35% by weight (alumina raw material: additive), preferably 65 to 75% by weight: 25 to 35% by weight (alumina raw material: additive).
  • alumina raw material additives
  • the solvent DI-water
  • the dispersant controls the viscosity of the slurry and is added in an amount of 0.5 to 1.5 parts by weight based on 100 parts by weight of the alumina raw material, preferably 0.5 to 1.5 parts by weight based on 100 parts by weight of the alumina raw material.
  • a black alumina slurry for secondary ball milling is prepared by adding a binder, a plasticizer, and an antifoaming agent to the first black alumina slurry.
  • the binder improves the formability of the alumina granules and serves to maintain the strength of the molded body.
  • the binder may use any one or a mixture of two or more selected from the group consisting of PVA (Polyvinyl alcohol), methyl cellulose, carboxymethyl cellulose, acrylic emulsion, and wax emulsion, PVA is preferably used.
  • PVA Polyvinyl alcohol
  • the plasticizer improves the flexibility of the binder film to improve the moldability of the alumina granules and promotes the plastic change of the granulated particles.
  • the plasticizer may be any one or a mixture of two or more selected from the group consisting of PEG (polyethylene glycol), glycerin, propylene glycol, and di-butyl phthalate, preferably PEG Use
  • the antifoaming agent serves to suppress the generation of air bubbles during ball milling.
  • the binder, plasticizer, and antifoaming agent may be included in 0.3 to 3.6 parts by weight, 0.5 to 3.1 parts by weight, and 0.001 to 0.8 parts by weight, respectively, based on 100 parts by weight of the alumina raw material, preferably 1.5 to 2.5 parts by weight, 0.5 to 1.5 parts by weight, respectively. It may be included in parts by weight and 0.0005 to 0.0015 parts by weight, and more preferably 2 parts by weight, 1 part by weight, and 0.001 parts by weight, respectively.
  • the black alumina slurry for secondary ball milling is subjected to secondary ball milling to prepare a second black alumina slurry, and a coagulant is added to the second black alumina slurry, followed by stirring to prepare a third black alumina slurry.
  • the coagulant serves to induce partial coagulation of the alumina included in the second black alumina slurry, and a pH adjusting agent is used.
  • the alumina included in the second black alumina slurry is coated with the binder through secondary ball milling. Therefore, when the pH of the second black alumina slurry is adjusted using the pH adjusting agent, aggregation is induced by the binder.
  • Nitric acid, sulfuric acid, hydrochloric acid, citric acid, stearic acid, hydrofluoric acid, acetic acid, etc. may be used as the pH adjusting agent, and nitric acid is preferably used.
  • the third black alumina slurry is partially agglomerated by the coagulant and may have a viscosity of 350 to 650 cPs, preferably 400 to 630 cPs, and preferably 449 to 605 cPs.
  • the third black alumina slurry in which the alumina is partially aggregated is spray-dried to prepare black alumina granules.
  • the black alumina granules have a spherical shape and an average particle size of 40 to 50 ⁇ m.
  • the spherical black alumina granules are compressed to prepare a black alumina powder molded body and heat-treated at 1250 to 1450 ° C. for 1 hour to prepare a black alumina sintered body.
  • the black alumina sintered body has a black color and has a reflectance of 5.5 to 9.7% for visible light (380 to 780 nm), a density of 3.8 to 4.3 g / cm 3 , and a hardness of 1100 to 1650 Hv.
  • alumina powder and black alumina powder used domestically produced iso-sintered alumina (ALG-ISH, Daehan Ceramics, purity 99.8%) as an alumina raw material.
  • Black alumina powder was prepared using the above alumina raw materials and additives.
  • the additives were TiO 2 (Samchun, 98.5%), Fe 2 O 3 (Duksan, 96%), Co 2 O 3 (Umicore, 95%), SiO 2 (Daejung, 99%), MnO (Sigma Aldrich, 99% ), ZrO 2 (Daejung, 99%), and ZnO (Daejung, 99%) were used.
  • Microstructures of the alumina raw materials and additives were confirmed using FE-SEM.
  • the average particle size of the alumina was 500 nm, and it was confirmed to have a microstructure as shown in FIG. 1.
  • the particle size of the additive was confirmed to have various sizes from sub-micron to 10 ⁇ m, and it was confirmed to have various shapes as shown in FIG. 1.
  • Table 1 shows the composition range of the composition for preparing black alumina powder.
  • Raw material composition range Alumina (Al 2 O 3 ) 95.24 to 66.4% by weight Titanium dioxide (TiO 2 ) 0.68 to 4.8% by weight Iron(III) oxide (Fe 2 O 3 ) 1.19 to 8.4% by weight Cobalt(III) oxide (Co 2 O 3 ) 1.56 to 11% by weight Silicon dioxide (SiO 2 ) 0.21 to 1.5% by weight Manganese oxide (MnO) 0.88 to 6.2% by weight Zirconium oxide (ZrO 2 ) 0.1 to 0.7% by weight Zinc Oxide (ZnO) 0.1 to 0.7% by weight
  • Table 2 shows the composition of the black alumina powder prepared by mixing the alumina raw material and additives of the present invention.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Alumina (Al 2 O 3 ) 95 weight% 90 weight% 85 weight% 75 weight% 70 weight% 65 weight% additive (TiO 2 and 6 other types) Titanium dioxide (TiO 2 ) 0.73 weight% 0.75 weight% 1.45 weight% 2.15 weight% 3.6 weight% 4.3 weight% Iron(III) oxide (Fe 2 O 3 ) 1.26 weight% 1.25 weight% 2.50 weight% 3.80 weight% 6.30 weight% 7.55 weight% Cobalt(III) oxide (Co 2 O 3 ) 1.67 weight% 1.65 weight% 3.30 weight% 4.95 weight% 8.25 weight% 9.90 weight% Silicon dioxide (SiO 2 ) 0.21 weight% 0.20 weight% 0.45 weight% 0.70 weight% 1.15 weight% 1.35 weight% Manganese oxide (MnO) 0.92 weight% 0.95 weight% 1.90 weight% 2.80 weight% 4.70 weight% 5.60 weight% Zirconium oxide (ZrO 2 ) 0.1 weight% 0.10 weight% 0.20 weight% 0.30 weight%
  • the alumina raw material and additives have different particle sizes and shapes, it is judged that the molding characteristics and sintering characteristics of normal alumina powder or black alumina powder containing the alumina raw material or additives are not good.
  • wet ball-milling was applied in order to have excellent molding and sintering characteristics by mixing the alumina raw material and additives in a uniform particle size.
  • an alumina mixture for primary ball milling is prepared by mixing an alumina raw material and a solvent (DI-water) at 50 wt% each, or a black alumina mixture is prepared by mixing an alumina raw material and additives, and the black alumina A black alumina mixture for primary ball milling was prepared by mixing the mixture for preparation and the solvent (DI-water) in an amount of 50 wt%, respectively.
  • the alumina mixture for primary ball milling and the black alumina mixture for primary ball milling were ball milled (60 cycles/hr) for 24 hours to prepare an alumina slurry.
  • the alumina slurry After completely drying the alumina slurry at 120° C., it was prepared in a powder state using a mortar and pestle, and sieved through a 240 mesh to obtain alumina powder.
  • the ball milling is a process for mixing alumina and additives for producing black alumina.
  • a heat treatment process In order to manufacture black alumina, a heat treatment process is required, and a black color is expressed due to a spinel-based compound produced by dissolving additives in alumina through the heat treatment process.
  • wet ball milling is used for mixing.
  • Plain alumina granules and black alumina granules were prepared.
  • a binder, a plasticizer, and an antifoaming agent were further added to the prepared general alumina powder or black alumina powder, followed by ball milling, and spray drying to prepare alumina granules.
  • the method for producing normal alumina granules or black alumina granules of the present invention includes the following steps:
  • 1st step preparing an alumina slurry for primary ball milling (in the case of an alumina slurry for primary ball milling, an additive is further included) by mixing an alumina raw material, a solvent, and a dispersant;
  • Step 2 preparing a first alumina slurry (first black alumina slurry) by performing primary ball milling on the alumina slurry for primary ball milling;
  • 4th step preparing a second alumina slurry (second black alumina slurry) by secondary ball milling of the alumina slurry for secondary ball milling (black alumina slurry for secondary ball milling);
  • Normal alumina granules and black alumina granules are determined by the addition of additives that make the color of alumina appear black. After producing normal alumina granules through the examples, this manufacturing method was applied to the production of black alumina granules.
  • An alumina slurry for primary ball milling was prepared by mixing an alumina raw material, a solvent (DI-water), and a dispersant (SN5468).
  • alumina raw material and a solvent were mixed in a ratio of 1:1, and a dispersant was added in an amount of 1 part by weight based on 100 parts by weight of the alumina raw material.
  • the viscosity of the alumina slurry for primary ball milling was 100 cPs or less.
  • Primary ball milling was performed on the prepared alumina slurry for primary ball milling.
  • the ball milling was performed in a 180 mm diameter PP ball milling container (4 L) using an alumina ball having a diameter of 5 mm.
  • the ball milling was performed for 1 to 72 hours under conditions of up to 60 cycles/min, and the optimal capacity of the alumina balls was set to 40 vol% of the vessel capacity, but was not included as a separate weight.
  • the spherical alumina granules of the present invention are prepared by spray drying after ball milling, and in detail, the spherical alumina granules are prepared by performing partial aggregation after ball milling and spray drying in the last step.
  • alumina slurry In order for the alumina slurry to be dried through spray drying, its viscosity must be at a sprayable level. Therefore, slurries prepared in each process must maintain an appropriate viscosity in consideration of subsequent processes, and in particular, the viscosity of the slurry in the last step must be controlled to be suitable for spray drying.
  • the appropriate viscosity of the alumina slurry (first alumina slurry) produced by the primary ball milling of the present invention was set to 100 cPs or less, preferably 20 cPs or less.
  • the dispersing agent cancels the van der Waals attraction between the particles, it has an effect of allowing the particles to exist uniformly and stably without agglomeration in the solvent.
  • the detailed optimal content of the dispersant was derived through examples.
  • the dispersant was added in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the alumina raw material to prepare an alumina slurry (alumina slurry for primary ball milling), and the alumina slurry was ball milled according to the above conditions, and then the viscosity of the slurry were analyzed for comparison (see Table 3).
  • the viscosity exceeds the appropriate viscosity (20 cPs) as 34 cPs, and when it exceeds 0.5 parts by weight, it decreases to less than the appropriate viscosity, and when it exceeds 0.6 parts by weight, it is confirmed that the viscosity is maintained below 14 cPs.
  • 0.8 parts by weight (12 cPs) was selected under the condition that it corresponds to an appropriate viscosity and does not affect other process variables.
  • a binder, a plasticizer, and an antifoaming agent were added to the first alumina slurry prepared by the first ball milling to prepare an alumina slurry for secondary ball milling, and secondary ball milling was performed on the alumina slurry for secondary ball milling.
  • the binder (PVA500, MW 500Da) was added in an amount of 0.3 to 3.6 parts by weight based on 100 parts by weight of alumina, and the plasticizer (PEG400, MW 400Da) was added in an amount of 0.2 to 3.1 parts by weight based on 100 parts by weight of alumina.
  • PEG400, MW 400Da was added in an amount of 0.2 to 3.1 parts by weight based on 100 parts by weight of alumina.
  • BYK028 was added in an amount of 0.001 to 0.8 parts by weight based on 100 parts by weight of alumina.
  • Ball milling was performed in a 180 mm diameter PP ball milling container (4 liters), and an alumina ball with a diameter of 5 mm was used and was performed for 2 hours under the condition of 60 cycles/min.
  • Table 4 shows the change in viscosity of the second alumina slurry according to the change in the content of the binder
  • Table 5 shows the change in viscosity of the second alumina slurry according to the change in the content of the plasticizer
  • Table 6 shows the change in the viscosity of the second alumina slurry according to the change in the content of the antifoaming agent. The viscosity change of the second alumina slurry is shown.
  • Binder content (parts by weight) 0.1 0.5 1.0 1.5 2.0 2.5 3.0 3.5 Viscosity (cPs) 12 14 15 18 21 25 25 26
  • the main viscosity control for preparing the alumina granules of the present invention is mainly determined by the degree of dispersion of the alumina powder through the dispersant and the degree of partial aggregation of the alumina powder due to the addition of the coagulant.
  • the viscosity of the second alumina slurry was maintained at 26 cPs when the additive was used in 1 part by weight of the binder binder, 0.5 part by weight of the plasticizer, and 0.001 part by weight of the defoamer.
  • An alumina slurry (third alumina slurry) for spray drying in which partial coagulation was induced was prepared by adding a pH coagulant to the second alumina slurry prepared through the secondary ball milling.
  • the alumina slurry having a fine particle size should be dried in a partially agglomerated state.
  • a method of inducing partial aggregation of the alumina slurry a method of coating the alumina particles by adding a polymer compound or changing the surface charge by adjusting the pH may be used.
  • a method of inducing partial aggregation by adjusting the pH was used.
  • pH adjusting agent for partial aggregation of the present invention nitric acid, sulfuric acid, hydrochloric acid, citric acid, stearic acid, hydrofluoric acid, acetic acid, and the like may be used. Since the pH adjusting agent can induce both dispersion and aggregation of alumina depending on the method of use, the method of use should also be optimized through examples.
  • 10% nitric acid was used as a pH coagulant (pH adjuster) that induces partial aggregation through pH control.
  • Partial aggregation of the alumina slurry was induced by adding 10% nitric acid to the second alumina slurry (viscosity 26 cPs) prepared above so as to be 1 to 7 parts by weight based on 100 parts by weight of the alumina raw material.
  • Alumina slurry for spray drying (third alumina slurry) was manufactured. The prepared third alumina slurry was spray dried to obtain alumina granules.
  • the spray drying is performed in a spray dryer (Disc type: 5,000 to 25,000 rpm, Nozzle type: 2 to 12 kPa) at an inlet temperature of 150 to 230 ° C, an outlet temperature of 70 to 110 ° C, a supply speed of 0.1 to 1 kg / min, and a hot air volume of 0.2 to 10 m3/min and the internal pressure of the spray dryer was 0 to -15 mmAq.
  • a spray dryer Disc type: 5,000 to 25,000 rpm, Nozzle type: 2 to 12 kPa
  • Table 7 shows the results of analyzing the viscosity and shape of spray-dried alumina granules of the alumina slurry for spray drying (third alumina slurry) in which partial aggregation was induced according to the present invention.
  • alumina granules were prepared by the same method as the above production method, but alumina slurry was prepared using only a dispersant without using a coagulant (pH coagulant), and then alumina granules were prepared by spray drying.
  • alumina granules were prepared in a disc type spray dryer under conditions of a disc speed of 15,000 rpm and a pump speed of 50 rpm.
  • alumina slurry was prepared using both the dispersing agent and the coagulant, and alumina granules were prepared by spray drying, and scanning electron microscopy analysis was conducted on them (see FIG. 2).
  • the alumina granules prepared using both the dispersing agent and the coagulant had a perfect spherical shape. Since the alumina granules having a spherical shape are completely broken by appropriate pressure during molding, the filling rate is uniformly increased. It is believed that the increase in the filling factor leads to an increase in molding density and sintering density, so that an alumina compact and sintered product having improved strength and hardness can be manufactured.
  • Molded bodies using the above-prepared spherical general alumina granules and hollow general alumina granules were prepared, and their microstructures were confirmed (see FIG. 3).
  • the molded body was prepared by uniaxially pressing at a pressure of 3 ton/cm 2 using a mold.
  • the spherical general alumina granule molded body forms a homogeneous microstructure due to the destruction of uniform granules and has excellent molding density, while the hollow general alumina granule molded body has uneven granule destruction, resulting in hollowness of the granules and voids between the granules. It was confirmed that this remained and had a reduced molding density due to this. In addition, it was confirmed that the difference in molding density directly affects the density of the final sintered product.
  • the spherical general alumina granule compact and the hollow general alumina granule compact were sintered at 1600 ° C to prepare a spherical general alumina granule compact and a hollow general alumina granule compact, and the microstructure of the fracture surface of each sintered body was confirmed (Fig. see 4).
  • Density of the spherical general alumina granule compact and hollow general alumina granule compact produced by uniaxial pressing (g/cm 3 )
  • density of the spherical general alumina granule compact and hollow general alumina granule compact prepared by sintering the compact ( g/cm 3 )
  • their relative densities (%) were calculated and compared.
  • the relative density (%) was calculated based on the theoretical density of alumina of 3.987 g/cm 3 and was calculated through Equation 1 below.
  • the density (g / cm 3 ) of the molded body of the spherical alumina granules and the hollow alumina granules prepared by further adding the cold isostatic pressing after the uniaxial pressing, and the molded body prepared by sintering The density (g/cm 3 ) of the sintered body of the spherical alumina granules and the sintered body of the hollow alumina granules and their relative density (%) were calculated and compared.
  • Table 8 shows the densities and relative densities of the molded body of spherical alumina granules, the sintered body of spherical alumina granules, the molded body of hollow alumina granules, and the sintered body of hollow alumina granules.
  • the reason why the molding density and sintering density of hollow general alumina granules are lower than that of spherical general alumina granules is that the microstructure of hollow general alumina granules has a donut or apple shape, so the fluidity is lower than that of spherical general alumina granules. This is considered to be due to the difficulty in uniformity and filling of the particles in the mold. In addition, empty spaces created when the filling of particles is insufficient remain as pores during sintering, and the pores are the main cause of the decrease in the sintered density of the sintered body.
  • Black alumina granules were prepared based on the general alumina granule production results.
  • Table 9 shows the composition of black alumina granules of the present invention.
  • the black alumina powder in Table 9 below has the same composition as Examples 1 to 6 in Table 2, and a dispersing agent, coagulant, binder, plasticizer, and antifoaming agent are added based on 100 parts by weight of alumina in the black alumina powder.
  • Example 7 Example 8 Example 9 Example 10
  • Example 11 comparative example black alumina powder Furtherance
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Example 1 dispersant type SN5468 SN5468 SN5468 SN5468 SN5468 SN5468 SN5468 content 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight 1 part by weight coagulant type nitric acid nitric acid nitric acid nitric acid nitric acid nitric acid nitric acid content 0.3 parts by weight 0.3 parts by weight 0.3 parts by weight 0.3 parts by weight 0.3 parts by weight 0 parts by weight bookbinder type PVA PVA PVA PVA PVA PVA PVA PVA content 2 parts by weight 2 parts by weight 2 parts by weight 2 parts by weight 2 parts by weight 2 parts by weight 2 parts by weight plasticizer type PEG400 PEG400 PEG400 PEG400 PEG400 PEG400 PEG400 PEG400 PEG400 PEG400 P
  • an alumina slurry for primary ball milling was prepared by mixing an alumina raw material, an additive, a solvent, and a dispersant.
  • the black alumina powder used in the alumina slurry for primary ball milling is the same as in Examples 1 to 6, including the alumina raw material and additives.
  • the alumina slurry for primary ball milling had a pH of 9.8 to 10.89 and a viscosity of 20 cPs or less.
  • a first black alumina slurry was prepared by performing primary ball milling on the alumina slurry for primary ball milling. The primary ball milling was performed for 24 hours under conditions of 60 cycles/min.
  • a black alumina slurry for secondary ball milling was prepared by adding a binder (PVA, MW 22,000 g/mol), a plasticizer (PEG4000, MW 380-420 g/mol), and an antifoaming agent to the first black alumina slurry, and the secondary ball milling
  • a second black alumina slurry was prepared by secondary ball milling of the black alumina slurry for use.
  • a coagulant was added to the second black alumina slurry and stirred to prepare a third black alumina slurry.
  • the third black alumina slurry was prepared into black alumina granules in a disc type spray dryer under conditions of a disc speed of 15,000 rpm and a pump speed of 50 rpm.
  • the prepared black alumina granules have an average particle size of 45 ⁇ m (see FIG. 5).
  • black alumina granules were prepared by spray-drying a comparative example in which black alumina slurry was prepared by preparing black alumina granules in the same manner as in the above manufacturing method, but without using a coagulant.
  • a black alumina slurry was prepared using both the dispersing agent and the coagulant, and black alumina granules were prepared by spray drying (Examples 7 to 12), and then scanning electron microscopy analysis was performed. As a result of the analysis, it was confirmed that the black alumina granules of Examples 7 to 12 had a perfect spherical shape (see FIG. 5). Since the black alumina granules having a spherical shape are completely broken by appropriate pressure during molding, the filling rate is uniformly increased. It is believed that the increase in the filling factor leads to an increase in molding density and sintering density, thereby making it possible to manufacture black alumina molded and sintered products having improved strength and hardness.
  • a black alumina molded body was prepared by uniaxially pressing the black alumina powder and the black alumina granules prepared in the above Examples and Comparative Examples using a circular mold with a diameter of 24 mm and a square mold with a diameter of 50 mm at a pressure of 1 ton/cm 2 .
  • the prepared black alumina molded body was heated to 1250 to 1450° C. at a heating rate of 3° C./min, maintained in an air atmosphere for 1 hour, and then cooled in a furnace to obtain a black alumina sintered body.
  • the microstructure of the surface and fracture surface of the prepared black alumina sintered body was analyzed using a field emission scanning electron microscope (FE-SEM, JSM-7100F, JEOL, Japan).
  • the density of the prepared black alumina sintered body was analyzed using the Archimedes method.
  • the hardness of the prepared black alumina sintered body was mirror-polished using $160 to #2000 SiC sandpaper, and then measured 5 times with a press-in load of 1 kgf using a micro Vickers hardness machine (ZH ⁇ -A, INDENTEC, UK), and the average value was obtained. It was analyzed by the calculation method.
  • the reflectance of the prepared black alumina sintered specimen was measured by using a high-resolution UV-VIS-NIR spectrophotometer (Varian, CARY 500 SCAN) to obtain an average value in the visible ray region, 380 to 780 nm wavelength. It was analyzed by the calculation method.
  • Example 6 shows the microstructure of the test piece of Example 12-2 prepared by sintering the black alumina granular shaped body of the present invention at a temperature of 1250 ° C.
  • liquid phase sintering does not appear to occur smoothly compared to sintering at a sintering temperature of 1350° C. or higher. Since the sintering temperature of 1250° C. is relatively low, the viscosity of the liquid phase is high and the filling of the solid particles is insufficient, so it is determined that the subsequent dissolution-re-precipitation and coalescence between the solid particles are not smooth.
  • Table 10 shows the results of analyzing the sintering temperature and density, hardness, and reflectance of the black alumina sintered body of the present invention.
  • the black alumina of the present invention can be densified through sintering at 1350 ° C.
  • Figure 7 shows the change in sintering density for each sintering temperature for Example 6 series and Example 12 series of the present invention.
  • Example 6 series prepared black alumina powder into a molded body and sintered it at 1200 to 1450 ° C.
  • Example 12 series further added a dispersant coagulant, binder, plasticizer and antifoaming agent to black alumina powder having the same composition as Example 6 series After preparing black alumina granules and using them to prepare a molded body, the molded body is sintered at 1200 to 1450 ° C.
  • Example 1 series and Example 7 series having a high alumina content it is confirmed that the decrease in density is insignificant even after 1350 ° C.
  • FIG 8 shows a fracture surface of the black alumina sintered body of the present invention.
  • the left panel shows the fracture surface of the sintered specimen of Example 6-1, and the right panel shows the fracture surface of the sintered specimen of Example 12-1.
  • the density of the sintered body was high compared to the example in which the black alumina powder was directly used, and when the sintered body was sintered at a relatively low temperature and the content of the additive was increased, the black alumina powder was granulated. It was confirmed that the density difference between the example using the black alumina powder and the example using the black alumina powder directly increased.
  • the compositions constituting the black alumina powder have various particle shapes and particle sizes. Therefore, when the type and amount of additives in the black alumina powder increase, the homogeneity of the particle shape and particle size decreases, resulting in a wide particle size distribution, which causes local aggregation. In the case of examples in which the black alumina powder of the present invention was directly used, local aggregation occurred due to the use of additives. In contrast, in the case of the embodiment in which the black alumina powder was granulated and used, the powder was homogenized in the form of granules, and then a molded body was prepared and sintered, so that the powder had a narrow particle size distribution even if the additive content increased. Therefore, it is determined that the difference in density between the examples in which the black alumina powder was directly used and the examples in which the black alumina powder was granulated and used increased as the content of the additive increased.
  • Another cause of the difference in density between the example in which the black alumina powder was directly used and the example in which the black alumina powder was granulated was determined to be due to the difference in molding density due to the filling rate of the solid particles during manufacture of the molded body.
  • the above results are supported by the densities (cuneiform density) of the molded bodies of the Example 6 series and the Example 12 series of 2.24 g/cm 3 and 2.28 g/cm 3 , respectively, and when the black alumina powder is granulated and then molded It has relatively excellent molding density, which means that excellent sintered density is obtained due to uniform filling of solid particles.
  • Table 10 shows the results of analyzing the sintering temperature and characteristics of the black alumina sintered body of the present invention.
  • the hardness of the sintered body shows high hardness in the sintered body having a high sintered density. It is believed that the above result is due to the high hardness measured in a sintered body having a sufficiently high density and sufficiently densified according to the hardness characteristics of the ceramic, which is greatly affected by the microstructure of the sintered body, such as the size of pores or crystal grains in the sintered body. In particular, in the case of examples using black alumina powder directly, it seems to show lower hardness than examples in which black alumina powder was granulated and used due to the effect of the pores found in the microstructure.
  • the hardness value decreases at 1400 ° C. or higher, which is a relatively high sintering temperature.
  • the result is judged to be due to the decrease in the density of the sintered body, and the fact that the surface area of the crystal grain interface decreases as the size of the crystal grain increases at high temperature is also believed to have had a great effect on the decrease in hardness. Since grain interfaces in ceramics hinder the movement of dislocations, small crystal grains with a large surface area show high hardness. For this reason, the increase in grain size due to the increase in sintering temperature leads to a decrease in the surface area of the grain interface, which causes a decrease in hardness.
  • the hardness of alumina is known to have a wide range of 1200 to 2000 Hv (12 to 20 GPa) depending on the additives, and it was confirmed that the hardness of the black alumina sintered body of the present invention also has a similar value to the above.
  • the hardness decreases, but the reduced level corresponds to a hardness similar to that of general alumina sintered bodies, so the black alumina sintered body having a level of hardness quality that can be commercialized and used It is considered possible to manufacture.
  • Figure 9 shows the surface of the black alumina sintered body sintered at 1350 °C of the present invention.
  • Example 6-4 The left panel shows the surface of Example 6-4 in which a molded body was prepared using black alumina powder directly and then sintered at 1350 ° C.
  • the right panel showed a molded body prepared after granulating black alumina powder and sintered at 1350 ° C.
  • the surface of one Example 12-4 is shown.
  • Example 6-4 compared to Example 12-4, relatively large pores due to coalescence of pores can be confirmed. Due to these pores, the hardness of Example 6-4 is comparable to the hardness of Example 12-4. It is considered to have a relatively low value.
  • Ceramic materials made of defect-free single crystals are transparent in the visible ray region, but ceramic sintered bodies are mostly opaque white because scattering and refraction occur due to surface defects, grain boundaries, and pores.
  • a pure alumina sintered body with a corundum structure is also white due to grain boundary scattering, but it is possible to manufacture alumina having a unique color through a reaction according to the addition of various transition metals.
  • Cobalt which is generally used in ceramics, is a representative example, and blue color development is possible with the Co-Al Spinel structure. Black alumina has a black color by absorbing all visible light due to a change in the d-orbital spin quantum arrangement of these mixtures due to the mixture of various transition elements.
  • a black alumina powder containing various transition metals as an additive is directly used to prepare a molded body and then sintered or black alumina powder containing various transition metals as an additive is granulated to prepare a molded body and sinter it.
  • reflectance was measured with a UV-Vis spectrophotometer (see Table 4). The reflectance of the test piece was calculated as an average value in the visible ray region at a wavelength of 380 to 780 nm.
  • the black alumina sintered body of the present invention was mostly close to black when viewed with the naked eye, but showed a difference in reflectance measured using a UV-Vis spectrophotometer.
  • Example 1 in which a molded body was prepared using black alumina powder directly and sintered, it can be seen that the high reflectance of 31.36% shows a dark blue color rather than black color. When the content of the additive is increased, it is confirmed that the reflectance decreases due to the black color. (See Figure 10).
  • Example 11 shows the color of the black alumina sintered body of the present invention.
  • the left side is a specimen of Example 7-1 prepared by sintering at 1200 ° C
  • the middle is a specimen of Example 9-1 prepared by sintering at 1200 ° C
  • the right side is a specimen of Example 12-1 prepared by sintering at 1200 ° C.
  • Example 12-1 which contains the most additives, showed black color (reflectance: 9.73%)
  • Examples 9-1 and 7-1 showed ultramarine blue (reflectance: 13.24%) and gray color (reflectance: 13.24%). reflectance: 28.95%).
  • the black alumina sintered body of FIG. 11 is prepared by granulating black alumina powder to prepare a molded body and sintering it at 1300, 1350, and 1400 ° C. for 1 hour.
  • black alumina sintered bodies having a sintering temperature of 1300 ° C or more were produced in all examples except for some of the Example 7 series, and that the reflectance was also low, less than 10%.
  • the example prepared by granulating the black alumina powder and sintering the molded body was found to have a low reflectance compared to the example in which the molded body was prepared by directly using the black alumina powder and then sintered. confirmed The above results show that black alumina powder and additives are more This is believed to be due to uniform mixing. As described above, when black alumina powder is directly used to manufacture a molded body, local aggregation occurs during the manufacturing process. This aggregation prevents sufficient reaction between alumina and additives, and rather, a reaction between additives or a second phase is formed. It is judged that the expression of the black color of the sintered body and the decrease in reflectance are suppressed.
  • the method for producing a black alumina sintered body it is preferable to granulate black alumina powder to prepare a compact and then sinter it, rather than to prepare a compact using black alumina powder directly and then sinter it. It has been found to be helpful in improving the characteristics of
  • sintering was required at a minimum of 1600 ° C. to produce an alumina sintered body having high density and hardness.
  • the manufacturing method of the present invention is used as an additive, liquid-phase sintering is possible, and a black alumina sintered body having high density and hardness can be manufactured at 1350 ° C., which is lower than the sintering temperature of pure alumina.
  • the hardness of the black alumina of the present invention changes according to the content of additives, but its mechanical properties are not significantly different from those of conventional pure alumina, and it was confirmed that it is at a level that can be commercialized through commercialization.
  • a molded body is prepared using the black alumina powder to which the additive is added at 35 wt%, or the black alumina powder to which the additive is added at 35 wt% is granulated, and then the molded body is prepared and the molded body is In contrast, when sintering at 1350 ° C., black alumina having excellent mechanical properties like a conventional pure alumina sintered body and having a black color and showing very low reflectance could be prepared.
  • the physical properties of the optimal black alumina sintered body that can replace the conventional black alumina produced in Japan due to its high density, high hardness, black color and low reflectance are a density of 3.45 cm 3 or more, a hardness of 800 Hv or more, and a reflectance of 9.7% or less. is a condition of It is preferably a density of 3.8 cm 3 or more, a hardness of 1104.21 Hv or more, and a reflectance of 9.7% or less, more preferably a density of 3.9 cm 3 or more, a hardness of 1104.21 Hv or more, and a reflectance of 8.5% or less.
  • the black alumina sintered body of the present invention has the most optimal density, hardness and reflectance at 1300 to 1400 ° C. in most compositions.
  • the above results mean that high density and excellent mechanical strength (hardness) are possible due to the densification of the alumina sintered body even at a relatively low sintering temperature (1300 ⁇ 1400 ° C) due to liquid phase sintering by additives, so energy consumption during black alumina production can be reduced. It is expected that savings can be expected and economic benefits can be expected.
  • the optimum sintering conditions for each content of alumina and additives in the black alumina powder established through the present invention are black alumina sintered body suitable for each use as well as chuck plate for PHOTO process, PE-CVD, etcher, supter, plasma cleaning equipment and It is expected that it will be possible to expand the product range with the same parts and materials.
  • the black alumina of the present invention has a low reflectance and can be used as a chuck plate for fixing a substrate in semiconductor and display manufacturing processes.

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Abstract

L'alumine noire de la présente invention est fabriquée à un niveau équivalent ou supérieur par utilisation de matières premières de type alumine domestique par remplacement des matières premières de type alumine japonaise et alumine noire, qui ont des prix unitaires élevés en raison de la réglementation de l'exportation du Japon, et a ainsi pour effet de remplacer les matières premières classiques d'alumine japonaise ou l'alumine noire. Un procédé de fabrication d'alumine noire selon l'invention vise à établir le rapport de l'alumine et d'un additif, ainsi que la température de frittage pour une densification, de sorte que l'alumine noire puisse avoir un faible facteur de réflexion en raison de sa couleur noire, tout en conservant les excellentes propriétés mécaniques de l'alumine classique. Dans la présente invention, un frittage en phase liquide est mis en œuvre grâce à un additif au cours d'une opération de frittage. Il est ainsi possible de densifier le matériau à une température inférieure à 1 600 °C, qui est la température de frittage de l'alumine dans le cas d'un frittage classique à l'état solide, ce qui présente ainsi l'avantage de pouvoir être utilisé dans un processus photographique, en présentant un faible facteur de réflexion en raison de sa couleur noire, ainsi qu'un avantage économique.
PCT/KR2021/017572 2021-11-24 2021-11-26 Corps fritté en alumine noire et son procédé de fabrication WO2023095954A1 (fr)

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KR0143070B1 (ko) * 1990-12-20 1998-07-15 한형수 전자부품용 착색 세라믹 조성물
JP2000044330A (ja) * 1998-07-29 2000-02-15 Sumitomo Chem Co Ltd アルミナ焼結体およびその製造方法
JP2008260645A (ja) * 2007-04-10 2008-10-30 Nitsukatoo:Kk 黒色アルミナ焼結体とその製造方法
KR20110116244A (ko) * 2009-02-23 2011-10-25 가부시키가이샤 소딕 착색 세라믹 진공 척 및 그 제조 방법
KR20150114616A (ko) * 2014-04-01 2015-10-13 목포대학교산학협력단 블랙 알루미나의 제조방법

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JP2000044330A (ja) * 1998-07-29 2000-02-15 Sumitomo Chem Co Ltd アルミナ焼結体およびその製造方法
JP2008260645A (ja) * 2007-04-10 2008-10-30 Nitsukatoo:Kk 黒色アルミナ焼結体とその製造方法
KR20110116244A (ko) * 2009-02-23 2011-10-25 가부시키가이샤 소딕 착색 세라믹 진공 척 및 그 제조 방법
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