CN111925205A - Low-thermal expansion coefficient complex phase ceramic and preparation method thereof - Google Patents
Low-thermal expansion coefficient complex phase ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-thermal expansion coefficient complex phase ceramic and a preparation method thereof, belonging to the technical field of complex phase ceramics. The invention provides a low-thermal expansion coefficient complex phase ceramic which is prepared from the following raw materials in parts by mass: 65-70 parts of zirconium phosphate powder; 20-25 parts of wollastonite powder; 2-4 parts of a sintering aid; 1.5-2 parts of polyvinyl alcohol. The invention takes zirconium phosphate powder and wollastonite powder as main raw materials, and the zirconium phosphate is layered from the microstructure, and the wollastonite has high length-diameter ratio and is needle-shaped, and can be inserted into the layered structure of the zirconium phosphate to form an intercalation structure with the zirconium phosphate, so that the complex phase ceramic has low thermal expansion coefficient. Meanwhile, the intercalation structure formed by the zirconium phosphate and the wollastonite can also improve the mechanical strength of the material and reduce the conductivity of the material, so that the complex phase ceramic material can be applied to severe use environments.
Description
Technical Field
The invention relates to the technical field of complex phase ceramics, in particular to a low thermal expansion coefficient complex phase ceramic and a preparation method thereof.
Background
The ceramic material is one of the most important inorganic non-metallic materials, is a material which has the common advantages of a metallic material and a high molecular material after being made of a metallic material and a non-metallic material, and is closely related to modern construction and human life. The ceramic technology in China is relatively mature, the ceramic modification step is never stopped from the previous fragile ceramic to the modern structural ceramic and functional ceramic, and the high-performance ceramic plays an important role in the future production and life.
The ceramic material has strict requirements on performance in a harsh environment, is easy to damage under impact under thermal stress generally, and has poor thermal shock resistance, which is related to the thermal expansion coefficient of the material, and the low-thermal expansion ceramic material has obvious advantages in thermal shock resistance. However, most of the raw materials for producing ceramic materials are inorganic mineral powders, and because of the difference in expansion properties of various minerals, the use of powders with higher thermal expansion coefficients affects the properties of the whole ceramic, cracks are easily generated during sintering, and the obtained ceramic product has poor thermal shock resistance.
Disclosure of Invention
In view of the above, the present invention aims to provide a low thermal expansion coefficient complex phase ceramic and a preparation method thereof. The complex phase ceramic provided by the invention has low thermal expansion coefficient, high mechanical strength and low dielectric coefficient.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a low-thermal expansion coefficient complex phase ceramic which is prepared from the following raw materials in parts by mass:
the low coefficient of thermal expansion complex phase ceramic includes a calcium silicate phase and a zirconium phosphate phase.
Preferably, the raw materials comprise:
preferably, the low coefficient of thermal expansion complex phase ceramic is 10-6The thermal expansion coefficient under/K is less than or equal to 4.1.
Preferably, the particle size of the zirconium phosphate powder is less than or equal to 1 mu m; the particle size of the wollastonite powder is more than or equal to 100 meshes, and the mass percentage content of calcium silicate in the wollastonite powder is more than or equal to 94%.
Preferably, the sintering aid is two or more of zinc oxide, magnesium oxide, copper oxide and boron oxide.
The invention provides a preparation method of low-thermal expansion coefficient complex phase ceramic, which comprises the following steps:
(1) mixing zirconium phosphate powder, wollastonite powder and sintering aid, and carrying out dry grinding to obtain mixed powder;
(2) mixing the mixed powder with a polyvinyl alcohol aqueous solution, and carrying out wet milling to obtain a mixed blank;
(3) and pre-pressing, cold isostatic pressing, drying and sintering the mixed blank in sequence to obtain the low-thermal expansion coefficient complex phase ceramic.
Preferably, the dry grinding speed is 45-60 r/min, the time is 10-30 min, and the fineness D of the mixed powder is50≤45μm。
Preferably, the mass concentration of the polyvinyl alcohol aqueous solution is 8-16%;
the rotation speed of the wet grinding is 50-60 r/min, and the time is 20-30 min;
the water content of the mixed blank is 15-25 wt%.
Preferably, the pre-pressing pressure is 10-15 MPa, and the time is 20-30 min;
the pressure of the cold isostatic pressing is 250-300 MPa, and the time is 20-40 min.
Preferably, the sintering temperature is 1100-1200 ℃, and the time is 3-5 h; the heating rate of heating to the sintering temperature is 100-120 ℃/h.
The invention provides a low thermal expansion coefficient complex phaseThe ceramic is prepared from the following raw materials in parts by mass: 65-70 parts of zirconium phosphate powder; 20-25 parts of wollastonite powder; 2-4 parts of a sintering aid; 1.5-2 parts of polyvinyl alcohol. The invention takes zirconium phosphate powder and wollastonite powder as main raw materials, and the zirconium phosphate is layered from the microstructure, and the wollastonite has high length-diameter ratio and is needle-shaped, and can be inserted into the layered structure of the zirconium phosphate to form an intercalation structure with the zirconium phosphate, so that the complex phase ceramic has low thermal expansion coefficient. Meanwhile, the intercalation structure formed by the zirconium phosphate and the wollastonite can also improve the mechanical strength of the material, so that the complex phase ceramic material can be applied to a severe use environment. The results of the examples show that the low coefficient of thermal expansion complex phase ceramic provided by the invention is 10-6The thermal expansion coefficient under/K can be as low as 3.9, the bending strength can reach 140MPa, and the dielectric constant can be as low as 3.4.
The invention provides a preparation method of low-thermal expansion coefficient complex phase ceramic, which is simple to operate and easy to realize industrialized mass production.
Detailed Description
The invention provides a low-thermal expansion coefficient complex phase ceramic which is prepared from the following raw materials in parts by mass:
the low coefficient of thermal expansion complex phase ceramic includes a calcium silicate phase and a zirconium phosphate phase.
The preparation raw material of the low-thermal expansion coefficient complex phase ceramic comprises, by mass, 65-70 parts of zirconium phosphate powder, preferably 66-68 parts. In the invention, the granularity of the zirconium phosphate powder is preferably less than or equal to 1 μm, and more preferably 0.5-1 μm; the purity of the zirconium phosphate powder is preferably not less than 97%, more preferably not less than 98%. The source of the zirconium phosphate powder is not particularly required in the present invention, and any commercially available or self-prepared zirconium phosphate powder conventionally used in the art may be used. When the zirconium phosphate powder is prepared by itself, it can be prepared using a chemical co-precipitation method well known to those skilled in the art.
Based on the mass parts of the zirconium phosphate powder, the raw material comprises 20-25 parts of wollastonite powder, and preferably 22-24 parts. In the invention, the granularity of the wollastonite powder is preferably not less than 100 meshes, and more preferably 100-300 meshes. In the present invention, the mass percentage content of calcium silicate in the wollastonite powder is preferably not less than 94%, and more preferably not less than 96%. The invention has no special requirement on the source of the wollastonite powder, and the wollastonite powder which is conventionally sold or prepared in the field can be used. When preparing wollastonite powder by itself, the method for preparing the wollastonite powder preferably includes the steps of:
and sequentially carrying out coarse crushing, grinding, washing and drying on the wollastonite concentrate to obtain wollastonite powder.
The invention has no special requirements on the source of the wollastonite concentrate, and the mass percentage of calcium silicate of the wollastonite concentrate can be more than or equal to 94 percent. In the invention, the particle size of the coarse-broken wollastonite concentrate is preferably 2-4 cm; in an embodiment of the invention, the rough breaking is preferably performed using a jaw crusher. In the invention, the grinding mode is preferably a water grinding method, the invention preferably uses a water grinding device for grinding, and the rotation speed of the grinding is preferably 45 r/min. In the invention, the product of water grinding is preferably wollastonite slurry with the solid content of 72%, and the particle size of wollastonite in the wollastonite slurry is preferably 100-300 meshes. The present invention has no particular requirement on the manner of washing and drying, and can be carried out by using a washing and drying manner well known to those skilled in the art.
Based on the mass parts of the zirconium phosphate powder, the raw material comprises 2-4 parts of sintering aid, preferably 2-3 parts. In the present invention, the sintering aid is preferably two or more of zinc oxide, magnesium oxide, copper oxide, and boron oxide. In the invention, the sintering aid plays roles of fluxing and compacting. The invention can play a synergistic role by using two or more composite sintering aids, such as magnesium oxide and aluminum oxide, and compared with the selection of a single sintering aid, the invention is easier to reduce the consumption of solid fuel, accelerate the combustion speed in the sintering process, increase the yield and the strength of sintered ores and improve the utilization coefficient of a sintering machine.
Based on the mass parts of the zirconium phosphate powder, the preparation raw material of the low-thermal expansion coefficient complex phase ceramic provided by the invention comprises 1.5-2 parts of polyvinyl alcohol, preferably 1.6-2 parts. In the invention, the polyvinyl alcohol has the function of promoting the formation of the zirconium phosphate powder and the wollastonite powder.
In the present invention, the low coefficient of thermal expansion complex phase ceramic is at 10-6The coefficient of thermal expansion at/K is preferably 4.1 or less, more preferably 3.9 or less.
The invention also provides a preparation method of the low-thermal expansion coefficient complex phase ceramic, which comprises the following steps:
(1) mixing zirconium phosphate, wollastonite and a sintering aid, and performing dry grinding to obtain mixed powder;
(2) mixing the mixed powder with a polyvinyl alcohol aqueous solution, and carrying out wet milling to obtain a mixed blank;
(3) and pre-pressing, cold isostatic pressing, drying and sintering the mixed blank in sequence to obtain the low-thermal expansion coefficient complex phase ceramic.
Zirconium phosphate, wollastonite and a sintering aid are mixed and dry-ground to obtain mixed powder. The present invention does not require any particular mixing means, and mixing means known to those skilled in the art may be used. The dry grinding is preferably carried out by using ball milling equipment, the rotating speed of the dry grinding is preferably 45-60 r/min, more preferably 50-55 r/min, and the time is preferably 10-30 min, more preferably 20 min. In the invention, the fineness D of the particle size of the powder mixture50Preferably 45 μm or less, and more preferably 40 to 45 μm.
After the mixed powder is obtained, the mixed powder is mixed with a polyvinyl alcohol aqueous solution, and wet grinding is carried out to obtain a mixed blank. In the present invention, the mass concentration of the polyvinyl alcohol aqueous solution is preferably 8 to 16%, more preferably 10 to 12%. The present invention does not require any particular mixing means, and mixing means known to those skilled in the art may be used. In the invention, the rotation speed of wet grinding is preferably 50-60 r/min, and more preferably 55 r/min; the time is preferably 20-30 min, and more preferably 25 min. In the present invention, the moisture content of the mixed material is preferably 15 to 25 wt%, and more preferably 18 to 22 wt%.
After the mixed blank is obtained, the mixed blank is sequentially subjected to pre-pressing, cold isostatic pressing, drying and sintering to obtain the low-thermal expansion coefficient complex phase ceramic. In the invention, the pre-pressing pressure is preferably 10-15 MPa, and more preferably 12-14 MPa; the time is preferably 20-30 min, and more preferably 25 min. In the present invention, the preliminary pressing is preferably performed at normal temperature. The invention makes the mixed blank preliminarily formed by the pre-pressing.
In the invention, the pressure of the cold isostatic pressing is preferably 250-300 MPa, more preferably 260-280 MPa, and the time is preferably 20-40 min, more preferably 25-35 min. In the present invention, the cold isostatic pressing is preferably performed under normal pressure. The invention obtains the formed complex phase ceramic blank through the cold isostatic pressing.
In the invention, the drying temperature is preferably 80-100 ℃, and more preferably 85-95 ℃; the time is preferably 4 to 8 hours, and more preferably 5 to 6 hours.
In the invention, the sintering temperature is preferably 1100-1200 ℃, more preferably 1140-1180 ℃, and the heating rate of heating to the sintering temperature is preferably 100-120 ℃/h, more preferably 110 ℃; according to the invention, the sintering time is calculated from the temperature rise to the sintering temperature, and the sintering time is preferably 3-5 h, and more preferably 4 h. According to the invention, through the sintering, the surface area of the blank is reduced, the porosity is reduced, the blank is densified, and the sintered crystalline phase is silicate and zirconium phosphate.
In the invention, wollastonite has the functions of fluxing and reducing sintering temperature, and can reduce the liquid-phase melting point temperature of zirconium phosphate (the liquid-phase melting point temperature of zirconium phosphate is 1400 ℃), thereby reducing energy consumption in the sintering process.
After the sintering, the invention preferably cools the sintered complex phase ceramic. The present invention does not require any particular cooling means, such as natural cooling, which is well known to those skilled in the art.
The low thermal expansion coefficient complex phase ceramics and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Selecting natural wollastonite ore with 96 percent of calcium silicate content, and sequentially performing rough crushing, water grinding, water washing and drying to obtain 300-mesh wollastonite powder, wherein the wollastonite powder comprises zirconium phosphate powder (with the purity of 97 percent and the granularity of 1 mu m) according to the mass ratio: wollastonite powder: magnesium oxide: adding zinc oxide at a ratio of 70:20:1:2 into ball milling equipment for mixing, carrying out dry milling at a rotating speed of 50r/min for 10 minutes, then adding 8% polyvinyl alcohol aqueous solution (the polyvinyl alcohol is 1.8 parts in parts) in mass concentration, carrying out wet milling at a rotating speed of 55r/min for 20 minutes to obtain a mixed blank, carrying out dry press molding at a pressure of 15MPa for 20 minutes, carrying out cold isostatic pressing at a pressure of 300MPa for 20 minutes to obtain a complex phase ceramic blank, drying the blank at 90 ℃ for 8 hours, placing the dried blank in a furnace, heating to 1150 ℃ at a speed of 120 ℃/hour, carrying out heat preservation sintering for 4 hours, and finally naturally cooling to obtain the low-thermal expansion coefficient complex phase ceramic.
The thermal expansion coefficient of the obtained low-thermal expansion coefficient complex phase ceramic is tested according to the standard of QB/T1321--6The thermal expansion coefficient at/K is 4.1;
the bending strength of the obtained low-thermal expansion coefficient complex phase ceramic is tested according to the standard of GBT 4741-1999, and the bending strength is 131MPa through the test;
the dielectric constant of the obtained low thermal expansion coefficient complex phase ceramic is tested according to the GBT5594.4-2015 standard, and the dielectric constant is 4.3 through the test.
Example 2
Selecting natural wollastonite ore with 98 percent of calcium silicate content, and sequentially performing rough crushing, water grinding, water washing and drying to obtain 200-mesh wollastonite powder, wherein the wollastonite powder comprises zirconium phosphate powder (with the purity of 97 percent and the granularity of 1 mu m) according to the mass ratio: wollastonite powder: magnesium oxide: adding zinc oxide (65: 25:2: 2), mixing in a ball milling device, carrying out dry milling at the rotating speed of 50r/min for 15min, then adding a polyvinyl alcohol aqueous solution with the mass concentration of 8% (the polyvinyl alcohol is 1.8 parts), carrying out wet milling at the rotating speed of 55r/min for 20min to obtain a mixed blank, carrying out dry press molding at the pressure of 15MPa for 20min, carrying out cold isostatic pressing at the pressure of 300MPa for 20min to obtain a complex phase ceramic blank, drying the blank at the temperature of 90 ℃ for 6h, placing the dried blank in a furnace, heating to 1200 ℃ at the speed of 100 ℃/h, carrying out heat preservation sintering for 3 h, and finally naturally cooling to obtain the low-thermal expansion coefficient complex phase ceramic.
The resulting low CTE complex phase ceramic was tested for CTE, flexural strength and dielectric constant in the manner of example 1 and was tested at 10-6The thermal expansion coefficient at/K was 3.9, the bending strength was 140MPa, and the dielectric constant was 3.4.
Example 3
Selecting natural wollastonite ore with 96 percent of calcium silicate content, and sequentially performing rough crushing, water grinding, water washing and drying to obtain 300-mesh wollastonite powder, wherein the wollastonite powder comprises zirconium phosphate powder (with the purity of 97 percent and the granularity of 1 mu m) according to the mass ratio: wollastonite powder: magnesium oxide: adding zinc oxide at a ratio of 70:25:1:2 into ball milling equipment for mixing, carrying out dry milling at a rotating speed of 55r/min for 15min, then adding 8% polyvinyl alcohol aqueous solution (the polyvinyl alcohol is 1.7 parts in parts) in mass concentration, carrying out wet milling at a rotating speed of 55r/min for 20min to obtain a mixed blank, carrying out dry press molding at a pressure of 15MPa for 20min, carrying out cold isostatic pressing at a pressure of 250MPa for 20min to obtain a complex phase ceramic blank, drying the blank at 90 ℃ for 6h, placing the dried blank in a furnace, heating to 1200 ℃ at a speed of 100 ℃/h, carrying out heat preservation sintering for 3 h, and finally naturally cooling to obtain the low-thermal expansion coefficient complex phase ceramic.
The resulting low CTE complex phase ceramic was tested for CTE, flexural strength and dielectric constant in the manner of example 1 and was tested at 10-6The thermal expansion coefficient at/K was 3.9, the bending strength was 135MPa, and the dielectric constant was 3.7.
Comparative example 1
This comparative example differs from example 1 in that wollastonite was not added and the conditions were the same to obtain a zirconium phosphate ceramic.
Thermal expansion of the resulting zirconium phosphate ceramic in the manner of example 1The coefficient of expansion, flexural strength and dielectric constant were tested and found to be 10-6The thermal expansion coefficient at/K was 5.2, the bending strength was 117MPa, and the dielectric constant was 4.8.
As can be seen from the above examples and comparative examples, the present invention provides a complex phase ceramic having a low coefficient of thermal expansion, while having high mechanical strength and a low dielectric coefficient.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The low-thermal expansion coefficient complex phase ceramic is prepared from the following raw materials in parts by mass:
the low coefficient of thermal expansion complex phase ceramic includes a calcium silicate phase and a zirconium phosphate phase.
2. The low coefficient of thermal expansion complex phase ceramic of claim 1, wherein the raw materials comprise:
3. the low cte complex phase ceramic of claim 1 or 2, wherein the low cte complex phase ceramic is at 10 f-6The thermal expansion coefficient under/K is less than or equal to 4.1.
4. The low coefficient of thermal expansion complex phase ceramic as claimed in claim 1 or 2, wherein the particle size of the zirconium phosphate powder is less than or equal to 1 μm; the particle size of the wollastonite powder is more than or equal to 100 meshes, and the mass percentage content of calcium silicate in the wollastonite powder is more than or equal to 94%.
5. The low coefficient of thermal expansion complex phase ceramic as claimed in claim 1 or 2, wherein the sintering aid is two or more of zinc oxide, magnesium oxide, copper oxide and boron oxide.
6. The preparation method of the low-thermal expansion coefficient complex phase ceramic as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) mixing zirconium phosphate powder, wollastonite powder and sintering aid, and carrying out dry grinding to obtain mixed powder;
(2) mixing the mixed powder with a polyvinyl alcohol aqueous solution, and carrying out wet milling to obtain a mixed blank;
(3) and pre-pressing, cold isostatic pressing, drying and sintering the mixed blank in sequence to obtain the low-thermal expansion coefficient complex phase ceramic.
7. The preparation method according to claim 6, wherein the dry-milling is performed at a rotation speed of 45-60 r/min for 10-30 min, and the fineness D of the mixed powder is50≤45μm。
8. The preparation method according to claim 6, wherein the mass concentration of the polyvinyl alcohol aqueous solution is 8-16%;
the rotation speed of the wet grinding is 50-60 r/min, and the time is 20-30 min;
the water content of the mixed blank is 15-25 wt%.
9. The preparation method according to claim 6, wherein the pre-pressing pressure is 10-15 MPa and the time is 20-30 min;
the pressure of the cold isostatic pressing is 250-300 MPa, and the time is 20-40 min.
10. The preparation method according to claim 6, wherein the sintering temperature is 1100-1200 ℃ and the sintering time is 3-5 h; the heating rate of heating to the sintering temperature is 100-120 ℃/h.
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| CN115368822A (en) * | 2022-09-20 | 2022-11-22 | 武汉理工大学 | Ceramizable high-temperature-resistant dimensional silicone rubber protective material and preparation method thereof |
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