CN113135746B - High-insulation low-heat-conduction high-compressive-strength ceramic material and preparation method thereof - Google Patents
High-insulation low-heat-conduction high-compressive-strength ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-insulation low-heat-conduction high-compressive-strength ceramic material and a preparation method thereof. The chemical composition of the ceramic material is as follows: xKAl2(AlSi3O10)(OH)2‑yAl2O3‑zZrO2X + y + z =100wt%, x is more than or equal to 10wt% and less than or equal to 40wt%, y is more than or equal to 10wt% and less than or equal to 80wt%, and z is more than or equal to 10wt% and less than or equal to 80 wt%.
Description
Technical Field
The invention relates to a high-insulation low-heat-conduction high-compressive strength ceramic material and a preparation method thereof, belonging to the field of electronic ceramic materials and manufacturing and using thereof.
Background
The heat flow detection technology can measure the heat flow in the industrial kiln to control and warn the safe use range of the equipment, and plays a role in safe production; in the field of aerospace, the device can measure space heat flow and detect heat change of space environment to ensure the safety of equipment and instruments. The heat flow detection technology needs a material with high insulation and low heat conductivity to support the normal work of the heat flow sensor, conditions such as welding process, surface treatment, high pressure and high temperature impact resistance and the like in the heat flow sensor put nearly strict requirements on the material, and a material with high insulation strength, low heat conductivity coefficient and high compressive strength is urgently needed to be found to meet the use requirement of the heat flow sensor.
In addition, the existing material can only meet the requirements on one or two indexes, and the three indexes cannot simultaneously meet the use conditions of the heat flow sensor.
In summary, materials with high insulation strength, low thermal conductivity and high compressive strength and preparation methods thereof are important for our research.
Disclosure of Invention
The invention aims to prepare a high-insulation low-heat-conduction high-compressive strength ceramic material which can meet the normal use of a heat flow sensor under the conditions of high temperature and high pressure.
The invention provides a high-insulation low-heat-conduction high-compressive-strength ceramic materialThe ceramic material has the chemical composition as follows: xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO2X + y + z is 100wt%, x is more than or equal to 10wt% and less than or equal to 40wt%, y is more than or equal to 10wt% and less than or equal to 80wt%, and z is more than or equal to 10wt% and less than or equal to 80 wt%.
The invention realizes the control of the insulativity, the thermal conductivity and the compressive strength of the material by adjusting the compositions of x, y and z in the material and the solid solution temperature. The main mechanism is KAl2(AlSi3O10)(OH)2The insulating material has a layered structure and a monoclinic system, and has very high insulating and heat-insulating properties; the alumina is a high-hardness compound, the melting point is 2054 ℃, and the boiling point is 2980 ℃; zirconium dioxide is chemically inert, has a melting point of about 2700 ℃, and has the characteristics of high melting point, high resistivity and low thermal expansion coefficient. The three materials are combined and solid-dissolved in different proportions to form a composite material.
Preferably, said xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO2Comprises the following raw materials: 10 to 20wt% of KAl2(AlSi3O10)(OH)240 to 60wt% of Al2O310 to 30wt% of ZrO2。
Preferably, said KAl2(AlSi3O10)(OH)2The raw materials comprise: 10-40 wt% of K source, 35-45 wt% of Al source and 40-50 wt% of Si source.
Preferably, the K source is K2O、KOH、K2CO3The Al source is Al2O3、Al(OH)3At least one of the Si source is silicon micropowder, silica sand and SiO2At least one of (1).
Preferably, the volume resistivity of the ceramic material at 25-600 ℃ is more than 1010Omega cm, a thermal conductivity of 3.55W/m k at 25-200 ℃, and a compressive strength of 1000-1300 MPa.
In a second aspect, the invention provides a preparation method of a high-insulation low-heat-conduction high-compressive-strength ceramic material, which comprises the following steps:
according to KAl2(AlSi3O10)(OH)2The raw materials are weighed, ball-milled, dried and sieved, and then presintered at 1000-1300 ℃ for 2-6 hours to obtain KAl2(AlSi3O10)(OH)2Powder; and
according to xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO2The raw materials consist of KAl2(AlSi3O10)(OH)2Powder of Al2O3And ZrO2And after ball milling, drying and sieving, adding a binder for granulation, after compression molding, sintering at 1300-1500 ℃ for 2-6 hours to obtain the high-insulation low-heat-conduction high-compressive-strength ceramic material.
Preferably, in and KAl2(AlSi3O10)(OH)2Before ball milling, the Al is2O3And ZrO2Presintering for 3-5 hours at 1100-1300 ℃.
Preferably, the addition amount of the binder is xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO21.0-5.0 wt% of the total mass of the raw materials.
Preferably, the binder is a polymer material solution with a concentration of 6-8 wt%, the polymer material includes at least one of polyvinyl butyral and polyvinyl alcohol, and the solvent is polyvinyl alcohol.
Preferably, the atmosphere of the pre-burning is air.
Preferably, the sintering atmosphere is air.
The present invention can be adjusted by adjusting KAl2(AlSi3O10)(OH)2And Al2O3And ZrO2The composite material with high insulation strength, low heat conductivity coefficient and high compressive strength is obtained by the following steps: and the preparation process is simple, the forming process is convenient, the sintered ceramic composite material is compact, has no defects of air holes, cracking and the like, can be produced in batches, can be used in a heat flow detection technology, and is a ceramic composite material with a very wide application prospect.
Drawings
FIG. 1 is an SEM image of a high-insulation, low-thermal-conductivity and high-compressive-strength ceramic material in example 3;
FIG. 2 is an XRD pattern of the high dielectric, low thermal conductivity, high compressive strength ceramic material of example 3;
FIG. 3 shows an example KAl2(AlSi3O10)(OH)2XRD pattern of (a);
FIG. 4 shows KAl2(AlSi3O10)(OH)2A foaming microscopic morphology picture with the proportion of the ceramic powder exceeding 40 percent;
FIG. 5 is ZrO2XRD pattern of (a);
FIG. 6 is Al2O3XRD pattern of (a).
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The ceramic material of the invention has a chemical composition xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO2X + y + z is 100wt%, x is more than or equal to 10wt% and less than or equal to 40wt%, y is more than or equal to 10wt% and less than or equal to 80wt%, and z is more than or equal to 10wt% and less than or equal to 80 wt%. In some embodiments, the xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO2The raw materials of (A) can be: 10 to 20wt% of KAl2(AlSi3O10)(OH)240 to 60wt% of Al2O310 to 30wt% of ZrO2。
In some embodiments, the KAl2(AlSi3O10)(OH)2The raw materials comprise: 10-40 wt% of K source, 35-45 wt% of Al source and 40-50 wt% of Si source. KAl as described above2(AlSi3O10)(OH)2In the raw material composition, the K source is K2O、KOH、K2CO3The Al source is Al2O3、Al(OH)3At least one of the Si source is silicon micropowder, silica sand and SiO2At least one of (1).
Preferably, the K source, the Al source and the Si source have the grain diameter less than or equal to 2.5 mu m and the purity more than 99.9 percent, and are subjected to iron removal treatment.
The volume resistivity of the ceramic material is more than 10 at 25-600 DEG C10Omega cm, and the compressive strength is 1000-1300 MPa. In some embodiments, the ceramic material has a thermal conductivity of up to 3.55W/m k at 25-200 ℃.
Due to KAl2(AlSi3O10)(OH)2And Al2O3And ZrO2Insulation resistance at normal temperature is more than 1013Omega cm, thus ensuring that the whole composite material has higher insulation resistance. Al (Al)2O3Compressive strength is more than 850MPa, and heat conductivity coefficient is 20W/m × k; ZrO (ZrO)2The thermal conductivity is 2.0W/m × k at 1000 ℃, and the compressive strength is more than 1200MPa at 1000 ℃. According to the material mixing rule, the forming pressure and the sintering temperature are simultaneously controlled, and the performance of the prepared composite material can reach the following performance: a volume resistivity at 600 ℃ higher than 1X 1010Omega cm, a thermal conductivity of 3.55W/m k at 200 ℃ and a compressive strength of more than 1000MPa at 20 ℃.
The ceramic material is convenient for batch production, the production process is green and pollution-free, the performance is stable and reliable, and the stability of the material plays a crucial role in the application of the heat flow sensor.
The invention also provides a preparation method of the high-insulation low-heat-conduction high-compressive-strength ceramic material, which comprises the following steps: KAl2(AlSi3O10)(OH)2Synthesis and KAl2(AlSi3O10)(OH)2And Al2O3And ZrO2After the combination and solid solution, adding a binder in a proper proportion, molding and sintering to obtain the ceramic material meeting the requirements.
The invention is realized by mixing KAl2(AlSi3O10)(OH)2And Al2O3And ZrO2Mixing and dissolving according to a certain mass ratio, then ball-milling, drying, granulating, press-forming and sintering to obtain the ceramic material with high insulation, low heat conduction and high compressive strengthAnd (5) feeding.
The preparation method of the ceramic material with high insulating strength, low thermal conductivity and high compressive strength provided by the invention is exemplarily described below.
Firstly, KAl is obtained by a solid phase reaction method2(AlSi3O10)(OH)2And (3) powder.
According to KAl2(AlSi3O10)(OH)2Weighing a K source, an Al source and a Si source for mixing the components of the ceramic powder, adding water, and performing rapid ball milling for 1-3 hours to obtain a material: grinding balls: the mass ratio of water is 1: (2-4): (1-3) obtaining the slurry. The ball milling speed can be 100-300 r/min.
And (3) removing iron from the obtained slurry, drying the slurry for 5-15 hours at 150 ℃, and sieving the dried slurry with a 20-mesh sieve to obtain powder. Presintering the sieved powder at 1000-1300 ℃ for 2-6 hours to obtain KAl2(AlSi3O10)(OH)2Ceramic powder. The pre-sintering temperature is preferably 1100-1300 ℃, and more preferably 1280 ℃. The calcination time is preferably 6 hours. The pre-firing atmosphere may be air.
Then, the obtained KAl2(AlSi3O10)(OH)2Ceramic powder of (2) and Al2O3And ZrO2Mixing, adding water, and ball milling for 1-3 hours, wherein the material is: grinding balls: the mass ratio of water is 1: (2-4): (1-3). The ball milling speed can be 100-300 r/min.
The KAl2(AlSi3O10)(OH)2The particle diameter of (B) is less than or equal to 3.0 μm, and the preferred median particle diameter is 2.0 μm.
The ZrO2The particle diameter of (B) is less than or equal to 2.5 μm, and the preferred median particle diameter is 0.5 μm.
The Al is2O3The particle diameter of (2) is 2.5 μm or less, and the median particle diameter is preferably 1.0. mu.m.
After ball milling is finished, drying at 150 ℃, adding a binder for granulation, sieving with a 20-mesh sieve, and then pressing and molding.
The adhesive can be obtained by uniformly stirring a high polymer material and a solvent according to a conventional mode. In some embodiments, the binder is a solution of 6-8 wt% of a polymer material, such thatThe high molecular material comprises at least one of polyvinyl butyral and polyvinyl alcohol. The solvent may be polyvinyl alcohol. The addition amount of the binder is xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO21.0-5.0 wt% of the total mass of the raw materials.
The pressing mode can be static pressing. The pressure of the static pressure forming can be 180-220 MPa, and the time can be 1-3 minutes.
And (3) sintering for 2-6 hours at 1300-1500 ℃ after static pressure forming to obtain the ceramic material with high insulation, low heat conduction and high compressive strength. The sintering temperature is preferably 1350-1450 ℃, and more preferably 1400 ℃. The sintering time is preferably 3 to 5 hours, and more preferably 4 hours. The atmosphere for the sintering may be air.
In some embodiments, in and KAl2(AlSi3O10)(OH)2Before ball milling, the Al is2O3And ZrO2Presintering for 3-5 hours at 1100-1300 ℃. The purpose of this calcination is to reduce the amount of shrinkage of the ceramic during sintering.
The diameter and thickness of the ceramic material samples were measured using a micrometer.
The thermal conductivity of the ceramic material sample is measured by a NETZSCH LFA467 laser stroboscope, the test temperature range is 30-200 ℃, and the nitrogen protection is adopted.
The volume resistivity of a sample of ceramic material was measured using an LCR analyzer.
The compressive strength of the ceramic material sample adopts a sans universal tester, and the loading speed is 1mm/sec when the sample bar size is phi 5 multiplied by 12.5mm according to the GB/T4740-1999 test standard.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(1) Press KAl2(AlSi3O10)(OH)2Proportioning and weighing 173.4 g of K2CO3384.0 g Al2O3452.5 g SiO2Adding the weighed materials, 3000g of zirconia balls and 2000mL of deionized water into a polyurethane tank, and ball-milling for 1h by using a planetary ball mill with the rotating speed of 200 r/min;
(2) putting the original powder slurry ball-milled in the step (1) into a constant-temperature drying box, drying at 150 ℃ for 10h, and sieving with a 20-mesh sieve after drying to obtain uniformly-mixed powder;
(3) placing the powder sieved in the step (2) in a muffle furnace, and pre-burning for 6h at 1280 ℃ in the air atmosphere to obtain KAl2(AlSi3O10)(OH)2Ceramic powder is used for standby;
(4) mixing Al2O3And ZrO2Weighing 1000 g of the mixture respectively, putting the mixture into crucibles, and presintering the crucibles for 4 hours at 1200 ℃ in an air atmosphere for later use; the purpose of the calcination is to reduce the shrinkage of the ceramic during sintering;
(5) subjecting 10.0g of KAl obtained in step (3)2(AlSi3O10)(OH)2Ceramic powder and 10.0g of Al obtained in step (4)2O3Powder and 80.0g ZrO2Mixing, and making total 100 g; adding 100g of material, 300g of zirconia balls and 200mL of deionized water into a polyurethane tank, and ball-milling for 1h by using a planetary ball mill with the rotating speed of 200 r/min; drying at 150 ℃, adding 1.0 wt% of polyvinyl alcohol solution as a binder for granulation, sieving with a 20-mesh sieve, and carrying out static pressure forming;
(6) and (4) placing the sample prepared in the step (5) into a muffle furnace, and sintering at 1400 ℃ for 4h in an air atmosphere to prepare the high-insulation low-heat-conduction high-compressive-strength ceramic material. Finally, the performance of the obtained sample is tested by a NETZSCH LFA467 laser flashing instrument, an LCR analyzer, a sans universal testing machine and related test fixtures.
Example 2
(1) Press KAl2(AlSi3O10)(OH)2Proportioning and weighing 173.4 g of K2CO3384.0 g Al2O3452.5 g SiO2Adding the weighed materials, 3000g of zirconia balls and 2000mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min;
(2) putting the original powder slurry ball-milled in the step (1) into a constant-temperature drying box, drying at 150 ℃ for 10h, and sieving with a 20-mesh sieve after drying to obtain uniformly-mixed powder;
(3) placing the powder sieved in the step (2) in a muffle furnace, and pre-burning for 6h at 1280 ℃ in air atmosphere to obtain KAl2(AlSi3O10)(OH)2Ceramic powder is used for standby;
(4) mixing Al2O3And ZrO2Weighing 1000 g of the mixture respectively, putting the mixture into a crucible, and presintering the mixture for 4 hours at 1200 ℃ in an air atmosphere for later use;
(5) subjecting 10.0g of KAl obtained in step (3)2(AlSi3O10)(OH)2Ceramic powder and 80.0g of Al obtained in step (4)2O3Powder and 10.0g ZrO2Mixing, and making total 100 g; adding 100g of material, 300g of zirconia balls and 200mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min; drying at 150 ℃, adding 1.0 wt% of polyvinyl alcohol solution as a binder for granulation, sieving with a 20-mesh sieve, and carrying out static pressure forming;
(6) and (4) placing the sample prepared in the step (5) into a muffle furnace, and sintering at 1400 ℃ for 4h in an air atmosphere to prepare the high-insulation low-heat-conduction high-compressive-strength ceramic material. Finally, the performance of the obtained sample is tested by a NETZSCH LFA467 laser flashing instrument, an LCR analyzer, a sans universal testing machine and related test fixtures.
Example 3
(1) Press KAl2(AlSi3O10)(OH)2Proportioning and weighing 173.4 g of K2CO3384.0 g Al2O3452.5 g SiO2Adding the weighed materials, 3000g of zirconia balls and 2000mL of deionized water into polyurethaneIn the tank, ball milling is carried out for 1h in a planetary ball mill with the rotating speed of 200 r/min;
(2) putting the original powder slurry ball-milled in the step (1) into a constant-temperature drying box, drying at 150 ℃ for 10h, and sieving with a 20-mesh sieve after drying to obtain uniformly-mixed powder;
(3) placing the powder sieved in the step (2) in a muffle furnace, and pre-burning for 6h at 1280 ℃ in the air atmosphere to obtain KAl2(AlSi3O10)(OH)2Ceramic powder is used for standby;
(4) mixing Al2O3And ZrO2Weighing 1000 g of the mixture respectively, putting the mixture into a crucible, and presintering the mixture for 4 hours at 1200 ℃ in an air atmosphere for later use;
(5) subjecting the 20.0g KAl obtained in step (3)2(AlSi3O10)(OH)2Ceramic powder and 10.0gAl obtained in step (4)2O3Powder and 70.0g ZrO2Mixing, and making total 100 g; adding 100g of material, 300g of zirconia balls and 200mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min; drying at 150 ℃, adding 1.0 wt% of polyvinyl alcohol solution as a binder for granulation, sieving with a 20-mesh sieve, and carrying out static pressure forming;
(6) and (4) placing the sample prepared in the step (5) into a muffle furnace, and sintering for 4 hours at 1400 ℃ in an air atmosphere to prepare the required composite ceramic. Finally, the performance of the obtained sample is tested by a NETZSCH LFA467 laser flashing instrument, an LCR analyzer, a sans universal testing machine and related test fixtures.
Example 4
(1) Press KAl2(AlSi3O10)(OH)2Proportioning and weighing 173.4 g of K2CO3384.0 g Al2O3452.5 g SiO2Adding the weighed materials, 3000g of zirconia balls and 2000mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min;
(2) putting the original powder slurry ball-milled in the step (1) into a constant-temperature drying box, drying at 150 ℃ for 10h, and sieving with a 20-mesh sieve after drying to obtain uniformly-mixed powder;
(3) will step withPlacing the powder sieved in the step (2) in a muffle furnace, and pre-burning for 6h at 1280 ℃ in the air atmosphere to obtain KAl2(AlSi3O10)(OH)2Ceramic powder is used for standby;
(4) mixing Al2O3And ZrO2Weighing 1000 g of the mixture respectively, putting the mixture into a crucible, and presintering the mixture for 4 hours at 1200 ℃ in an air atmosphere for later use;
(5) subjecting the 20.0g KAl obtained in step (3)2(AlSi3O10)(OH)2Ceramic powder and 70.0gAl obtained in step (4)2O3Powder and 10.0g ZrO2Mixing, and making total 100 g; adding 100g of material, 300g of zirconia balls and 200mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min; drying at 150 ℃, adding 1.0 wt% of polyvinyl alcohol solution as a binder for granulation, sieving with a 20-mesh sieve, and carrying out static pressure forming;
(6) and (4) placing the sample prepared in the step (5) into a muffle furnace, and sintering for 4 hours at 1400 ℃ in an air atmosphere to prepare the required composite ceramic. Finally, the performance of the obtained sample is tested by a NETZSCH LFA467 laser flashing instrument, an LCR analyzer, a sans universal testing machine and related test fixtures.
Comparative example 1
(1) Mixing Al2O3And ZrO2Weighing 1000 g of the mixture respectively, putting the mixture into crucibles, and presintering the crucibles for 4 hours at 1200 ℃ in an air atmosphere for later use;
(2) subjecting 10.0g of Al obtained in step (1)2O3Powder and 90.0g ZrO2Mixing, and making total 100 g; adding 100g of material, 300g of zirconia balls and 200mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min; drying at 150 ℃, adding 1.0 wt% of polyvinyl alcohol solution as a binder for granulation, sieving with a 20-mesh sieve, and carrying out static pressure forming;
(3) and (3) placing the sample prepared in the step (2) into a muffle furnace, and sintering for 4 hours at 1400 ℃ in an air atmosphere to prepare the required composite ceramic. Finally, the performance of the obtained sample is tested by a NETZSCH LFA467 laser flashing instrument, an LCR analyzer, a sans universal testing machine and related test fixtures.
Comparative example 2
(1) Mixing Al2O3And ZrO2Weighing 1000 g of the mixture respectively, putting the mixture into crucibles, and presintering the crucibles for 4 hours at 1200 ℃ in an air atmosphere for later use;
(2) subjecting 90.0g of Al obtained in step (1)2O3Powder and 10.0g ZrO2Mixing, and making total 100 g; adding 100g of material, 300g of zirconia balls and 200mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min; drying at 150 ℃, adding 1.0 wt% of polyvinyl alcohol solution as a binder for granulation, sieving with a 20-mesh sieve, and carrying out static pressure forming;
(3) and (3) placing the sample prepared in the step (2) into a muffle furnace, and sintering for 4 hours at 1400 ℃ in an air atmosphere to prepare the required composite ceramic. Finally, the performance of the obtained sample is tested by a NETZSCH LFA467 laser flashing instrument, an LCR analyzer, a sans universal testing machine and related test fixtures.
Comparative example 3
(1) Press KAl2(AlSi3O10)(OH)2Proportioning and weighing 173.4 g of K2CO3384.0 g Al2O3452.5 g SiO2Adding the weighed materials, 3000g of zirconia balls and 2000mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min;
(2) putting the original powder slurry ball-milled in the step (1) into a constant-temperature drying box, drying at 150 ℃ for 10h, and sieving with a 20-mesh sieve after drying to obtain uniformly-mixed powder;
(3) placing the powder sieved in the step (2) in a muffle furnace, and pre-burning for 6h at 1280 ℃ in the air atmosphere to obtain KAl2(AlSi3O10)(OH)2Ceramic powder is used for standby;
(4) mixing Al2O3And ZrO2Weighing 1000 g of the mixture respectively, putting the mixture into crucibles, and presintering the crucibles for 4 hours at 1200 ℃ in an air atmosphere for later use;
(5) subjecting 40.0g KAl obtained in step (3)2(AlSi3O10)(OH)2Ceramic powder and the ceramic powder obtained in step (4)10.0g Al2O3Powder and 50.0g ZrO2Mixing, and making total 100 g; adding 100g of material, 300g of zirconia balls and 200mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min; drying at 150 ℃, adding 1.0 wt% of polyvinyl alcohol solution as a binder for granulation, sieving with a 20-mesh sieve, and carrying out static pressure forming;
(6) and (4) placing the sample prepared in the step (5) into a muffle furnace, and sintering for 4 hours at 1400 ℃ in an air atmosphere to prepare the required composite ceramic. Finally, the performance of the obtained sample is tested by a NETZSCH LFA467 laser flashing instrument, an LCR analyzer, a sans universal testing machine and related test fixtures.
Comparative example 4
(1) Press KAl2(AlSi3O10)(OH)2Proportioning and weighing 173.4 g of K2CO3384.0 g Al2O3452.5 g SiO2Adding the weighed materials, 3000g of zirconia balls and 2000mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min;
(2) putting the original powder slurry ball-milled in the step (1) into a constant-temperature drying box, drying at 150 ℃ for 10h, and sieving with a 20-mesh sieve after drying to obtain uniformly-mixed powder;
(3) placing the powder sieved in the step (2) in a muffle furnace, and pre-burning for 6h at 1280 ℃ in the air atmosphere to obtain KAl2(AlSi3O10)(OH)2Ceramic powder is used for standby;
(4) mixing Al2O3And ZrO2Weighing 1000 g of the mixture respectively, putting the mixture into crucibles, and presintering the crucibles for 4 hours at 1200 ℃ in an air atmosphere for later use;
(5) subjecting 40.0g KAl obtained in step (3)2(AlSi3O10)(OH)2Ceramic powder and 50.0gAl obtained in step (4)2O3Powder and 10.0g ZrO2Mixing, and making total 100 g; adding 100g of material, 300g of zirconia balls and 200mL of deionized water into a polyurethane tank, and carrying out ball milling for 1h in a planetary ball mill with the rotating speed of 200 r/min; drying at 150 ℃, adding 1.0 wt% of polyvinyl alcohol solution as a binderGranulating, sieving with 20 mesh sieve, and performing static pressure molding;
(6) and (4) placing the sample prepared in the step (5) into a muffle furnace, and sintering for 4 hours at 1400 ℃ in an air atmosphere to prepare the required composite ceramic. Finally, the performance of the obtained sample is tested by a NETZSCH LFA467 laser flashing instrument, an LCR analyzer, a sans universal testing machine and related test fixtures.
Table 1 shows the relevant performance parameters and performance test results of the composite ceramics prepared in examples 1-4 of the present invention and comparative examples 1-4 after sintering at 1400 deg.C:
as can be seen from fig. 2 and 3: press KAl2(AlSi3O10)(OH)2The main crystal phase after the proportioning weighing and synthesis is the design material KAl2(AlSi3O10)(OH)2Plays an important role in reducing the heat conductivity coefficient of the system material, and is additionally added with xAl2O3-zZrO2The subsequent main crystal phase is ZrSiO4And Al2O3Description of ZrO2And KAl2(AlSi3O10)(OH)2In the sintering process, a crystalline phase ZrSiO is formed in a solid solution mode4，Al2O3It is still present in a free state and serves to improve the compressive strength and insulating properties of the composite.
From Table 1, it can be seen that along with KAl2(AlSi3O10)(OH)2The proportion of the ceramic powder is increased, the thermal conductivity of the material is reduced, the lowest thermal conductivity can reach 3.55W/m x k (see example 3), and the volume resistivity is more than 1.00 multiplied by 1010Omega cm, and simultaneously satisfies the compressive strength of more than 1000 MPa. The main difference between example 3 and example 4 is Al2O3And ZrO2The ratio of (a) to (b) is changed, so that the difference of the thermal conductivity is large, and ZrO can be obtained2Specific to Al2O3The thermal conductivity coefficient of the insulating material is low, but the insulating material plays a certain role in improving the insulating strength and the compressive strength.
Without addition of KAl2(AlSi3O10)(OH)2In the case of ceramic powders (see comparative examples 1 and 2), the thermal conductivity of the material is too high to be useful for thermal insulation, while the compressive strength is less than 900MPa to be useful under high pressure, indicating KAl2(AlSi3O10)(OH)2The ceramic powder plays an important role in reducing the thermal conductivity of the material.
KAl2(AlSi3O10)(OH)2When the proportion of the ceramic powder exceeds 40% (see comparative examples 3 and 4), the material foams after sintering (as shown in fig. 4), reducing the compressive strength of the material, and the volume resistivity and the thermal conductivity cannot be measured due to the increase in porosity after foaming.
As can be seen from Table 1, some of the examples showed no significant improvement in volume resistivity and thermal conductivity, but showed a significant increase in compressive strength, compared to the comparative examples, mainly due to the pure ZrO2And Al2O3The sintering temperatures of (2) both exceed 1600 ℃ in comparative examples 1 and 2, since there is no KAl2(AlSi3O10)(OH)2The sintering is not compact at 1400 ℃, and more pores are formed, so that the compressive strength of the comparative example material is reduced.
Claims (10)
1. The ceramic material with high insulation, low heat conduction and high compressive strength is characterized by comprising the following chemical components: xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO2X + y + z =100wt%, x is more than or equal to 10wt% and less than or equal to 40wt%, y is more than or equal to 10wt% and less than or equal to 80wt%, and z is more than or equal to 10wt% and less than or equal to 80 wt%.
2. The high dielectric, low thermal conductivity, high compressive strength ceramic material of claim 1, wherein said xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO2Comprises the following raw materials: 10 to 20wt% of KAl2(AlSi3O10)(OH)240 to 60wt% of Al2O310 to 30wt% of ZrO2。
3. The high dielectric, low thermal conductivity, high compressive strength ceramic material of claim 2, wherein said KAl2(AlSi3O10)(OH)2The raw materials comprise: 10-40 wt% of K source, 35-45 wt% of Al source and 40-50 wt% of Si source.
4. The ceramic material with high insulation, low thermal conductivity and high compressive strength as claimed in claim 3, wherein the K source is K2O、KOH、K2CO3The Al source is Al2O3、Al（OH）3At least one of the Si source is silicon micropowder, silica sand and SiO2At least one of (1).
5. The ceramic material with high insulation, low thermal conductivity and high compressive strength as claimed in claim 1, wherein the ceramic material has a volume resistivity of more than 10 at 25-600 ℃10Omega cm, and the compressive strength is 1000-1300 MPa.
6. The preparation method of the ceramic material with high insulation, low thermal conductivity and high compressive strength as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
according to KAl2(AlSi3O10)(OH)2The raw materials are weighed, ball-milled, dried and sieved, and then presintered at 1000-1300 ℃ for 2-6 hours to obtain KAl2(AlSi3O10)(OH)2Powder; and
according to xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO2The raw materials consist of KAl2(AlSi3O10)(OH)2Powder of Al2O3And ZrO2And after ball milling, drying and sieving, adding a binder for granulation, after compression molding, sintering at 1300-1500 ℃ for 2-6 hours to obtain the high-insulation low-heat-conduction high-compressive-strength ceramic material.
7. The method of claim 6, wherein the amino acid sequence is KAl2(AlSi3O10)(OH)2Before ball milling, the Al is2O3And ZrO2Pre-sintering at 1100-1300 ℃ for 3-5 hours.
8. The method of claim 6, wherein the binder is added in an amount of xKAl2(AlSi3O10)(OH)2-yAl2O3-zZrO21.0-5.0 wt% of the total mass of the raw materials.
9. The preparation method according to claim 6, wherein the binder is 6 to 8wt% of a polymer material solution, the polymer material comprises at least one of polyvinyl butyral and polyvinyl alcohol, and a solvent of the polymer material solution is polyvinyl alcohol.
10. The method according to claim 6, wherein the atmosphere for sintering is air.
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