CN114195510B - Pure crystal phase high-quality factor nano-sized magnesium calcium titanate ceramic powder and preparation method thereof - Google Patents

Pure crystal phase high-quality factor nano-sized magnesium calcium titanate ceramic powder and preparation method thereof Download PDF

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CN114195510B
CN114195510B CN202111625561.7A CN202111625561A CN114195510B CN 114195510 B CN114195510 B CN 114195510B CN 202111625561 A CN202111625561 A CN 202111625561A CN 114195510 B CN114195510 B CN 114195510B
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calcium titanate
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CN114195510A (en
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朱洪伟
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Yuanjie New Material Technology Zhejiang Co ltd
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Abstract

The invention relates to a pure crystal phase high-flatness factor nano-size magnesium calcium titanate ceramic powder material and a preparation method thereof, wherein the material is nano-size magnesium calcium titanate nano-ceramic powder with an irregular pure crystal phase structure, the particle size of the material is 60-150nm, the particle size D50 after drying and crushing treatment is less than 200nm, the specific surface area is 1-30m 2/g, and a ceramic device after processing and sintering has an ultrahigh quality factor and an adjustable dielectric constant within a range of 20-40. Compared with the prior art, the preparation process is simple and convenient to operate, the reaction can be carried out under normal temperature and normal pressure without additional complex conditions and complex equipment, and the practical raw materials are cheap and easy to obtain, so that the preparation cost of the material is relatively low, the particle size of the particles is small, and the prepared magnesium calcium titanate can be used for various purposes such as manufacturing electronic ceramic devices, filter ceramic devices and the like.

Description

Pure crystal phase high-quality factor nano-sized magnesium calcium titanate ceramic powder and preparation method thereof
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to pure crystal phase nano-sized magnesium calcium titanate ceramic powder with granularity D50 smaller than 200nm and a preparation method thereof.
Background
The magnesium calcium titanate-based ceramic is a common dielectric ceramic material with good application performance in daily life, has relatively good dielectric stability, and has been widely applied to various fields such as electronic information, articles for daily use, biological medicine and the like. However, with the expansion of application fields and the improvement of performance indexes, the performance requirements on the magnesium calcium titanate-based ceramic material are also higher and higher, particularly the indexes of dielectric constant and quality factor, and the stable dielectric constant and high quality factor are often required. Therefore, the performance of the magnesium calcium titanate ceramic powder is a fundamental factor for determining the filter dielectric ceramic product obtained by future processing, and the preparation of the magnesium calcium titanate-based ceramic powder material with special excellent performance has become a research hot spot in the material world. The mechanical property and the thermal sintering property of the ceramic can be improved by controlling the crystal phase structure, the size and the morphology of the ceramic. The characteristics of the purity, the particle size, the crystal phase, the surface structure, the morphology and the like of the magnesium calcium titanate ceramic powder in the processing process of the dielectric filter ceramic device directly determine the processing yield and the subsequent service performance of the ceramic device. The preparation of the high-performance magnesium calcium titanate nano ceramic powder is a current research hot spot and a technical difficulty. However, the magnesium calcium titanate ceramic powder particles obtained by the conventional common solid-phase method are often relatively large, and even if the particle size can reach the nanometer level, the product is always seriously agglomerated or has impure crystalline phases after being dried, so that the development and application of the magnesium calcium titanate ceramic material are greatly limited. The preparation and the structural control of the high-quality nanoscale magnesium calcium titanate-based ceramic powder with a specific dielectric constant are key technical problems for determining the application of the magnesium calcium titanate-based ceramic.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a pure crystal phase high-quality factor nano-size magnesium calcium titanate ceramic powder material with the granularity D50 smaller than 200nm and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme: the nano-size magnesium calcium titanate-based powder material with the pure crystal phase and the high quality factor is characterized in that the material is nano-size magnesium calcium titanate nano-ceramic powder with the pure crystal phase structure in an irregular shape, the particle size of the material is 60-150nm, the particle size D50 after drying and crushing treatment is less than 200nm, the D90 is less than 300nm, the specific surface area is 1-30m 2/g, the ceramic device after processing and sintering has an ultrahigh quality factor, the dielectric constant is adjustable within the range of 20-40, and the apparent density is 3.0-4.0g/cm 3.
The invention provides a preparation method of a pure crystal phase high quality factor nano-size magnesium calcium titanate ceramic powder material with the granularity D50 smaller than 200nm, which comprises the following steps: firstly dispersing a water-insoluble magnesium-containing compound precursor, a calcium-containing compound precursor and a certain amount of surfactant into a mixed solution of water and organic alcohol, slowly introducing a titanium chloride solution into the mixed solution, performing subsequent centrifugation, washing, drying and roasting treatment in a liquid phase reaction process to obtain pure-crystal-phase nano-size magnesium calcium titanate ceramic powder, and then performing gas grinding treatment to obtain the pure-crystal-phase nano-size magnesium calcium titanate ceramic powder material with the granularity D50 smaller than 200 nm. The method comprises the following specific steps:
(1) Dissolving a certain amount of water-insoluble magnesium-containing compound precursor, calcium-containing compound precursor and surfactant into a mixed solvent of water and organic alcohol (the volume ratio of water to organic alcohol is 1:0.1-1), performing ultrasonic dispersion, obtaining a suspension under mechanical stirring, and recording the solution as a solution A.
(2) A certain amount of titanium chloride was weighed and dissolved in a certain volume of deionized water solution, which was designated as solution B.
(3) Uniformly mixing the solution A and the solution B by adopting peristaltic pumps in a positive adding, reverse adding or parallel flow mode respectively, reacting at room temperature, then continuously stirring for 1-2 days to obtain white gel, centrifugally separating to obtain a precipitate, washing, drying and roasting, and finally carrying out gaseous grinding treatment on the obtained solid powder sample to obtain the pure crystal phase high-quality factor nano-size magnesium calcium titanate ceramic powder material with the granularity D50 of less than 200 nm.
In the invention, the water-insoluble magnesium-containing compound precursor and the calcium-containing compound precursor are subjected to ultrasonic dispersion to form suspension, and the titanium chloride can be severely hydrolyzed to generate hydrogen chloride with strong acidity, so that the magnesium-containing mixture can be effectively promoted to be dissolved to generate magnesium ions and calcium ions, and the titanic acid generated by the hydrolysis of the titanium chloride can also be subjected to precipitation reaction with the magnesium ions or the calcium ions to generate a complex precipitation-dissolution-precipitation process, and the existence of the surfactant can weaken the interaction between sol particles and change the surface state of corresponding precipitates, thereby effectively preventing the occurrence of agglomeration among the precipitated particles and having an effective regulation and control effect on the magnesium calcium titanate crystalline phase. Therefore, the magnesium calcium titanate ceramic powder material with the granularity D50 smaller than 200nm, the pure crystal phase and the high quality factor and the nano size can be obtained through a relatively simple treatment process.
The concentration of the water-insoluble magnesium-containing compound precursor in the reaction system formed by the solution A and the solution B is 1-15wt%; the mass concentration of the calcium-containing compound precursor is 0.5-10%; the mass ratio of the water-insoluble magnesium-containing compound precursor to the titanium-containing chloride is 0.5-2.5:1, a step of; the reaction temperature can be controlled in the range of 0-40 ℃ under the room temperature condition, namely, along with the season change.
The water-insoluble magnesium-containing compound precursor is an inorganic magnesium salt or organic acid magnesium salt which is insoluble in water and organic alcohol; the magnesium salt precursor is one or more of magnesium carbonate, magnesium oxalate, magnesium citrate, magnesium tartrate, magnesium sulfite and magnesium hydroxide;
The calcium-containing compound precursor is inorganic calcium salt, organic acid calcium salt or hydroxide containing calcium, such as one or more of calcium carbonate, calcium oxalate, calcium citrate, calcium chloride, calcium nitrate and calcium hydroxide;
The titanium chloride is one or more of titanium tetrachloride, titanium trichloride and titanium oxychloride;
The surfactant is mainly nonionic high molecular polymer; the surfactant is one or more of polyethylene glycol, PVP, polyacrylic acid, polyether and F127; the mass ratio of the magnesium-containing compound precursor to the surfactant is 10:0.2-1.
The organic alcohol is liquid straight-chain alkyl alcohol or isomer alcohol thereof; the organic alcohol is one or more of ethanol, methanol, propanol, isopropanol, n-butanol and benzyl alcohol.
The water is water obtained through water purification treatment, wherein the content of heavy metal ions, iron, cobalt and nickel ions is lower than ppm.
The solution A and the solution B are contained in a glass container, an organic plastic container or a ceramic enamel container, and comprise one or more of a glass flask, a glass beaker, a surface dish, a conical flask, a wide-mouth bottle, a weighing bottle, a test tube, a measuring cup, a plastic beaker, a ceramic reaction kettle, an enamel reaction kettle and a centrifuge tube.
The centrifugal speed of the centrifugal separation in the step (3) is 4000-10000rpm, and the centrifugal time is 5-10min each time.
The solvent selected for washing in the step (3) is one or more of water, methanol, ethanol and isopropanol.
The temperature range of the drying treatment in the step (3) is 70-120 ℃; the roasting treatment is carried out at 700-1200 ℃ for 3-10 hours under the air atmosphere which is continuously blown by an air compressor.
The equipment selected by the solid powder sample through gaseous grinding treatment is an air flow pulverizer with the power of 5KW, the powder product is collected through a cyclone separator, the power of an air compressor is 80KW, and 10.0Mpa of compressed air is provided for pulverization.
Compared with the prior art, the magnesium-containing compound precursor and the calcium-containing compound precursor which are insoluble in water in the mixed solvent of water and organic alcohol can be severely hydrolyzed to generate hydrogen chloride with strong acidity to react with titanium chloride and then react with titanic acid to generate a complex process of precipitation-dissolution-precipitation, the organic alcohol plays a vital role in the reaction system, the existence of the organic alcohol can weaken the interaction among sol particles and change the surface state of corresponding precipitation, thereby preventing the agglomeration among the precipitation particles, in addition, the particle agglomeration in the product can be effectively relieved through effectively regulating and controlling the structure of the magnesium calcium titanate crystalline phase, and the particle size distribution in the product can be effectively controlled through the subsequent gaseous crushing technology. The whole preparation reaction process is carried out under the static condition at room temperature, the pure crystal phase high-quality factor nano-size magnesium calcium titanate ceramic powder obtained by energy conservation and environmental protection has irregular particle morphology, uneven surface, good particle dispersibility, uniform granularity and smaller particle size, and has wide application prospect, in particular to the field of ceramic device processing in the electronic information industry.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a pure crystalline phase high-quality factor nano-sized magnesium calcium titanate ceramic powder with a particle size D50 less than 200nm, which is obtained by the preparation method, and is prepared in example 1.
FIG. 2 is a characteristic large angle X-ray spectrum of a pure crystalline phase high quality factor nano-sized magnesium calcium titanate ceramic powder having a monodispersed particle size D50 less than 200nm, prepared from example 1.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
Dissolving 10g of magnesium carbonate, 0.5g of calcium carbonate and 1.0g of PEG-10000 by using 500ml of mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.1), adding 100ml of solution containing 40g of titanium tetrachloride into the solution after stirring for half an hour by a peristaltic pump, stirring for 12 hours, centrifuging the generated gel solution product at 11000rpm for 5 minutes to obtain gel, washing twice by using water and ethanol respectively, drying at 80 ℃ for 12 hours in air, calcining at 1100 ℃ for 4 hours, treating by using a gas state pulverizer with the gas pressure of 8.0MPa, and collecting the obtained powder sample by a cyclone separator to obtain the magnesium calcium titanate ceramic powder with the D50 of 70nm and the pure crystal phase nano size, wherein the dielectric constant test result is 20.6, and the quality factor can reach 110000. The morphology and the characteristics are shown in figures 1-2.
Example 2
10G of magnesium oxalate, 1g of calcium chloride and 1.0g of PEG-40000 are dissolved by 500ml of mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.1), 100ml of aqueous solution containing 50g of titanium oxychloride is added into the solution through a peristaltic pump after stirring for half an hour, the obtained gel solution product is centrifugated for 5 minutes at 11000rpm to obtain gel after stirring for 12 hours, and then the gel product is washed twice by water and ethanol respectively, dried for 12 hours at 110 ℃ in air, and calcined for 4 hours at 900 ℃ to obtain the pure-crystal-phase high-quality-factor nano-size magnesium calcium titanate ceramic powder with the D50 of 90 nm.
Example 3
Dissolving 10g of magnesium carbonate, 1g of calcium carbonate and 1.0g of PEG-10000 in 500ml of mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.2), slowly dripping the solution into 400ml of aqueous solution containing 80g of titanium trichloride by adopting a peristaltic pump after stirring for half an hour, centrifuging the generated gel solution product at 8000rpm for 5 minutes to obtain gel after stirring for 12 hours, washing the gel with water and ethanol twice, drying the gel in air at 100 ℃ for 12 hours, calcining the gel at 1000 ℃ for 4 hours, treating the gel by adopting a gas state pulverizer with the gas pressure of 1.0MPa, and collecting the obtained powder sample by adopting a cyclone separator to obtain the pure crystal phase high quality factor nano-size magnesium calcium titanate ceramic powder with the D50 of 105 nm.
Example 4
Dissolving 10g of magnesium carbonate, 2g of calcium hydroxide and 2.0g of P123 in 500ml of a mixed solvent of water and ethanol (the volume ratio of water to organic alcohol is 1:0.1), slowly dripping the solution into 400ml of an aqueous solution containing 60g of titanium trichloride by adopting a peristaltic pump after stirring for half an hour, centrifuging the generated gel solution product at 8000rpm for 5 minutes to obtain gel after stirring for 12 hours, washing the gel with water and ethanol twice, drying the gel in air at 100 ℃ for 12 hours, calcining the gel at 1000 ℃ for 4 hours, treating the gel by adopting a gas state pulverizer with the gas pressure of 1.0MPa, and collecting a powder sample by adopting a cyclone separator to obtain the pure crystal phase high quality factor nano-size magnesium calcium titanate ceramic powder with the D50 of 130 nm.
Example 5
The preparation method of the nano-size magnesium calcium titanate ceramic powder with the granularity D50 smaller than 200nm and a pure crystal phase and a high quality factor comprises the following specific steps:
(1) A certain amount of magnesium salt precursor magnesium carbonate, calcium salt precursor calcium carbonate (the atomic ratio of magnesium to calcium is 10:1) and surfactant PVP are dissolved in a mixed solvent of water and organic alcohol and ethanol (the volume ratio of water to organic alcohol is 1:0.1), a suspension is obtained under mechanical stirring, and the solution is recorded as solution A.
(2) A certain amount of aqueous solution of titanium trichloride was weighed and was designated as solution B. The mass ratio of the magnesium salt precursor to the titanium trichloride aqueous solution is 0.8:2;
(3) And uniformly mixing the solution A and the solution B by adopting peristaltic pumps in a positive adding mode, a reverse adding mode or a parallel flow mode respectively, reacting at room temperature, wherein the concentration of the magnesium salt precursor in the formed reaction system is 1wt%, continuously stirring for 1 day to obtain a gel solution, and centrifugally separating to obtain a precipitate product, wherein the centrifugal speed of centrifugal separation is 5000rpm, and the centrifugal time is 10min each time. Washing with water, drying at 120 ℃ and roasting at 1100 ℃ for 3 hours, and finally, carrying out gaseous grinding treatment on the obtained solid powder sample to obtain the pure crystal phase high-quality factor nano-sized magnesium calcium titanate ceramic powder material with the granularity D50 smaller than 200 nm. The equipment selected by the solid powder sample through gaseous grinding treatment is an air flow pulverizer with the power of 5KW, the powder product is collected through a cyclone separator, the power of an air compressor is 80KW, and 10.0Mpa of compressed air is provided for pulverization.

Claims (1)

1. The preparation method of the pure crystal phase high-quality factor nano-sized magnesium calcium titanate ceramic powder material is characterized by comprising the following steps of:
Dissolving 10g of magnesium carbonate, 0.5g of calcium carbonate and 1.0g of PEG-10000 by using 500ml of mixed solvent of water and ethanol, wherein the volume ratio of water to organic alcohol is 1:0.1, adding 100ml of solution containing 40g of titanium tetrachloride into the solution by a peristaltic pump after stirring for half an hour, centrifuging the generated gel solution product at 11000rpm for 5 minutes to obtain gel after stirring for 12 hours, washing the gel product twice by using water and ethanol respectively, drying the gel in air at 80 ℃ for 12 hours, calcining the gel product at 1100 ℃ for 4 hours, treating the gel product by using a gaseous pulverizer with the gas pressure of 8.0MPa, and collecting the obtained powder sample by using a cyclone separator to obtain the magnesium calcium titanate ceramic powder with the D50 of 70nm and the pure crystal phase nanometer size.
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CH284586A (en) * 1948-11-16 1952-07-31 Csf Process for preparing a ceramic dielectric based on double titanate of magnesium and calcium.
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CN112624755A (en) * 2020-12-02 2021-04-09 无锡市高宇晟新材料科技有限公司 Microwave dielectric ceramic material and preparation method thereof

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