CN114751733B - Production method of spherical ceramic filler with low temperature coefficient - Google Patents
Production method of spherical ceramic filler with low temperature coefficient Download PDFInfo
- Publication number
- CN114751733B CN114751733B CN202210436123.4A CN202210436123A CN114751733B CN 114751733 B CN114751733 B CN 114751733B CN 202210436123 A CN202210436123 A CN 202210436123A CN 114751733 B CN114751733 B CN 114751733B
- Authority
- CN
- China
- Prior art keywords
- parts
- ceramic
- stirring
- spray drying
- temperature coefficient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/47—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B2235/3265—Mn2O3
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
A production method of spherical ceramic filler with low temperature coefficient belongs to the field of electronic materials, and comprises the processes of proportioning, ball milling, stirring, spray drying, ceramic powder preparation and the like of 100 parts of ceramic filler, 0.5-10 parts of modifier, 50 parts of deionized water, 8-12 parts of PVA solution, 3-8 parts of PEG solution and 0.5-3 parts of silane coupling agent. The grain diameter of the prepared ceramic powder is between 8 and 40 mu m. The method solves the problems that in the prior art, large-particle-size ceramic fillers are irregular in appearance and randomly distributed, the ceramic fillers have large temperature coefficient, long-chain ends are easy to soft agglomerate after surface modification, the composite interface of resin and ceramics is poor, the powder thickness is different, the yield of particle size classification screening is not high, and the batch production cost is high. The preparation method has the characteristics of higher dielectric constant, small temperature coefficient, high sphericity, simple production process, capability of batch production and the like. The method is widely applied to the field of high-speed microwave composite medium substrates.
Description
Technical Field
The invention belongs to the field of electronic materials, and further relates to the field of high-frequency electronic materials, in particular to a spherical ceramic filler with high dielectric constant, low temperature coefficient and large particle size for a high-frequency plate and a batch production method thereof.
Background
In high-frequency circuit base materials, one of the main application directions of ceramic powder is as a filler, and the ceramic powder is often used in high frequencyThe copper-clad plate is used as a functional material for adjusting the dielectric constant of the copper-clad plate, increasing the functionality, improving the comprehensive performance, reducing the cost and the like. In high-frequency copper-clad plate production enterprises, the American Rogers company is used as an industry leading unit, a great amount of ceramic fillers are used in the existing copper-clad plates such as RT6000 series and TMM series, the ceramic addition amount is up to 50-90 wt%, and the particle size D50 is between 5 and 30 mu m. The domestic ceramic powder manufacturers mainly produce microwave ceramic powder, MLCC ceramic powder and LTCC powder, the main application directions of the ceramic powder manufacturers are 5G filters, MLCC devices and LTCC devices, the particle size D50 of the powder is basically between 0.2 and 3 mu m, the powder is used in ceramic filling type copper-clad plates, such as Rogers 6000 series and TMM series, the phenomena of easy agglomeration and the like are presented, and the high-frequency loss of the prepared plate is high; and often high dielectric ceramic fillers such as TiO 2 、BaTiO 3 、CaTi0 3 、SrTiO 3 When the dielectric constant temperature coefficient of the materials is negative and is more than 800 ppm/DEG C, and the zero temperature coefficient copper-clad plate is prepared, the positive temperature coefficient ceramic filler such as SiO is often used 2 、Al 2 O 3 The materials being multiphase-compounded, e.g. SiO 2 /TiO 2 Resin, al 2 O 3 /TiO 2 In the preparation process of the composite system such as resin, due to different fillers, the volume density of the composite system is inconsistent, and the layering is easy to occur in the composite process, so that the three-phase composite is not uniform; meanwhile, the inorganic oxide is polar molecules and shows hydrophilicity, and the common resin of the high-frequency copper-clad plate is polytetrafluoroethylene resin, hydrocarbon resin, polyphenyl ether resin and other materials which all show hydrophobicity, so that the composite interface of the two materials is poor.
In the prior art, the main production scheme of the ceramic filler is that inorganic oxides are subjected to high-temperature calcination, crushing and airflow classification to prepare ceramic powder, and then the ceramic powder is subjected to surface treatment by a silane coupling agent to prepare the ceramic filler, the micro-morphology of the ceramic filler prepared by the method is irregular and randomly distributed as shown in figure 1, meanwhile, the process is physically crushed, the powder is different in fineness in the crushing process, a large amount of fine powder is generated, the powder is wide in particle size distribution as shown in figure 2, and although particle size screening can be performed by airflow classification, the yield is not high, and the mass production cost is high. In addition, in subsequent application, a silane coupling agent is used for carrying out surface modification on ceramic powder, media such as alcohol and deionized water are usually used as dispersion liquid in the modification process, dehydration and drying are carried out after the modification is finished, and the phenomenon of soft agglomeration and hardening of the powder is caused because the long chain section of the silane coupling agent is easy to physically wind in the drying process. The filler prepared by the method is combined with resin to prepare the high-frequency microwave dielectric substrate, and the comprehensive performance is poor.
Therefore, according to the invention, the inorganic ceramic powder is doped in a trace manner, the dielectric constant temperature coefficient of the powder is improved, the spherical filler is prepared in a spray granulation and high-temperature sintering manner, the surface of the spherical filler is treated by using the silane coupling agent, and the spherical filler is dried by using the spray tower, so that the long chain end of the silane coupling agent is more prone to winding and wrapping the spherical powder under the action of centrifugal force, and the prepared filler with better flowability is prepared, thereby improving the compounding uniformity of the powder and resin and optimizing the compounding interface.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the problems that in the prior art, high dielectric constant and large-particle size ceramic fillers are irregular in appearance and randomly distributed, high in temperature coefficient, easy to agglomerate in a coupling agent modified long chain segment, poor in resin and ceramic composite interface, different in powder thickness degree, low in particle size grading screening output and high in batch production cost are solved.
Therefore, the invention provides a large-particle-diameter spherical ceramic filler with high dielectric constant and low temperature coefficient for a high-frequency plate, which comprises the following components: tiO 2 2 、CaTiO 3 、SrTiO 3 、BaTiO 3 Weighing 100 parts of ceramic filler and 0.5-10 parts of doping modifier which is SiO 2 、Al 2 O 3 、CuO、ZnO、Mn 2 O 3 50 parts of deionized water, 8-12 parts of PVA solution, 3-8 parts of PEG solution and 0.5-3 parts of silane coupling agent.
The invention provides a production method of a spherical ceramic filler with a low temperature coefficient, which comprises the following processes:
(1) Preparing materials: the ceramic filler is TiO 2 、CaTiO 3 、SrTiO 3 One of the materials is 100 parts of ceramic filler, 0.5-10 parts of doping modifier, 50 parts of deionized water, 8-12 parts of PVA solution and 3-8 parts of PEG solution.
(2) Ball milling: and mixing and ball milling the ceramic filler for 4-6 h.
(3) Stirring: after the ball milling is finished, the mixed solution is led into a stirring device for stirring, and the stirring speed is 100 r/min-300 r/min.
(4) And (3) spray drying: in the stirring process, a spray drying device is used for spray drying the mixed solution, the inlet temperature of the spray drying device is 220-260 ℃, the outlet temperature is 110-130 ℃, the rotating speed of an atomizer is 8000-16000 r/min, and the rotating speed of the atomizer is controlled to prepare the granulating powder with different grain diameters.
(5) Preparing ceramic powder: and (3) calcining the spray granulation powder at high temperature, wherein the high-temperature sintering temperature is 1000-1400 ℃, the heat preservation time is 4h +/-11 h, and the grain size of the prepared ceramic powder is 8-40 mu m.
(6) Surface modification: and preparing a mixed solution by using deionized water and alcohol, wherein the mass ratio of the deionized water to the alcohol is 15. Taking 50 parts of the prepared ceramic powder and 75 parts of deionized water/alcohol mixed solution, and stirring and dispersing at a high speed by using a high-speed dispersion machine, wherein the stirring speed is 800 r/min-3000 r/min, and the stirring time is 2 h-6 h. And after stirring, adding 0.5 to 3 parts of silane coupling agent, and stirring for 2 hours.
(7) Secondary spray drying: (6) And (3) carrying out spray drying on the mixed solution by using a spray drying device, wherein the inlet temperature of the spray drying device is 220-260 ℃, the outlet temperature of the spray drying device is 110-130 ℃, and the rotating speed of an atomizer is 8000-16000 r/min, so as to prepare the surface modified ceramic powder.
The large-particle-size ceramic filler has the characteristics of high dielectric constant, low temperature coefficient, high sphericity, centralized particle size distribution, good high-frequency performance, simple production process, capability of batch production and the like. The method is suitable for the field of manufacturing high-speed microwave composite dielectric substrates.
Drawings
FIG. 1 is a schematic diagram of the effect of a large-particle-size filler after air flow classification in the prior art.
FIG. 2 is a schematic diagram of the effect of the crushed large-particle-size filler in the prior art.
FIG. 3 shows TiO of the present invention 2 The granulation effect is shown schematically.
FIG. 4 shows TiO of the present invention 2 The effect of the spherical filler is shown schematically.
FIG. 5 is a view of TiO in accordance with the present invention 2 The contact angle test results after surface modification are shown schematically.
FIG. 6 shows BaTiO of the present invention 3 Schematic diagram of spray granulation effect.
FIG. 7 shows BaTiO of the present invention 3 The effect of the spherical filler is shown schematically.
FIG. 8 shows BaTiO of the present invention 3 The contact angle test results after surface modification are shown schematically.
Detailed Description
A production method of spherical ceramic filler with low temperature coefficient comprises the following specific embodiments:
example 1:
(1) Using TiO 2 As ceramic filler, al 2 0 3 One or more of MnO and CuO as doping modifier, tiO 2 Weighing 50 parts, weighing 3-8 parts of modifier, adding 100 parts of deionized water, 10 parts of PVA solution, 6.4 parts of PEG solution, and ball-milling for 5 hours.
(2) After the ball milling is finished, the mixed solution is led into a stirring tank, and the stirring speed is 100 r/min-300 r/min.
(3) In the stirring process, a spray drying tower is used for spray drying the mixed solution, the inlet temperature of the spray drying tower is 220-260 ℃, the outlet temperature is 110-130 ℃, the rotation speed of an atomizer is 8000 r/min-16000 r/min, and the granulation is shown in figure 3.
(4) Spray granulating powder, and calcining at high temperature, wherein the high-temperature sintering temperature is 1000-1400 ℃, the heat preservation time is 4h +/-11 h, the particle size of the prepared ceramic powder is 10-20 μm, as shown in figure 4, the dielectric constant of the synthesized spherical titanium dioxide is 83, and the temperature coefficient of the dielectric constant is-152 ppm/DEG C.
(5) And (2) taking 30 parts of synthesized spherical titanium dioxide and 45 parts of deionized water/alcohol mixed solution, stirring at a high speed of 2000r/min for 3 hours, adding 2 parts of silane coupling agent after stirring, wherein the silane coupling agent is one or more of Z6214, KH550, KH570 and F8261, and continuously stirring for 2 hours.
(6) And stirring the mixed solution, and performing spray drying, wherein the inlet temperature of a spray drying device is 220-260 ℃, the outlet temperature is 110-130 ℃, the rotating speed of an atomizer is 8000-16000 r/min, the prepared surface modified ceramic powder is hydrophobic, and the test of the surface contact angle is shown in figure 5.
Example 2:
(1) Using BaTiO 3 As ceramic filler, tiO 2 ZnO, cuO as doping modifier, baTiO 3 50 parts of filler, 0.5-10 parts of modifier, 100 parts of deionized water, 11 parts of PVA solution, 5 parts of PEG solution and ball milling for 4 hours.
(2) After the ball milling is finished, the mixed solution is led into a stirring tank, and the stirring speed is 100 r/min-300 r/min.
(3) And in the stirring process, spray drying the mixed solution by using a spray drying tower, wherein the inlet temperature of the spray drying tower is 220-260 ℃, the outlet temperature is 110-130 ℃, the rotating speed of an atomizer is 8000-16000 r/min, and granulating powder is prepared by spray drying, the granulation is shown in figure 5, the grain diameter of the granules is 40-60 mu m, the dielectric constant of the synthesized spherical barium titanate material is 38, and the temperature coefficient of the dielectric constant is 2 ppm/DEG C.
(4) Spraying and granulating the powder, and calcining at high temperature, wherein the high-temperature sintering temperature is 1000-1400 ℃, the heat preservation time is 4h +/-11 h, and the particle size of the prepared ceramic powder is 30-40 mu m, as shown in figure 6.
(5) And (2) taking 30 parts of synthesized spherical barium titanate and 45 parts of deionized water/alcohol mixed solution, stirring at a high speed of 1800r/min for 3 hours, adding 2 parts of silane coupling agent after stirring, wherein the silane coupling agent is one or more of Z6214, KH550, KH570 and F8261, and continuously stirring for 2 hours.
(6) And stirring the mixed solution, and performing spray drying, wherein the inlet temperature of a spray drying device is 220-260 ℃, the outlet temperature is 110-130 ℃, the rotating speed of an atomizer is 8000-16000 r/min, the prepared surface modified ceramic powder is hydrophobic, and the test of the surface contact angle is shown in figure 8.
Finally, it should be noted that: the above examples are given for clarity of illustration only, and the present invention includes but is not limited to the above examples, which are neither exhaustive nor exhaustive of all embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Embodiments that meet the requirements of the present invention are within the scope of the present invention.
Claims (3)
1. A production method of spherical ceramic filler with low temperature coefficient is characterized by comprising the following processes:
(1) Preparing materials: the ceramic filler is TiO 2 Or BaTiO 3 Weighing 100 parts of ceramic filler, 0.5-10 parts of doping modifier, 50 parts of deionized water, 8-12 parts of PVA solution and 3-8 parts of PEG solution;
(2) Ball milling: mixing and ball milling the ceramic filler for 4-6 h;
(3) Stirring: after the ball milling is finished, introducing the mixed solution into a stirring device for stirring, wherein the stirring speed is 100 r/min-300 r/min;
(4) And (3) spray drying: in the stirring process, a spray drying device is used for spray drying the mixed solution, the inlet temperature of the spray drying device is 220-260 ℃, the outlet temperature is 110-130 ℃, the rotating speed of an atomizer is 8000-16000 r/min, and the rotating speed of the atomizer is controlled to prepare the granulation powder with different grain diameters;
(5) Preparing ceramic powder: carrying out high-temperature calcination on the spray granulation powder, wherein the high-temperature sintering temperature is 1000-1400 ℃, the heat preservation time is 9 hours, and the particle size of the prepared ceramic powder is 8-40 mu m;
(6) Surface modification: preparing a mixed solution by using deionized water and alcohol, wherein the mass ratio of the deionized water to the alcohol is 15;
(7) Secondary spray drying: spray-drying the mixed solution in the step (6) by using a spray-drying tower, wherein the inlet temperature of a spray-drying device is 220-260 ℃, the outlet temperature is 110-130 ℃, and the rotating speed of an atomizer is 8000 r/min-16000 r/min, so as to prepare surface-modified ceramic powder;
the doping modifier is SiO 2 、Al 2 O 3 One or more of ZnO and CuO;
the silane coupling agent is one or more of Z6214, KH550, KH570 and F8261.
2. The method for producing spherical ceramic packing with low temperature coefficient according to claim 1, wherein the stirring device is a stirring tank.
3. The method for producing spherical ceramic packing with low temperature coefficient according to claim 1, wherein the spray drying apparatus is a spray drying tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210436123.4A CN114751733B (en) | 2022-04-25 | 2022-04-25 | Production method of spherical ceramic filler with low temperature coefficient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210436123.4A CN114751733B (en) | 2022-04-25 | 2022-04-25 | Production method of spherical ceramic filler with low temperature coefficient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114751733A CN114751733A (en) | 2022-07-15 |
| CN114751733B true CN114751733B (en) | 2023-03-21 |
Family
ID=82333835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210436123.4A Active CN114751733B (en) | 2022-04-25 | 2022-04-25 | Production method of spherical ceramic filler with low temperature coefficient |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114751733B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115610045B (en) * | 2022-12-20 | 2023-05-23 | 中国电子科技集团公司第四十六研究所 | Preparation method of low-loss and low-water-absorption copper-clad plate containing core-shell structure powder |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002355544A (en) * | 2001-05-30 | 2002-12-10 | Tdk Corp | Method of producing spherical ceramic powder, spherical ceramic powder, and composite material |
| US20030059366A1 (en) * | 2001-09-21 | 2003-03-27 | Cabot Corporation | Dispersible barium titanate-based particles and methods of forming the same |
| JP3930814B2 (en) * | 2003-01-24 | 2007-06-13 | Ｔｄｋ株式会社 | Composite dielectric material and substrate |
| US8080357B2 (en) * | 2006-01-30 | 2011-12-20 | Nippon Chemical Industrial Co., Ltd. | External additive for toner and method for producing the same |
| EP2530049B1 (en) * | 2010-01-29 | 2016-07-20 | Tokuyama Corporation | Process for production of spherical aluminum nitride powder, and spherical aluminum nitride powder produced by the process |
| CN102219232B (en) * | 2011-03-30 | 2013-05-01 | 北京矿冶研究总院 | Efficient compact spherical agglomerated particle of superfine boron powder and preparation method thereof |
| CN103435946A (en) * | 2013-08-27 | 2013-12-11 | 电子科技大学 | Method for preparing polytetrafluoroethylene (PTFE) compounded microwave ceramic substrate |
| CN104098290B (en) * | 2014-07-25 | 2016-01-13 | 中国电子科技集团公司第四十六研究所 | A kind of ball-type ceramic powder is the microwave composite medium substrate preparation technology of filler |
| CN105504769B (en) * | 2015-12-25 | 2018-02-13 | 福建慧思通三维技术有限公司 | High-fluidity elastic powder for three-dimensional printing and preparation method thereof |
| CN109181316B (en) * | 2018-08-31 | 2021-03-02 | 清华大学深圳研究生院 | Heat-conducting composite material and preparation method thereof |
| CN109093528B (en) * | 2018-10-16 | 2019-07-23 | 郑州磨料磨具磨削研究所有限公司 | A kind of metal anchoring agent diamond wheel and the method that the grinding wheel is prepared using atomizing granulating technology |
| CN111303666B (en) * | 2018-12-12 | 2021-08-10 | 介休市博创纳米材料科技有限公司 | Method for preparing lipophilic spherical zinc oxide dry powder by ultrasonic wet grinding |
| CN109648935B (en) * | 2018-12-24 | 2021-04-20 | 嘉兴佳利电子有限公司 | Preparation process of PTFE ceramic composite high-frequency copper-clad plate |
| CN112679890B (en) * | 2020-10-16 | 2023-09-12 | 高绍兵 | Flexible copper-clad plate base material, preparation method and application thereof, and circuit board |
| CN112592174A (en) * | 2020-12-10 | 2021-04-02 | 无锡市高宇晟新材料科技有限公司 | Microwave dielectric ceramic material with high thermal shock resistance and preparation method thereof |
| CN112851344B (en) * | 2021-01-26 | 2023-03-10 | 山东丁鼎科技发展有限公司 | Microwave dielectric ceramic with medium dielectric constant and preparation method thereof |
| CN113214582A (en) * | 2021-06-01 | 2021-08-06 | 江苏旭氟新材料有限公司 | Preparation process of PTFE (polytetrafluoroethylene) film with spherical ceramic powder as filler |
| CN113400544B (en) * | 2021-06-03 | 2023-03-24 | 中国振华集团云科电子有限公司 | Preparation method of ceramic composite polytetrafluoroethylene microwave composite dielectric substrate |
| CN113135752A (en) * | 2021-06-03 | 2021-07-20 | 中国振华集团云科电子有限公司 | Production method of high-dielectric low-loss high-frequency microwave composite dielectric substrate |
| CN113604095B (en) * | 2021-06-29 | 2022-06-24 | 东南大学 | Porous powder loaded with super-hydrophobic particles and preparation method and application thereof |
-
2022
- 2022-04-25 CN CN202210436123.4A patent/CN114751733B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114751733A (en) | 2022-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10899669B2 (en) | Boron aluminum silicate mineral material, low temperature co-fired ceramic composite material, low temperature co-fired ceramic, composite substrate and preparation methods thereof | |
| CA2506367A1 (en) | Copper flake powder, method for producing copper flake powder, and conductive paste using copper flake powder | |
| CN114751733B (en) | Production method of spherical ceramic filler with low temperature coefficient | |
| CN106927792B (en) | Low-dielectric-constant low-loss near-zero-temperature-coefficient LTCC (Low temperature Co-fired ceramic) material and preparation method thereof | |
| CN111099892A (en) | Barium titanate-based two-phase composite microwave dielectric ceramic material and preparation method thereof | |
| CN113329608B (en) | Preparation method of nano barium titanate/ferroferric oxide hybrid material with high wave-absorbing performance | |
| CN107746272B (en) | Microwave dielectric ceramic, polytetrafluoroethylene-ceramic composite substrate and preparation method | |
| CN111116197B (en) | Barium niobate system microwave dielectric ceramic material and preparation method and application thereof | |
| CN110981439A (en) | Microwave ceramic powder, preparation method thereof and application thereof in dielectric filter | |
| CN111170738A (en) | Two-phase composite microwave dielectric ceramic material and preparation method and application thereof | |
| CN113400544A (en) | Preparation method of ceramic composite polytetrafluoroethylene microwave composite dielectric substrate | |
| CN111138193B (en) | Microwave dielectric ceramic material with medium dielectric constant and preparation method and application thereof | |
| CN113402774B (en) | Titanium dioxide filler with high dielectric property and application thereof in preparation of PTFE (polytetrafluoroethylene) high-frequency substrate | |
| CN108485133B (en) | high-energy-storage-density composite material and preparation method thereof | |
| CN111925199B (en) | Low-temperature sintered microwave dielectric ceramic material and preparation method thereof | |
| CN110475751B (en) | Powder mixture | |
| CN109369173B (en) | Preparation method of tetragonal phase barium titanate powder and product | |
| CN115784243A (en) | Preparation method for constructing monodisperse hollow-structure silicon oxide microsphere material by using salt as template | |
| CN115087338A (en) | Electromagnetic loss material with uniform electromagnetism and impedance matching and preparation method thereof | |
| CN114409965B (en) | Functionalized titanium dioxide filler, preparation method thereof and PTFE (polytetrafluoroethylene) high-frequency copper-clad laminate | |
| CN116396072B (en) | Ceramic powder with high dielectric constant for microwave composite substrate and application thereof | |
| CN113149445A (en) | Method for uniformly refining low-temperature lead-free glass powder by using ultrahigh-pressure microjet and application thereof | |
| CN110465671B (en) | Preparation method of flaky silver powder | |
| CN115959895B (en) | Microwave dielectric ceramic material, preparation method thereof and microwave dielectric ceramic device | |
| TWI766494B (en) | Low-k material and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |