CN112321164A - Calcium borosilicate glass powder-based composite ceramic powder and preparation process thereof - Google Patents
Calcium borosilicate glass powder-based composite ceramic powder and preparation process thereof Download PDFInfo
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Abstract
The invention relates to a calcium borosilicate glass powder-based composite ceramic powder and a preparation process thereof, wherein the softening point of glass is improved by adopting low-content boron trioxide, a proper channel is provided for gas emission in a sintered body, the purpose of adding aluminum oxide is to improve the crystallization temperature of the glass, and the addition of calcium fluoride is beneficial to improving the water resistance of the glass; the process comprises calcining treatment to remove carbonate, avoids the problem that molten glass foams or boils and overflows a crucible when carbonate is decomposed at high temperature, and simultaneously eliminates the problem that the carbonate is not completely decomposed due to high viscosity of the molten glass.
Description
Technical Field
The invention belongs to the technical field of material processing, and particularly relates to calcium borosilicate glass powder-based composite ceramic powder and a preparation process thereof.
Background
Low temperature co-fired ceramic (LTCC) technology is an important approach for realizing miniaturization, integration, multi-functionalization and system level packaging (SiP) of high-frequency microwave devices. Calcium borosilicate (CBS: CaO-B)2O3-SiO2) The microcrystalline glass has excellent comprehensive properties such as low loss, high reliability and moderate thermal expansion coefficient, and especially has the frequency range of 10MHz-100GHzThe LTCC substrate material is of great interest because of its excellent dielectric properties. The CBS material is actually a material which is obtained by converting glass powder through compaction and sintering and contains a small amount of glass phase, a small amount of air holes and CaSiO3Microcrystalline glass with a main ceramic phase. The method for realizing the CBS microcrystalline glass is not a heat treatment crystallization method after glass liquid is poured and formed, but is realized by the traditional ceramic process (comprising glass powder, blank forming, binder removal and sintering), wherein the sintering process comprises the crystallization and densification processes. The sintering method has the advantages of low sintering temperature, short sintering time and flexible forming method, and has the defects that the glass powder is easily exposed to the environment atmosphere in the manufacturing process, so that the risks of surface moisture and volatile matter adsorption are caused, and the adverse interference is caused on the densification and crystallization processes of the glass powder.
In the prior art, the preparation method of the glass powder suitable for the CBS glass ceramic sintering method comprises the following three steps: (1) sol-gel method: its advantages are low calcining temp. and no need of smelting glass, so it can use ceramic crucible instead of expensive platinum crucible, but its disadvantage is strict requirement for raw material mixing uniformity in preparing process, high cost of raw material, high sintering temp. of glass powder and not easy to sinter compact sintered body. (2) Solid-phase reaction method: the method is a common dielectric ceramic powder production method and has the advantages of simple process, high stability, low raw material cost and the like, but the CBS ceramic powder prepared by solid phase reaction (or crystallization) can be sintered and compacted at higher temperature, so that the low temperature co-fired ceramic (LTCC) technology is inconvenient to adopt. (3) Melting-water quenching: the method has the advantages of low raw material cost and suitability for mass production, but has the defect of high glass melting temperature (such as higher than 1400 ℃), which leads to the component B2O3The volatilization loss of the CBS glass liquid affects the batch consistency of product performance, and the CBS glass liquid has serious corrosion to a common ceramic crucible, so that an expensive platinum crucible is usually required to be adopted during smelting. Table 1 is a summary table of related patents in China, and the subsequent ball milling process of the glass powder is the most critical.
TABLE 1 comparison of the patents on CBS glass ceramics and the patents on the invention
In the process of preparing CBS glass frit by the fusion method, it is often found that the sintered body of the glass frit undergoes a phenomenon of expansion, resulting in severe deformation of the sintered body and formation of pores in the sintered body, and these structural defects also impair dielectric properties of the sintered body, and thus cannot be used for LTCC substrate materials. The reasons for the problem may be (1) the low softening point of CBS glass, leading to premature densification of the sintered body surface, which is detrimental to volatile emission; (2) the presence of a material that is easily volatilized at high temperature in or on the surface of the glass powder is confirmed by FTIR analysis, as shown in FIG. 1, and the FTIR spectrum of the glass powder has-OH functional groups and-CO3Characteristic absorption peaks (valleys) of the functional groups. As can be seen from FIG. 1, several valleys around wave number 3414 belong to-OH hydroxyl groups, valleys around wave number 1617 are C ═ O bonds, valleys around wave number 1034 are C-O bonds, carbonate groups contain exactly C ═ O bonds and C-O bonds, the source of the hydroxyl groups-OH may be hydrolysis or hydration of the powder surface caused by the water in the aqueous medium or air in wet ball milling, and-CO3The sources of the carbon dioxide can be that the glass contains carbonate which is not completely decomposed and volatilized or the surfaces of the hydrolyzed glass powder and CO in the air during smelting2React to form-CO3Functional groups, e.g. Ca- (OH)2+CO2 ->CaCO3+H2O, and CaCO3Has a decomposition temperature of 825 deg.C, so that it is sintered at a low temperature of (C:)<Potential causes of bulging or foaming at 950 ℃).
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides calcium borosilicate glass powder-based composite ceramic powder and a preparation process thereof.
The invention provides a calcium-boron-silicon glass powder-based composite ceramic powder, which comprises, by mass, 70-96% of CBS glass powder serving as a matrix and 4-30% of ceramic phase filler:
wherein, the CBS glass powder consists of 12-19% of B2O3、40-50％SiO2、35-43％CaO、0.5-3.5％Al2O 3And 0.5-3.0% CaF2Composition is carried out;
the ceramic phase filler comprises 0.5-1.5% of nucleating agent and 3.5-28.5% of modifier.
Furthermore, the granularity D50 of the CBS glass powder is 1.5-5 μm, and the CBS glass powder is amorphous powder.
Further, the nucleating agent is crystalline ZrO2Granular or/and crystalline CaSiO3And (3) granules.
Further, crystalline ZrO2The particles are in the monoclinic phase.
Further, the particle size of the nucleating agent is 0.1-1.5 μm.
Further, the modifier is one or two of spherical or equiaxed mullite powder and cordierite powder.
Furthermore, the particle size D50 of the modifying agent is 1-3 μm.
The second purpose of the invention provides a preparation process of the composite porcelain powder, which comprises the following steps:
(1) calculating the required weight of each raw material according to the formula, and respectively weighing boric acid and SiO2、Al2O3Calcium fluoride and calcium carbonate, wherein boric acid and calcium carbonate are used as B2O3The calculation of the mass of precursors of CaO and B is based on keeping the number of moles of B and Ca constant;
(2) preparing CBS glass powder:
firstly, boric acid and SiO2、Al2O3、CaF2Mixing with calcium carbonate, grinding uniformly to obtain mixed powder, pressing the mixed powder into blocks, and crushing into particles without dust emission;
secondly, heating the crucible which is resistant to the CBS molten glass corrosion, then putting the crushed particles of the mixed powder into the crucible for high-temperature and long-time smelting, and rapidly cooling the molten glass to obtain glass fragments;
thirdly, crushing the glass fragments into coarse glass powder, and crushing the dry coarse glass powder into fine glass powder by adopting a dry process;
(3) pretreatment of ceramic phase filler: mixing the nucleating agent and the modifying agent, and carrying out high-temperature calcination treatment to obtain calcined filler;
(4) and weighing the glass fine powder and the calcined filler according to a ratio, and performing ball milling treatment to obtain the calcium borosilicate glass powder-based composite ceramic powder.
Due to B2O3CaO absorbs water easily, and high-purity B is difficult to find2O3And CaO, so that these raw materials are replaced by boric acid and calcium carbonate, which are precursors thereof, and are generally in a dispersed powder state (if the raw materials are wetted and agglomerated, need to be dried and ground into powder),
the purity of each substance in the invention is as follows: boric acid (purity ≧ 99.5%), SiO2(purity ≧ 99.5%) and Al2O3Purity ≧ 99%, calcium fluoride (purity ≧ 98.5%) and calcium carbonate (purity ≧ 99.9%).
Further, the step of (I) is boric acid and SiO2、Al2O3、CaF2Mixing with calcium carbonate for two or more times.
Further, in the second or multiple times of mixing, the first time of mixing is to mix the silicon dioxide and the calcium carbonate and then calcine the mixture for 1 to 3 hours at the temperature of 900-1000 ℃ to obtain the oxide mixture without carbonate, and the second time of mixing is to ball mill and mix the calcined oxide mixture without carbonate and proper amount of alumina, boric acid and calcium fluoride, wherein the mixing mode is dry mixing.
The set addition amounts of alumina, calcium fluoride and boric acid may be added on average according to the number of times of mixing. The mixed powder is pressed into small pieces and then broken into small pieces or granules with the particle size of 0.5-10mm, for example, the mixed powder is agglomerated into small pieces or granules by a roller mill or a screw granulator made of ceramic materials. The particles treated in the way are beneficial to eliminating the problem of dust flying during the subsequent smelting and feeding, are environment-friendly, and can ensure that the components of the glass do not deviate from the originally designed formula.
Further, in the step II, the mixture is heated to 1420-.
Furthermore, the glass fragments obtained by the water quenching method also need to be dried, the drying temperature is 90-150 ℃, and the drying time is 2-10 hours.
The crucible which can resist the CBS molten glass corrosion can be selected from a plurality of ceramic crucibles, such as a zirconia-corundum crucible, or a corundum-mullite crucible of which the inner surface contains a corundum or zirconia-corundum compact layer, and can also be selected from a platinum crucible, such as any refractory ceramic crucible which contains a platinum-gold lining, or a platinum crucible with a certain thickness. The crucible containing the discharge port is suitably a glass frit furnace (a high temperature furnace of the lift or push-pull type or other type). And after the smelting time is up, opening a molten glass discharge port of the crucible, wherein the molten glass flows into a water tank containing deionized water by the aid of the gravity of the molten glass, and the water tank can move or rotate to ensure that the molten glass cannot be accumulated at the same position. The molten glass may be directly poured into a vessel containing liquid nitrogen or dry ice, and the quenching or quenching is a necessary condition for forming glass.
If the amount of glass to be smelted is small, a crucible without a discharge hole can be used, and a common muffle furnace can be used for smelting, and at the moment, the raw material mixed powder can be put into the crucible before the temperature of the furnace is raised, and the crucible can be directly put into a glowing hearth after the material is added. After the smelting time is up, taking out the crucible without the discharge port by using refractory tongs, and pouring the molten glass into deionized water (water quenching). The deionized water quenching method is relatively simple and low in cost, and the specific surface area of the water-quenched glass fragments is relatively small, so that the practice proves that the water-quenching method can be used for preparing the glass fragments firstly even for the CBS glass powder which cannot be water-milled.
If the glass cullet is moist or contains moisture, a drying process is required.
Furthermore, in the third step, the coarse glass powder is sieved by a sieve with the pore diameter of 300 mu m, and the granularity D50 of the fine glass powder is 1.5-5 mu m.
Furthermore, the preparation of the glass fine powder by adopting a dry grinding or ball milling process is carried out under the protection of inert gas.
Furthermore, hydrophobic grinding aid with the mass fraction of less than 0.25 percent is added when the glass fine powder is prepared by dry ball milling. A horizontal ball mill with ceramic lining (corundum or zirconia) is adopted, and the balls are preferably yttria-stabilized zirconia balls, and are subjected to ball milling and screening, so that the dried glass fragments are crushed into coarse glass powder. Other methods such as a crusher with two or 4 rolls are also possible. And then, adopting a dry stirring ball mill, wherein balls, the lining and a stirring rod are all made of stabilized zirconia materials, carrying out ball milling and screening to grind the glass coarse powder into glass fine powder. The dry ball milling or pulverizing may also include air flow milling and vibration milling. Further, the dry ball milling is carried out under the protection of inert gas when the glass fine powder is prepared.
In the case of dry ball milling to obtain fine powder, it is preferable to control the atmosphere or humidity in the ball mill pot, for example, by using an inert gas (e.g., N)2) And the protection is carried out, so that the surface of the powder absorbs less moisture and carbon dioxide in the air. In N2The dry milling rather than the water-added ball milling under the protection condition has the function of preventing the powder particle surface from absorbing water to generate hydrolysis reaction, and reactants of the dry milling are volatile matters which are easy to volatilize during sintering, and the volatile matters are not favorable for sintering compactness and even cause bad swelling phenomenon.
Further, the temperature of the calcination in the step (3) is 900-.
The nucleating agent and the modifying agent are mixed, and different mixing methods can be adopted according to different conditions; if the amount is small, the powder is filled into a plastic bag for manual mixing (such as turning, kneading and other actions), and if the amount is large, a V-shaped mixer is adopted for mixing. Placing the mixed powder into a ceramic crucible, then placing the ceramic crucible into a high-temperature furnace, calcining the ceramic crucible for 1 to 4 hours at the temperature of 900 to 1000 ℃ in the atmospheric environment, and then cooling the ceramic crucible to room temperature along with the furnace. The calcining treatment of the nucleating agent and modifier is to eliminate the water and other volatile pollutants on the surface of the porcelain powder.
Further, during ball milling treatment in the step (4), inert gas protective powder or/and hydrophobic grinding aid with mass fraction of less than 0.25% are added.
In order to make the fine powder after dry grinding less prone to moisture absorption, an oily or non-hydrophilic hydrophobic treatment agent, such as a release agent paraffin powder or/and a binder PVB (polyvinyl butyral) powder, etc., is additionally added in the dry ball milling process of the steps (2) and (4), so that the oily or non-hydrophilic hydrophobic treatment agent does not interfere with the performance of a subsequent casting slurry system and is easy to remove glue. When the fine powder is dry-ground, the particle size of the composite porcelain powder is measured at intervals until the median diameter D50 of the powder particle size reaches 1.5-3 microns. The composite ceramic powder with the fineness is beneficial to compact sintering, control of sintering shrinkage and low-temperature sintering matching of silver paste. And finally, separating the ball from the composite porcelain powder, packaging the composite porcelain powder in a plastic bag, and marking for later use.
The dry ball milling composite ceramic powder has the advantages of overcoming the hydrolysis problem during water milling, saving the procedures of drying and powder dispersion, overcoming the problem of color change (such as grey) caused by ball milling of an organic solvent, and avoiding the problems of easy combustion and explosion of the organic solvent. The hydrophobic treatment agent added during dry grinding not only has the function of preventing moisture absorption, but also has the function of improving the ball milling efficiency, namely the grinding assisting function. Adding nucleating agent and modifier after the glass powder is formed, belonging to an external doping means, and the function of the nucleating agent is relative to the internal doping of ZrO in a glass network2And is doped with ZrO2The high stability of the prior glass can not be influenced by details, or the crystallization temperature of the prior glass is kept at a level higher than 840 ℃, which is beneficial to the densification and crystallization of the composite porcelain powder body at higher temperature. On the other hand, the modifier is added among the glass powder particles rather than in the glass network structure, one of the functions is to increase the sintering temperature, and the other functions includes adjusting dielectric properties such as dielectric constant, increasing mechanical strength, reducing sintering deformation or sintering shrinkage, and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts low content of boron trioxide to improve the softening point of the glass, thereby improving the glassThe starting temperature of densification, which provides a suitable path for the emission of gases from the sintered body, is increased by the addition of alumina in order to increase the devitrification temperature of the glass, while preventing the appearance of a second devitrification peak (valley), i.e. suppressing CaB2O4The appearance of the phase (the phase is slightly soluble in water), and the addition of the calcium fluoride is beneficial to improving the water resistance of the CBS glass, which is also beneficial to the subsequent electroplating process when the CBS glass ceramic substrate is used for manufacturing microwave devices. The glass phase in the composite ceramic powder forms CaSiO after the sintering temperature is higher than 840 DEG C3A ceramic main phase (first crystallization peak (valley)) and a small amount of residual glass phase microcrystalline glass matrix;
(2) the process of the invention removes carbonate through calcination treatment, avoids the problem that molten glass foams or boils and overflows a crucible when carbonate is decomposed at high temperature, and simultaneously solves the problem that carbonate is not completely decomposed because of high viscosity of the molten glass, the softening point of Calcium Borosilicate (CBS) glass is about 720 ℃, and a main crystal phase CaSiO is3The crystallization temperature is up to 840 ℃, the sintering finishing temperature of the Calcium Borosilicate (CBS) glass-based composite ceramic powder is up to 850 ℃, and the temperature is higher than that of CaCO3Even if the surface carbonate radicals generated by the surface reaction of the CBS glass powder are removed before the sintering of the composite ceramic powder blank is finished. After sintering treatment, a compact, well-shaped, smooth-surfaced (without bulge, expansion or/and foaming) and highly crystallized CBS microcrystalline glass-based composite substrate material can be obtained, the dielectric property of the material is that the dielectric constant is 5.9-6.6, the dielectric loss is 0.0011-0.0019@14-16GHz, and the material meets the use requirements of the industry on high-frequency LTCC ceramic circuit substrates;
(3) due to the excellent dielectric property under high frequency, the CBS microcrystalline glass based composite substrate material produced by the invention can be applied to the fields of 5G communication radio frequency devices, military phased array radars, unmanned vehicles, intelligent sensing chips of the Internet of things and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an FTIR plot of a prior art calborosilicate glass frit;
FIG. 2 is a flow chart of the preparation process of the composite porcelain powder.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
100kg of calcium borosilicate glass powder-based composite ceramic powder comprises 70% of CBS glass powder serving as a matrix and 30% of ceramic phase filler;
wherein, the CBS glass powder consists of 12 percent of B2O3、47％SiO2、35％CaO、3％Al2O 3And 3% CaF2Composition is carried out; the ceramic phase filler comprises 0.5 percent of nucleating agent and 28.5 percent of modifier, the particle size D50 of the CBS glass powder is 1.5-5 mu m, and the nucleating agent is ZrO2The particle size of the nucleating agent is 0.1-1.5 mu m, the modifying agent is spherical mullite powder, and the particle size D50 of the modifying agent is 1-3 mu m.
The preparation process of the calcium borosilicate glass powder-based composite ceramic powder comprises the following steps:
(1) according to the weight of each raw material, B is calculated according to the molar conservation of B and Ca2O3Respectively weighing boric acid and SiO according to the mass of boric acid and calcium carbonate corresponding to CaO2、Al2O3、CaF2And calcium carbonate;
(2) preparing CBS glass powder:
firstly, boric acid and SiO2、Al2O3、CaF2Mixing with calcium carbonate, grinding, mixing with boric acid and SiO2、Al2O3、CaF2Mixing the calcium carbonate with silica, calcining the mixture at 900 ℃ for 3 hours to obtain an oxide mixture without carbonate, mixing the mixture with the calcium carbonate for the first time to obtain a mixture of oxides without carbonate, performing ball milling treatment on the calcined mixture of oxides without carbonate, alumina, calcium fluoride and boric acid to obtain mixed powder, pressing the mixed powder into small blocks, and crushing the small blocks to obtain crushed particles with the particle size of 0.5-10 mm;
secondly, putting the crushed particles into a zirconia corundum crucible which is resistant to CBS glass liquid corrosion, then putting the zirconia corundum crucible into a furnace for smelting, heating the crucible to 1420 ℃, smelting for 5 hours, taking out the crucible, pouring glass liquid into deionized water, and drying the crucible for 10 hours at the temperature of 90 ℃ after the glass is drained to obtain glass blocks;
thirdly, crushing the glass blocks into coarse glass powder, wherein the particle size of the coarse glass powder is less than 300 mu m, grinding the coarse glass powder into fine glass powder by using a dry stirring ball mill, wherein the D50 of the fine glass powder is 1.5-5 mu m, and the dry ball milling is carried out under the protection of nitrogen when the fine glass powder is prepared;
(3) pretreatment of ceramic phase filler: mixing the nucleating agent and the modifying agent, and carrying out high-temperature calcination treatment at 900 ℃ for 4h to obtain calcined filler;
(4) weighing the glass fine powder and the calcined filler according to a ratio, putting the glass fine powder and the calcined filler into a ball milling tank of a planetary ball mill for ball milling treatment, adding 1 g of paraffin as a ball milling grinding aid and a hydrophobing agent, tightly covering the ball milling grinding aid and the hydrophobing agent, moving out a glove box capable of being filled with nitrogen, and carrying out planetary dry ball milling to 1.5-3 microns, wherein the ratio of grinding balls to material powder is 2: 1, ball milling speed is 250 r/min, ball milling time is 14h, and the calcium borosilicate glass powder-based composite ceramic powder is obtained.
Example 2
100kg of calcium borosilicate glass powder-based composite ceramic powder comprises 83% of CBS glass powder serving as a matrix and 17% of ceramic phase filler;
wherein, the CBS glass powder consists of 15 percent of B2O3、45％SiO2、39％CaO、0.5％Al2O 3And 0.5% CaF2Composition is carried out; the ceramic phase filler comprises 1% of nucleating agent and 16% of modifier, the particle size D50 of the CBS glass powder is 1.5-5 mu m, and the nucleating agent is CaSiO3The particle size of the nucleating agent is 0.1-1.5 mu m, the modifying agent is spherical cordierite powder, and the particle size D50 of the modifying agent is 1-3 mu m.
The preparation process of the calcium borosilicate glass powder-based composite ceramic powder comprises the following steps:
(1) according to the weight of each raw material, calculating B according to the molar conservation of B and Ca2O3Respectively weighing boric acid and SiO according to the mass of boric acid and calcium carbonate corresponding to CaO2、Al2O3、CaF2And calcium carbonate;
(2) preparing CBS glass powder:
firstly, boric acid and SiO2、Al2O3、CaF2Mixing with calcium carbonate, grinding, mixing with boric acid and SiO2、Al2O3、CaF2Mixing the calcium carbonate with silica, calcining the mixture at 950 ℃ for 2 hours to obtain an oxide mixture without carbonate, mixing the mixture with the calcium carbonate for the first time to obtain a mixture of oxides without carbonate, performing ball milling treatment on the calcined mixture of oxides without carbonate, alumina, calcium fluoride and boric acid to obtain mixed powder, pressing the mixed powder into small blocks, and crushing the small blocks to obtain crushed particles with the particle size of 0.5-10 mm; secondly, putting the crushed particles into a zirconia corundum crucible which is resistant to CBS glass liquid corrosion, then putting the zirconia corundum crucible into a furnace for smelting, heating the crucible to 1470 ℃, smelting for 3 hours, taking out the crucible, pouring glass liquid into deionized water, and drying the glass for 8 hours at the temperature of 120 ℃ after the glass is drained to obtain glass blocks;
thirdly, crushing the glass blocks into coarse glass powder, wherein the particle size of the coarse glass powder is less than 300 mu m, grinding the coarse glass powder into fine glass powder by using a dry stirring ball mill, wherein the D50 of the fine glass powder is 1.5-5 mu m, and the dry ball milling is carried out under the protection of nitrogen when the fine glass powder is prepared;
(3) pretreatment of ceramic phase filler: mixing the nucleating agent and the modifying agent, and carrying out high-temperature calcination treatment at 950 ℃ for 2.5 hours to obtain calcined filler;
(4) weighing the glass fine powder and the calcined filler according to a ratio, putting the glass fine powder and the calcined filler into a ball milling tank of a planetary ball mill for ball milling treatment, adding 1 g of paraffin as a ball milling grinding aid and a hydrophobing agent, tightly covering the ball milling grinding aid and the hydrophobing agent, removing a glove box capable of being filled with nitrogen, and carrying out planetary dry ball milling to 1.5-3 microns, wherein the ratio of grinding balls to material powder is 2.5: 1, ball milling speed is 260 r/min, ball milling time is 5h, and the calcium borosilicate glass powder-based composite ceramic powder is obtained. Example 3
100kg of calcium borosilicate glass powder-based composite ceramic powder comprises 96% of CBS glass powder serving as a matrix and 4% of ceramic phase filler;
wherein, the CBS glass powder consists of 18 percent of B2O3、40％SiO2、38.5％CaO、2％Al2O 3、1.5％CaF2Composition is carried out; the ceramic phase filler comprises 1.5 percent of nucleating agent and 3.5 percent of modifier, the particle size D50 of the CBS glass powder is 1.5-5 mu m, and the nucleating agent is ZrO2Particles and CaSiO3The particle size of the nucleating agent is 0.1-1.5 mu m, the modifying agent is a mixture of spherical mullite powder and cordierite powder, and the particle size D50 of the modifying agent is 1-3 mu m.
The preparation process of the calcium borosilicate glass powder-based composite ceramic powder comprises the following steps:
(1) according to the weight of each raw material, calculating B according to the molar conservation of B and Ca2O3Respectively weighing boric acid and SiO according to the mass of boric acid and calcium carbonate corresponding to CaO2、Al2O3、CaF2And calcium carbonate;
(2) preparing CBS glass powder:
firstly, boric acid and SiO2、Al2O3、CaF2Mixing with calcium carbonate, grinding, mixing with boric acid and SiO2、Al2O3、CaF2Mixing the calcium carbonate with silica, calcining the mixture at 1000 ℃ for 1 hour to obtain an oxide mixture without carbonate, mixing the mixture with calcium carbonate for the first time to obtain a calcined oxide mixture without carbonate, performing ball milling treatment on the calcined oxide mixture without carbonate, alumina, calcium fluoride and boric acid to obtain mixed powder, pressing the mixed powder into small blocks, and crushing the small blocks to obtain crushed particles with the particle size of 0.5-10 mm;
secondly, putting the crushed particles into a CBS glass liquid corrosion resistant fused zirconia alumina crucible, then putting the fused zirconia alumina crucible into a furnace for smelting, heating the fused zirconia alumina crucible to 1520 ℃, smelting for 1 hour, taking out the crucible, pouring the glass liquid into deionized water, and drying the glass for 2 hours at the temperature of 150 ℃ after the glass is discharged to obtain glass blocks;
thirdly, crushing the glass blocks into coarse glass powder, wherein the particle size of the coarse glass powder is less than 300 mu m, grinding the coarse glass powder into fine glass powder by using a dry stirring ball mill, wherein the D50 of the fine glass powder is 1.5-5 mu m, and the dry ball milling is carried out under the protection of nitrogen when the fine glass powder is prepared;
(3) pretreatment of ceramic phase filler: mixing the nucleating agent and the modifying agent, and carrying out high-temperature calcination treatment at 1000 ℃ for 1h to obtain calcined filler;
(4) weighing the glass fine powder and the calcined filler according to a ratio, putting the glass fine powder and the calcined filler into a ball milling tank of a planetary ball mill for ball milling treatment, adding 1 g of paraffin as a ball milling grinding aid and a hydrophobing agent, tightly covering the ball milling grinding aid and the hydrophobing agent, moving out a glove box capable of being filled with nitrogen, and carrying out planetary dry ball milling to 1.5-3 microns, wherein the ratio of grinding balls to material powder is 3: 1, ball milling speed is 250 r/min, ball milling time is 0.5h, and the calcium borosilicate glass powder-based composite ceramic powder is obtained. Comparative example 1
The preparation method of the calcium borosilicate glass powder-based composite ceramic powder of the comparative example is the same as that of the example 2, except that a nucleating agent is not added.
Comparative example 2
The preparation method of the calcium borosilicate glass powder-based composite ceramic powder of the comparative example is the same as that of the example 2, except that no modifier is added.
Comparative example 3
The preparation method of the calcium borosilicate glass powder-based composite ceramic powder of the comparative example is the same as that of the example 2, except that the nucleating agent in the ceramic phase filler in the preparation process is directly mixed with the CBS glass powder raw material and then smelted, namely, the nucleating agent is used as the inner doping of the CBS glass.
Test example 1
The composite porcelain powders prepared in examples 1 to 3 and comparative examples 1 to 3 were pressed into a compact at a pressure of 150MP, and then heated to 870 ℃ over 240 minutes, and sintered for 30 minutes, after which they were cooled to room temperature with a furnace being turned off, and the sample was observed for swelling or bulging, and the results are shown in table 2.
TABLE 2
As can be seen from Table 2, the addition of the nucleating agent and the modifying agent in the composite porcelain powder prepared by the invention can improve the sintering compactness, has a complete structure and a flat surface, and has no bulge or swelling phenomenon, and the composite porcelain powder prepared by the invention is easy to swell or swell by adopting an internal doping method in a comparative example 3.
Test example 2
The composite ceramic powder sintered bodies prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for dielectric constant and dielectric loss, and the results obtained by the resonator method are shown in Table 3.
TABLE 3
As can be seen from Table 3, the samples of the comparative examples resulted in an unfavorable increase in dielectric loss due to the presence of the swelling phenomenon.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The calcium borosilicate glass powder-based composite ceramic powder is characterized by comprising 70-96% of CBS glass powder serving as a matrix and 4-30% of ceramic phase filler in percentage by mass:
wherein, the CBS glass powder consists of 12-19% of B2O3、40-50％SiO2、35-43％CaO、0.5-3.5％Al2O3And 0.5-3.0% CaF2Composition is carried out;
the ceramic phase filler comprises 0.5-1.5% of nucleating agent and 3.5-28.5% of modifier.
2. The calcium-boron-silicon glass powder-based composite ceramic powder as claimed in claim 1, wherein the CBS glass powder has a particle size D50 of 1.5-5 μm, and is amorphous powder.
3. The calcium-borosilicate glass powder-based composite ceramic powder according to claim 1 or 2, wherein the nucleating agent is crystalline ZrO2Granular or/and crystalline CaSiO3Particles, preferably crystalline ZrO2The particles are in the monoclinic phase, and more preferably, the particle size of the nucleating agent is 0.1-1.5 μm.
4. The calcium-borosilicate glass powder-based composite porcelain powder as claimed in claim 1 or 2, wherein the modifier is one or both of spherical or equiaxed mullite powder and cordierite powder, and preferably, the particle size D50 of the modifier is 1-3 μm.
5. A process for preparing the composite porcelain powder according to any one of claims 1 to 4, wherein the process comprises the following steps:
(1) calculating the required weight of each raw material according to the formula, and respectively weighing boric acid and SiO2、Al2O3Calcium fluoride and calcium carbonate, wherein boric acid and calcium carbonate are used as B2O3The calculation of the mass of precursors of CaO and B is based on keeping the number of moles of B and Ca constant; (2) preparing CBS glass powder:
firstly, boric acid and SiO2、Al2O3、CaF2Mixing with calcium carbonate, grinding uniformly to obtain mixed powder, pressing the mixed powder into blocks, and crushing into particles without dust emission;
secondly, heating the crucible which is resistant to the CBS molten glass corrosion, then putting the crushed particles of the mixed powder into the crucible for high-temperature and long-time smelting, and rapidly cooling the molten glass to obtain glass fragments;
thirdly, crushing the glass fragments into coarse glass powder, and crushing the dry coarse glass powder into fine glass powder by adopting a dry process;
(3) pretreatment of ceramic phase filler: mixing the nucleating agent and the modifying agent, and carrying out high-temperature calcination treatment to obtain calcined filler;
(4) and weighing the glass fine powder and the calcined filler according to a ratio, and performing dry mixed grinding treatment to obtain the calcium-boron-silicon glass powder-based composite ceramic powder.
6. The process for preparing composite porcelain powder according to claim 5, wherein the steps of (i) boric acid and (ii) SiO2、Al2O3、CaF2And calcium carbonate, preferably, when mixing twice or more, the first mixing is to mix silicon dioxide and calcium carbonate and then calcine the mixture at the temperature of 900-1000 ℃ for 1-3 hours to obtain the oxide mixture without carbonate, and the second mixing is to ball mill and mix the calcined oxide mixture without carbonate with proper amount of alumina, boric acid and calcium fluoride, wherein the mixing mode is dry mixing.
7. The process for preparing composite porcelain powder according to claim 5, wherein the heating to 1420-.
8. The preparation process of composite ceramic powder as claimed in claim 5, wherein in the third step, the coarse glass powder is sieved with a 300 μm pore size sieve, and the granularity D50 of the fine glass powder is 1.5-5 μm, preferably, the preparation process of the fine glass powder by dry grinding or ball milling is carried out under the protection of inert gas; preferably, the hydrophobic grinding aid with the mass fraction of less than 0.25 percent is added when the glass fine powder is prepared by dry ball milling.
9. The process for preparing composite porcelain powder according to claim 5, wherein the calcination temperature in the step (3) is 900-1000 ℃ and the calcination time is 1-4 h.
10. The preparation process of the composite porcelain powder according to claim 5, wherein in the ball milling treatment in the step (4), inert gas protective powder or/and hydrophobic grinding aid with the mass fraction of less than 0.25% are added.
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