CN112079632A - Beta-phase eucryptite ceramic powder, preparation method and application thereof - Google Patents

Beta-phase eucryptite ceramic powder, preparation method and application thereof Download PDF

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CN112079632A
CN112079632A CN202010983734.1A CN202010983734A CN112079632A CN 112079632 A CN112079632 A CN 112079632A CN 202010983734 A CN202010983734 A CN 202010983734A CN 112079632 A CN112079632 A CN 112079632A
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beta
phase
eucryptite
ceramic powder
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王德彬
文明
沈晓燕
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Suzhou Jinyi New Material Technology Co.,Ltd.
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Abstract

The invention provides beta-phase eucryptite ceramic powder, a preparation method and application thereof, wherein the beta-phase eucryptite ceramic powder is prepared by taking a lithium source, silicon dioxide and aluminum hydroxide as raw materials, firstly calcining and grinding the raw materials into beta-phase eucryptite powder, and then sintering the beta-phase eucryptite powder and grinding the beta-phase eucryptite powder into the beta-phase eucryptite ceramic powder. The beta-phase eucryptite ceramic powder has higher negative expansion coefficient, and simultaneously has high purity which can reach more than 99.5 percent.

Description

Beta-phase eucryptite ceramic powder, preparation method and application thereof
Technical Field
The invention relates to the technical field of inorganic non-metallic materials, in particular to beta-phase eucryptite ceramic powder with high negative expansion coefficient and a preparation method of a copper-clad plate made of the beta-phase eucryptite ceramic powder.
Background
With the development of 5G communication technology, the use of ceramic devices in electronic equipment is increasing. However, the thermal expansion coefficient of the existing commonly-used copper-clad plate is higher than that of a ceramic device by about 50%, the thermal expansion coefficients of the two are not matched, and the device is easy to fail due to thermal stress in the actual use process. Therefore, it is necessary to develop a copper clad laminate filler material with high negative expansion coefficient to reduce the thermal expansion coefficient of the copper clad laminate. The eucryptite has higher negative expansion coefficient, high insulativity and excellent alkali resistance, and is suitable for being used as a filler for reducing the thermal expansion coefficient of a copper-clad plate.
Currently, the prior art has some methods for preparing eucryptite powders. However, the existing preparation method has some defects, such as complex preparation process and higher cost; the organic acid used in the preparation process has great environmental pollution; the purity of beta-phase eucryptite can only reach 90%, etc.
The Chinese patent with the patent number of CN108584970A discloses a method for preparing high-temperature negative expansion micro-nano powder with a beta-eucryptite-like structure. See the description [0017 ] for details]Paragraph stating that the present invention utilizes low cost natural spodumene ore as the primary source of lithium, aluminum, silicon, and nitrogen elements to significantly reduce the cost … … by an average coefficient of thermal expansion of about-3.6 x 10-6℃-1". Because the raw material adopts natural spodumene ore, the quality of the raw material is uncontrollable, and byproducts easily generated in the preparation process are alumina and silicon dioxide which both have higher positive thermal expansion coefficients (alumina: 7.2 multiplied by 10)-6ppm/deg.C; silicon dioxide: > 10.3X 10-6ppm/° c), the negative expansion coefficient of the eucryptite powder prepared thereby is low. Meanwhile, the treatment temperature in the preparation process is as high as 1500 ℃, the treatment process is complex, and the energy consumption is high.
The Chinese patent with the publication number of CN106379908A discloses a preparation method of beta-eucryptite powder, which has the advantages of short preparation period, simpler preparation process and environmental protection. See the description [0005 ]]Paragraph describes "the beta-eucryptite powder is sintered into dense ceramics by isostatic pressing, and the coefficient of thermal expansion is measured to be-7.09X 10-6V. C. Although this production method can also obtain eucryptite powder with satisfactory performance, the XRD pattern thereof has some hetero peaks (e.g. positions of 16 °, 24 °, 67 °) which are not labeled as β -eucryptite phase, so that eucryptite powder thereof is non-pure-phase eucryptite, and has a disadvantage that the purity of the powder is insufficient, resulting in that the powder purity is insufficientThe negative expansion performance is not ideal.
Disclosure of Invention
In order to solve the technical problems, the invention provides beta-phase eucryptite ceramic powder, a preparation method and application thereof. The beta-phase eucryptite ceramic powder has a large negative expansion coefficient and high powder purity.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides beta-phase eucryptite ceramic powder, which is prepared by taking a lithium source, silicon dioxide and aluminum hydroxide as raw materials, calcining and grinding the raw materials into beta-phase eucryptite powder, and then sintering the beta-phase eucryptite powder and grinding the beta-phase eucryptite powder into the beta-phase eucryptite ceramic powder.
Preferably, the lithium source is any one or a combination of several of lithium hydroxide, lithium oxide and lithium carbonate.
Preferably, the mass ratio of the lithium source to the silica to the aluminum hydroxide is 1: 1-10.
More preferably, the mass ratio of the lithium source to the silica to the aluminum hydroxide is 1:1 to 5.
More preferably, the mass ratio of the lithium source, the silicon dioxide and the aluminum hydroxide is 1: 1-1.5.
Preferably, the calcining temperature is 600-1800 ℃, and the calcining time is 1-10 hours.
Further preferably, the calcining temperature is 700-1500 ℃, and the calcining time is 1-7 hours.
More preferably, the calcination temperature is 800-1200 ℃, and the calcination time is 3-6 hours. By adjusting the calcining temperature and the calcining time and combining the calcining temperature and the calcining time synergistically, higher purity of the beta-phase eucryptite powder can be obtained.
Preferably, the sintering temperature is 800-1800 ℃, and the sintering time is 1-20 hours.
Further preferably, the sintering temperature is 1200-1400 ℃, and the sintering time is 2-16 hours.
More preferably, the sintering temperature is 1250-1300 ℃, and the sintering time is 3-12 hours. By adjusting the sintering temperature and the sintering time and combining the sintering temperature and the sintering time synergistically, higher purity of the beta-phase eucryptite ceramic powder can be obtained, and a larger negative expansion coefficient can be obtained.
Preferably, the sintering temperature is controlled to be higher than the calcining temperature, and the sintering time is controlled to be longer than or equal to the calcining time.
Preferably, the grain diameter D50 of the beta-phase eucryptite powder is controlled to be 1-3 μm, and D100 is not more than 15 μm.
Preferably, the grain diameter D50 of the beta-phase eucryptite ceramic powder is 1-10 μm, D100 is less than or equal to 20 μm, and the content of the beta-phase eucryptite in the beta-phase eucryptite ceramic powder is more than or equal to 99.5%.
Secondly, the invention also provides a preparation method of the beta-phase eucryptite ceramic powder, which comprises the following steps:
(1) mixing the lithium source, the silicon dioxide and the aluminum hydroxide, adding water, stirring and mixing to prepare slurry;
(2) drying the slurry to obtain dry powder;
(3) dry-mixing and grinding the dry powder to obtain precursor powder;
(4) calcining the precursor powder, and then grinding to obtain the beta-phase eucryptite powder;
(5) stirring and mixing the beta-phase eucryptite powder, water, a binder and a defoaming agent, and then carrying out spray granulation;
(6) sintering the powder after spray granulation into a ceramic body under a pressure condition;
(7) and grinding, scattering and grading the ceramic body to obtain the beta-phase eucryptite ceramic powder.
Preferably, in the step (1), the mass ratio of the water to the total mass of the lithium source, the silica and the aluminum hydroxide is 1: 1-5.
More preferably, in the step (1), the mass ratio of the water to the total mass of the lithium source, the silica and the aluminum hydroxide is 1:1 to 3.
More preferably, in the step (1), the mass ratio of the water to the total mass of the lithium source, the silica and the aluminum hydroxide is 1: 1-2.
Preferably, the stirring speed in the step (1) is controlled to be 100-500 rpm, and the stirring time is controlled to be 1-10 hours.
Further preferably, the stirring speed in the step (1) is controlled to be 150-300 rpm, and the stirring time is controlled to be 2-8 hours.
Further preferably, the stirring speed in the step (1) is controlled to be 180-220rpm, and the stirring time is controlled to be 3-5 hours.
Preferably, the drying temperature in the step (2) is controlled to be 60-150 ℃, and the drying time is 1-10 hours.
Further preferably, the drying temperature in the step (2) is controlled to be 80-120 ℃, and the drying time is 1-5 hours.
Further preferably, the drying temperature in the step (2) is controlled to be 90-110 ℃, and the drying time is 1-2.5 hours.
Preferably, the dry-mixing grinding in the step (3) is to grind the dry powder and the zirconia ball-milling medium in a grinding device for 0.5-5 hours according to the mass ratio of 1: 1-5.
More preferably, the dry-mixing grinding in the step (3) is to grind the dry powder and the zirconia ball-milling medium in a grinding device for 0.8-2 hours according to the mass ratio of 1: 1-4.
More preferably, the dry-mixing grinding in the step (3) is to grind the dry powder and the zirconia ball-milling medium in a grinding device for 0.9 to 1.1 hours according to a mass ratio of 1:2.5 to 3.5.
Preferably, in the step (5), the mass ratio of the beta-phase eucryptite powder, the water, the binder and the defoaming agent is 300-1000: 300-1000: 10-20: 1.
more preferably, in the step (5), the mass ratio of the beta-phase eucryptite powder, the water, the binder and the defoaming agent is 350-700: 350-700: 10.5-13: 1.
more preferably, in the step (5), the mass ratio of the beta-phase eucryptite powder, the water, the binder and the defoaming agent is 450-550: 450-550: 11-12: 1.
preferably, in the step (5), the stirring time is controlled to be 1-10 hours.
Further preferably, in the step (5), the stirring time is controlled to be 2 to 7 hours.
More preferably, in the step (5), the stirring time is controlled to be 3 to 5 hours.
Preferably, in the step (5), the temperature of spray granulation is controlled to be 150-300 ℃.
Further preferably, in the step (5), the temperature of spray granulation is controlled to 190 to 220 ℃.
More preferably, in the step (5), the temperature for spray granulation is controlled to be 200 to 210 ℃.
Preferably, the mesh number of the powder after spray granulation is 50-400 meshes.
More preferably, the mesh number of the powder after spray granulation is 90-350 meshes.
More preferably, the mesh number of the powder after spray granulation is 95 to 330 meshes.
Preferably, the pressure is controlled to be 100-150 MPa.
Further preferably, the pressure is controlled to be 120-150 MPa.
Further preferably, the pressure is controlled to be 140-150 MPa.
Preferably, the ceramic body is wet milled in step (7).
Thirdly, the invention also provides an application of the beta-phase eucryptite ceramic powder in a copper-clad plate.
Fourthly, the invention also provides a copper-clad plate taking the beta-phase eucryptite ceramic powder as a filler.
Compared with the prior art, the invention has the following advantages:
in the process of preparing the beta-phase eucryptite ceramic powder, the raw materials are calcined and ground into the beta-phase eucryptite powder, then the beta-phase eucryptite powder is sintered and ceramic-treated, and then the beta-phase eucryptite powder is ground into powder, so that the beta-phase eucryptite ceramic powder has higher negative expansion coefficient than the directly synthesized beta-phase eucryptite ceramic powder, and simultaneously has high purity and content of more than 99.5 percent.
The preparation method of the beta-phase eucryptite ceramic powder provided by the invention has the advantages of relatively simple process, low preparation cost and no pollution in the preparation process.
Drawings
FIG. 1 is a graph of the beta-phase eucryptite powder ceramic morphology obtained in example 2;
FIG. 2 is a graph of the beta-phase eucryptite powder ceramic morphology obtained in example 6;
FIG. 3 is a graph of the beta-phase eucryptite powder ceramic morphology obtained in example 7;
FIG. 4 is a graph of the beta-phase eucryptite powder ceramic morphology obtained in example 8;
FIG. 5 is a graph of the beta-phase eucryptite powder ceramic morphology obtained in example 9.
Detailed Description
The invention will be further described with reference to examples of embodiments shown in the drawings to which the invention is attached. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1:
step 1: putting lithium hydroxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 800 ℃ for 3 hours to obtain beta-phase eucryptite powder with the purity of 74.6%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 6 hours under the conditions of 150MPa pressure and 1300 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 not more than 16 μm, and thermal expansion coefficient of-7.19.
Example 2:
step 1: putting lithium hydroxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1000 ℃ for 3 hours to obtain beta-phase eucryptite powder with the purity of 100%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 6 hours under the conditions of 150MPa pressure and 1300 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 not more than 16 μm, and thermal expansion coefficient of-7.75.
Example 3:
step 1: putting lithium hydroxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1200 ℃ for 3 hours to obtain beta-phase eucryptite powder with the purity of 100%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 6 hours under the conditions of 150MPa pressure and 1300 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 not more than 16 μm, and thermal expansion coefficient of-7.68.
Example 4:
step 1: putting lithium oxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1200 ℃ for 6 hours to obtain beta-phase eucryptite powder with the purity of 87.9%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 6 hours under the conditions of 150MPa pressure and 1300 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 not more than 16 μm, and thermal expansion coefficient of-6.43.
Example 5:
step 1: putting lithium carbonate, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1200 ℃ for 6 hours to obtain beta-phase eucryptite powder with the purity of 93 percent;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 6 hours under the conditions of 150MPa pressure and 1300 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 not more than 16 μm, and thermal expansion coefficient of-6.94.
Example 6:
step 1: putting lithium hydroxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1000 ℃ for 3 hours to obtain beta-phase eucryptite powder with the purity of 100%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 6 hours under the conditions of 150MPa pressure and 1250 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 not more than 16 μm, and thermal expansion coefficient of-6.25.
Example 7:
step 1: putting lithium hydroxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1000 ℃ for 3 hours to obtain beta-phase eucryptite powder with the purity of 100%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 3 hours under the conditions of 150MPa pressure and 1300 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 not more than 16 μm, and thermal expansion coefficient of-7.05.
Example 8:
step 1: putting lithium hydroxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1000 ℃ for 3 hours to obtain beta-phase eucryptite powder with the purity of 100%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 12 hours under the conditions of 150MPa pressure and 1300 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 not more than 16 μm, and thermal expansion coefficient of-7.28.
Example 9:
step 1: putting lithium hydroxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1000 ℃ for 3 hours to obtain beta-phase eucryptite powder with the purity of 100%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain fine powder with D50 being 2 microns and D100 being less than 15 microns;
and 7: putting the fine powder, pure water, a polyvinyl alcohol binder and a defoaming agent into a stirring device according to the mass ratio of 500:500:11.5:1, and uniformly stirring for 4 hours;
and 8: carrying out spray granulation on the mixed slurry obtained in the step 7 at the temperature of 205 ℃;
and step 9: selecting the granulation powder within the range of 100-325 meshes, and sintering for 6 hours under the conditions of 150MPa pressure and 1350 ℃ to obtain a ceramic body;
step 10: carrying out wet grinding treatment on the ceramic body obtained in the step 9;
step 11: and (3) scattering and grading the powder obtained in the step (10) to obtain a powder with a particle size of D50: 3-5 μm, D100 is less than or equal to 16 μm, and the thermal expansion coefficient is-3.56.
Comparative example 1:
step 1: putting lithium hydroxide, silicon dioxide and aluminum hydroxide into a stirring device according to the mass ratio of 1:1:1 to obtain mixed powder;
step 2: mixing according to the mass ratio of the pure water to the mixed powder of 2:3, and then stirring at a rotating speed of 220rpm for 4 hours at a high speed of 180-;
and step 3: putting the slurry into an oven to be dried for 2 hours at the temperature of 100 ℃ to obtain dry powder;
and 4, step 4: putting the dry powder and zirconia ball-milling medium into a grinding device according to the mass ratio of 1:3, and dry-mixing and grinding for 1 hour to obtain precursor powder;
and 5: calcining the precursor powder at 1000 ℃ for 3 hours to obtain beta-phase eucryptite powder with the purity of 100%;
step 6: further grinding and refining the powder obtained in the step 5 to obtain the beta-phase eucryptite powder with D50 being 2 mu m, D100 being less than 15 mu m and the thermal expansion coefficient being-4.99.
FIGS. 1 to 5 show the morphology of the beta-phase eucryptite ceramic powder prepared in the above examples, which was measured by Zeiss tungsten filament scanning electron microscope (ZEISS EVO) at room temperature (25 ℃). As can be seen from the figure, the beta-phase eucryptite ceramic powder prepared under different conditions has larger shape difference.
The beta-phase eucryptite ceramic powder prepared by the above examples and comparative examples was tested for powder purity and thermal expansion coefficient. Wherein, the powder purity test is carried out by using a Bruker D8 ADVANCE X-ray diffractometer at room temperature (25 ℃), and the thermal expansion coefficient test is carried out by using a relaxation-resistant DIL 402 type thermal expansion instrument at the temperature of 50-150 ℃ (temperature rise speed: 5 ℃/min).
Referring to the first embodiment of the patent CN105968714A, the inorganic filler is replaced by beta-phase eucryptite ceramic powder from modified chlorite powder, and the filling amount is 25%; the CTE value was measured by using a relaxation-resistant DIL 402 type thermal expansion instrument under the condition of 25 to 150 ℃ at a temperature rise rate of 5 ℃/min.
The results of testing the powder purity, the coefficient of thermal expansion and the CTE value of the finished copper clad laminate under different conditions of the calcining process and the sintering process are shown in Table 1.
TABLE 1 results of powder purity and thermal expansion coefficient test under different conditions of calcination process and sintering process
Figure BDA0002688396710000101
Figure BDA0002688396710000111
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.

Claims (11)

1. A beta-phase eucryptite ceramic powder is characterized in that: the method comprises the steps of taking a lithium source, silicon dioxide and aluminum hydroxide as raw materials, calcining and grinding the raw materials into beta-phase eucryptite powder, and then sintering the beta-phase eucryptite powder and grinding the beta-phase eucryptite powder into the beta-phase eucryptite ceramic powder.
2. The beta-phase eucryptite ceramic powder of claim 1, wherein: the lithium source is any one or a combination of more of lithium hydroxide, lithium oxide and lithium carbonate; the mass ratio of the lithium source to the silicon dioxide to the aluminum hydroxide is 1: 1-10.
3. The beta-phase eucryptite ceramic powder of claim 1, wherein: the calcining temperature is 600-1800 ℃, and the calcining time is 1-10 hours; the sintering temperature is 800-1800 ℃, and the sintering time is 1-20 hours; and controlling the sintering temperature to be higher than the calcining temperature, and controlling the sintering time to be more than or equal to the calcining time.
4. The beta-phase eucryptite ceramic powder of claim 1, wherein: controlling the grain diameter D50 of the beta-phase eucryptite powder to be 1-3 mu m, wherein D100 is less than or equal to 15 mu m; the grain size D50 of the beta-phase eucryptite ceramic powder is 1-10 mu m, D100 is less than or equal to 20 mu m, and the content of the beta-phase eucryptite in the beta-phase eucryptite ceramic powder is more than or equal to 99.5%.
5. A method of making the beta-phase eucryptite ceramic powder of any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) mixing the lithium source, the silicon dioxide and the aluminum hydroxide, adding water, stirring and mixing to prepare slurry;
(2) drying the slurry to obtain dry powder;
(3) dry-mixing and grinding the dry powder to obtain precursor powder;
(4) calcining the precursor powder, and then grinding to obtain the beta-phase eucryptite powder;
(5) stirring and mixing the beta-phase eucryptite powder, water, a binder and a defoaming agent, and then carrying out spray granulation;
(6) sintering the powder after spray granulation into a ceramic body under a pressure condition;
(7) and grinding, scattering and grading the ceramic body to obtain the beta-phase eucryptite ceramic powder.
6. The method of preparing beta-phase eucryptite ceramic powder according to claim 5, wherein: in the step (1), the mass ratio of the water to the total mass of the lithium source, the silicon dioxide and the aluminum hydroxide is 1: 1-5; and (2) controlling the stirring speed in the step (1) to be 100-500 rpm, and the stirring time to be 1-10 hours.
7. The method of preparing beta-phase eucryptite ceramic powder according to claim 5, wherein: and (3) controlling the drying temperature in the step (2) to be 60-150 ℃, and the drying time to be 1-10 hours.
8. The method of preparing beta-phase eucryptite ceramic powder according to claim 5, wherein: in the dry mixing grinding in the step (3), the dry powder and the zirconia ball-milling medium are ground in a grinding device for 0.5-5 hours according to the mass ratio of 1: 1-5.
9. The method of preparing beta-phase eucryptite ceramic powder according to claim 5, wherein: in the step (5), the mass ratio of the beta-phase eucryptite powder, the water, the binder and the defoaming agent is 300-1000: 300-1000: 10-20: 1; controlling the stirring time to be 1-10 hours; controlling the temperature of the spray granulation to be 150-300 ℃; the mesh number of the powder after spray granulation is 50-400 meshes.
10. The method of preparing beta-phase eucryptite ceramic powder according to claim 5, wherein: the pressure in the step (6) is 100-150 MPa.
11. Use of the beta-phase eucryptite ceramic powder of any one of claims 1 to 4 in copper clad laminate.
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