CN113845362A - Method for preparing microwave dielectric ceramic based on solid waste - Google Patents
Method for preparing microwave dielectric ceramic based on solid waste Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002910 solid waste Substances 0.000 title claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 57
- 239000000843 powder Substances 0.000 claims abstract description 55
- 238000000498 ball milling Methods 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 32
- 239000010802 sludge Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 16
- 238000012545 processing Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 238000003825 pressing Methods 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 8
- 238000007650 screen-printing Methods 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000004891 communication Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 238000007873 sieving Methods 0.000 description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 235000015895 biscuits Nutrition 0.000 description 11
- 238000000227 grinding Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 238000009270 solid waste treatment Methods 0.000 description 6
- 239000002912 waste gas Substances 0.000 description 6
- 230000003009 desulfurizing effect Effects 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
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- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000005433 ionosphere Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing microwave dielectric ceramics based on solid wastes, which comprises the steps of processing sludge of an electronic factory at a high temperature to prepare a molten block, crushing the obtained molten block, adding water, carrying out ball milling and drying to obtain powder; chemical method is used for quantifying the proportion of Ca and Al elements in the powder, the powder is weighed, and TiO is added into the powder2Mixing with rare earth oxide, ball milling for the first time, synthesizing, and ball milling for the second time to obtain ceramic powder; adding a binder into the ceramic powder for granulation, aging, pressing for molding, and then heating for plastic removal to obtain a ceramic green body; sintering the obtained ceramic blank to obtain the ceramic plate; and processing the ceramic chip, ultrasonically cleaning, screen-printing silver, drying and burning the silver to obtain the microwave dielectric ceramic material. The microwave dielectric ceramic prepared by the invention has good dielectric constant and resonance frequency temperature coefficient close to zero, and can be used for micro-electronicsWave communication field, circuit board base material, etc.
Description
Technical Field
The invention relates to industrial solid waste material recycling, in particular to a method for preparing microwave dielectric ceramics based on solid waste.
Background
The industrial solid waste has huge yield every year, but the treatment mode is mainly storage, which leads to the gradual accumulation of the industrial solid waste and the gradual aggravation of the industrial solid waste treatment problem. The industrial solid waste treatment is gradually promoted to the high-quality direction in the future, the technical innovation is taken as the power, the talent culture is enhanced, and a sustainable development mode is formed. The industrial solid waste treatment is an important component of the solid waste treatment industry in China, and the industrial solid waste is divided into general industrial solid waste and industrial dangerous waste. Because the industrial solid waste is influenced by factors such as industrial production process and the like, the components are changed frequently, which causes difficulty in treatment and utilization; in addition, the industrial solid waste treatment requires special equipment and professional technicians, which brings high cost to the industrial solid waste treatment.
The microwave frequency band used for the microwave dielectric ceramic is an electromagnetic wave between an ultrashort wave and an infrared wave in a radio spectrum, the frequency range of the electromagnetic wave is 300 MHz-300 GHz, and the wavelength of the electromagnetic wave is 1 m-0.1 mm. The microwave has short wavelength and strong directivity, and is very suitable for finding and tracking targets by radars, navigation and the like; the microwave has high frequency range and large information capacity, and the number of usable wave bands contained in the range of 300MHz to 300GHz is 1000 times of that of usable wave bands contained in the range of 0MHz to 300MHz, and the usable wave bands contained in the range of medium and short wave, thereby being favorable for information transmission. In addition, the microwave can penetrate the high-altitude ionosphere, so that the microwave is particularly suitable for satellite communication transmission. The microwave technology is mainly applied to radar, communication, navigation and other special occasions at first, and in recent years, along with the rapid development of microwave communication, the application of the microwave technology in civil products is rapidly increased. Microwave dielectric ceramic materials having excellent properties are receiving wide attention and rapidly coming to the market, and have made a key contribution to miniaturization and portability of wireless communication devices such as car phones, mobile phones, interphones, and the like.
The yield of the electronic sludge is huge every year, most of the electronic sludge is buried, the electronic sludge cannot be effectively utilized, and hidden dangers are hidden in the soil, so that a method for effectively utilizing the electronic sludge is needed, and the utilization rate and the utilization value of the electronic sludge are increased.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a method for preparing microwave dielectric ceramics based on solid wastes, which is a method for preparing microwave dielectric ceramics with high microwave dielectric property and low production cost.
The technical scheme is as follows: in order to achieve the purpose, the invention provides a method for preparing microwave medium ceramic based on solid waste, which comprises the following steps:
(1) processing sludge of an electronic factory at high temperature to prepare a molten block, crushing the obtained molten block, adding water, ball-milling and drying to obtain powder;
(2) chemical method is used for quantifying the proportion of Ca and Al elements in the powder, the powder is weighed, and TiO is added into the powder2Mixing with rare earth oxide, ball milling for the first time, synthesizing, and ball milling for the second time to obtain ceramic powder;
(3) adding a binder into the ceramic powder for granulation, aging, pressing for molding, and then heating for plastic removal to obtain a ceramic green body;
(4) sintering the ceramic blank obtained in the step (3) to obtain the ceramic plate;
(5) and processing the ceramic wafer into a required size, ultrasonically cleaning, screen-printing silver, drying and burning the silver to obtain the microwave dielectric ceramic material.
Wherein, the high-temperature treatment conditions in the step (1) are as follows: heating to 1500-1600 ℃ at a heating rate of not higher than 2 ℃/min, preserving the heat for 1-3 hours, and cooling to room temperature along with the furnace.
Wherein, the molten block in the step (1) mainly comprises metal oxides of CaO and Al2O3And (4) forming.
Wherein, the water adding ball milling in the step (1) is a wet ball milling method, and the raw materials are as follows: ball: the mass ratio of water to water is 1 (2.8-5.2) to (0.6-1.5), wherein the ball milling medium is zirconia balls, and the ball milling time is 20-24 hours.
And (2) feeding the relevant waste gas generated in the step (1) into a sulfur removal tower, crushing the obtained molten block, adding water, ball-milling for 24 hours, and drying to obtain powder with the granularity of about one micron.
Wherein TiO is added thereto in the step (2)2With rare earth oxide to which TiO is added in an amount equimolar to Ca2And rare earth oxide in an amount equal to one-half mole of Al.
Wherein the rare earth oxide is R2O3. Such as Pr2O3、La2O3、Ce2O3And the like.
Wherein, the synthesis in the step (2) is carried out by heating to 1100-1300 ℃ at a heating rate of not higher than 2 ℃/min, preserving the heat for 1-3 hours, and cooling to room temperature along with the furnace.
Wherein, the conditions of the ball milling twice in the step (2) are the same as those of the ball milling in the step (1).
Wherein the binder in the step (3) is polyvinyl alcohol (PVA), and the addition amount of the binder is 5-7 wt% of the weight of the ceramic powder; the plastic removing condition is that the temperature is raised to 650-750 ℃ at the temperature raising rate of not higher than 2 ℃/min, and the temperature is kept for 1-3 hours.
And (4) heating to 1400-1600 ℃ at a heating rate of not higher than 2 ℃/min, preserving heat for 1-3 hours, and cooling to room temperature along with the furnace.
Wherein, the silver firing condition in the step (5) is 700-800 ℃, and the temperature is kept for 5-40 minutes.
The microwave dielectric ceramic prepared by the preparation method has good dielectric constant and resonant frequency temperature coefficient close to zero, and can be used for the microwave communication field, circuit board base materials and the like.
The sludge of the electronic factory used in the invention mainly contains CaSO4、Al(OH)3Organic solvents, microorganisms and trace amounts of other metal compounds, which are calcined at high temperature to form SO2Water vapor, CH gas, and metal oxides, mainly CaO and Al2O3. The microwave dielectric ceramic material prepared by using the raw materials such as Ti, rare earth elements and the like can expand the dielectric constant range of the microwave dielectric ceramic material, form a stable structure and improve the quality factor of the microwave dielectric ceramic material. The invention has novel material composition and simple process flow, and can consume the sludge generated by an electronic factory and reduce the harm to the ecology. The preparation process of the invention can be industrialized, and the production period is reduced.
In addition, since the sludge of the electronic factory contains more metal elements, has relatively high content, and contains certain heavy metals, if the sludge is buried or discarded anywhere, the sludge causes land pollution and resource waste. The invention adds other raw materials (such as TiO) on the basis of the original sludge2) And the atomic proportion of chemical elements is well prepared, and then microwave materials can be prepared and utilized according to the preparation principle of microwave dielectric ceramics. The key point of the invention is to firstly utilize the sludge of the electronic factory to prepare the microwave material with high added value, so that the sludge generated by the electronic factory has commercial value and is prevented from being discarded and polluted.
Meanwhile, the sludge of the electronic factory is very important in the whole preparation link at the high-temperature treatment temperature and the sintering temperature of the ceramic body, and the dielectric property of the final microwave dielectric ceramic can be obviously reduced due to the change of any temperature (such as low temperature). The quality factor Q and Q & f are lowered by the excessive temperature, and the comprehensive properties of the product are lost.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the invention provides a method for preparing microwave dielectric ceramics based on solid wastes, which is a method for preparing microwave dielectric ceramics with high microwave dielectric property and low production cost, effectively utilizes sludge of an electronic factory, the prepared microwave dielectric ceramics comprises 20-40% of sludge from the electronic factory, can effectively treat and recycle sludge of industrial solid wastes of the electronic factory, can purify and improve the environment to the maximum extent, has low product cost, can ensure that indexes such as the dielectric property and the like of the prepared microwave dielectric ceramics can reach standard requirements, has good dielectric constant and resonant frequency temperature coefficient close to zero, and can be used for the microwave communication field, circuit board base materials and the like.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The sludge of the electronic factory used in the embodiment of the invention can adopt most sludge of the electronic factory on the market, which does not contain radioactive elements.
Example 1
The composition of the material is as follows: ca0.6Ti0.6Pr0.4Al0.4O3
(1) Heating the sludge of the electronic factory to 1500 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, processing to obtain a molten block, feeding related waste gas into a desulfurizing tower, crushing the molten block, sieving with a 40-mesh sieve, and processing by a wet ball milling method, wherein a ball milling medium is zirconia balls, and mixing for 24 hours according to a mass ratio of the raw materials, namely balls and water, of 1:4.5:1.2, so that the components are uniformly mixed and the particle size of powder is reduced. After drying, sieving by a 40-mesh sieve.
(2) The molar ratio of Ca to Al in the powder is 3:2 by chemical titration, a certain mass of the powder is weighed, TiO with the molar quantity equal to that of Ca is added into the powder2Equal molar amount of Pr to 0.5Al2O3The raw materials are mixed by a wet ball milling method, and the raw materials are mixed for 24 hours according to the mass ratio of ball to water of 1:4.5:1.2, so that the components are uniformly mixed. After drying, sieving with a 40-mesh sieve, pressing the blocks under 5MPa, raising the temperature to 1200 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 2 hours to synthesize the ceramic powder.
(3) Grinding the ceramic powder in the step (2), and sieving with a 40-mesh sieve. And mixing according to a wet ball milling method, finely milling for 24 hours according to the mass ratio of the ball to the water of 1:4.5:1.0, and drying the finely milled ceramic powder. Then 6 wt.% of PVA binder (molecular weight 12 ten thousand) is added, granulation is carried out, briquetting and aging are carried out for 24 hours, the mixture is sieved by a 20-mesh sieve, compression molding is carried out under the pressure of 1.5MPa, and then the temperature is raised to 700 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 2 hours, and plastic discharging is carried out, thus obtaining the ceramic biscuit.
(4) And (3) putting the ceramic biscuit into an alumina crucible, heating to 1500 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 2 hours, and cooling along with the furnace to obtain the ceramic wafer. And grinding the sintered ceramic wafer to be 0.5mm thin, cleaning, drying, screen-printing silver paste, drying again, raising the temperature to 750 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation for 30 minutes to burn the silver to obtain the microwave dielectric ceramic material.
Comparative example 1:
the composition of the material is as follows: ca0.6Ti0.6Pr0.4Al0.4O3
(1) Heating sludge of an electronic factory to 1400 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, processing to obtain a molten block, feeding related waste gas into a desulfurizing tower, crushing the molten block, sieving the crushed molten block by a 40-mesh sieve, and processing by a wet ball milling method, wherein a ball milling medium is zirconia balls, and mixing the zirconia balls and the water for 24 hours according to a mass ratio of 1:4.5:1.2, so that the components are uniformly mixed and the particle size of powder is reduced. After drying, sieving by a 40-mesh sieve.
(2) The molar ratio of Ca to Al in the powder was 3:2 by chemical titration, a certain mass of the powder was weighed, TiO2 in an amount equimolar to Ca and Pr in an amount equimolar to 0.5Al were added to the powder2O3The raw materials are mixed by a wet ball milling method, and the raw materials are mixed for 24 hours according to the mass ratio of ball to water of 1:4.5:1.2, so that the components are uniformly mixed. After drying, sieving with a 40-mesh sieve, pressing the blocks under 5MPa, raising the temperature to 1200 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 2 hours to synthesize the ceramic powder.
(3) Grinding the ceramic powder in the step (2), and sieving with a 40-mesh sieve. And mixing according to a wet ball milling method, finely milling for 24 hours according to the mass ratio of the ball to the water of 1:4.5:1.0, and drying the finely milled ceramic powder. Then adding 6 wt.% of PVA binder, granulating, briquetting and aging for 24 hours, sieving with a 20-mesh sieve, pressing and molding under the pressure of 1.5MPa, then heating to 700 ℃ at the heating rate of 2 ℃/min, preserving heat for 2 hours, and removing plastic to obtain the ceramic biscuit.
(4) And (3) putting the ceramic biscuit into an alumina crucible, heating to 1500 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 2 hours, and cooling along with the furnace to obtain the ceramic wafer. And grinding the sintered ceramic wafer to be 0.5mm thin, cleaning, drying, screen-printing silver paste, drying again, raising the temperature to 750 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation for 30 minutes to burn the silver to obtain the microwave dielectric ceramic material.
Comparative example 2:
the composition of the material is as follows: ca0.6Ti0.6Pr0.4Al0.4O3
(1) Heating the sludge of the electronic factory to 1500 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, processing to obtain a molten block, feeding related waste gas into a desulfurizing tower, crushing the molten block, sieving with a 40-mesh sieve, and processing by a wet ball milling method, wherein a ball milling medium is zirconia balls, and mixing for 24 hours according to a mass ratio of the raw materials, namely balls and water, of 1:4.5:1.2, so that the components are uniformly mixed and the particle size of powder is reduced. After drying, sieving by a 40-mesh sieve.
(2) The molar ratio of Ca to Al in the powder is 3:2 by chemical titration, a certain mass of the powder is weighed, TiO with the molar quantity equal to that of Ca is added into the powder2Equal molar amount of Pr to 0.5Al2O3The raw materials are mixed by a wet ball milling method, and the raw materials are mixed for 24 hours according to the mass ratio of ball to water of 1:4.5:1.2, so that the components are uniformly mixed. After drying, sieving with a 40-mesh sieve, pressing the blocks under 5MPa, raising the temperature to 1200 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 2 hours to synthesize the ceramic powder.
(3) Grinding the ceramic powder in the step (2), and sieving with a 40-mesh sieve. And mixing according to a wet ball milling method, finely milling for 24 hours according to the mass ratio of the ball to the water of 1:4.5:1.0, and drying the finely milled ceramic powder. Then adding 6 wt.% of PVA binder, granulating, briquetting and aging for 24 hours, sieving with a 20-mesh sieve, pressing and molding under the pressure of 1.5MPa, then heating to 700 ℃ at the heating rate of 2 ℃/min, preserving heat for 2 hours, and removing plastic to obtain the ceramic biscuit.
(4) And (3) putting the ceramic biscuit into an alumina crucible, heating to 1300 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 2 hours, and cooling along with the furnace to obtain the ceramic wafer. And grinding the sintered ceramic wafer to be 0.5mm thin, cleaning, drying, screen-printing silver paste, drying again, raising the temperature to 750 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation for 30 minutes to burn the silver to obtain the microwave dielectric ceramic material.
Comparative example 3
Comparative example 3 the same procedure as in example 1, except that: in the step (1), the sludge in the electronic factory is heated to 1800 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 2 hours.
Comparative example 4
Comparative example 4 is the same as example 1 except that: and (4) putting the ceramic biscuit into an alumina crucible, raising the temperature to 1800 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 2 hours.
Example 2
The composition of the material is as follows: ca0.6Ti0.6Pr0.4Al0.4O3
(1) Heating the sludge of the electronic factory to 1600 ℃ at a heating rate of 2 ℃/min, preserving heat for 1 hour, processing to obtain a molten block, feeding related waste gas into a desulfurizing tower, crushing the molten block, sieving with a 40-mesh sieve, and processing by a wet ball milling method, wherein a ball milling medium is zirconia balls, and mixing for 20 hours according to a mass ratio of the raw materials, namely balls and water, of 1:2.8:0.6, so that the components are uniformly mixed and the particle size of powder is reduced. After drying, sieving by a 40-mesh sieve.
(2) The molar ratio of Ca to Al in the powder is 3:2 by chemical titration, a certain mass of the powder is weighed, TiO with the molar quantity equal to that of Ca is added into the powder2Equal molar amount of Pr to 0.5Al2O3The raw materials are mixed by a wet ball milling method, and the raw materials are mixed for 24 hours according to the mass ratio of ball to water of 1:4.5:1.2, so that the components are uniformly mixed. After drying, sieving the mixture by a 40-mesh sieve, pressing the mixture into blocks under the pressure of 5MPa, raising the temperature to 1100 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 3 hours to synthesize the ceramic powder.
(3) Grinding the ceramic powder in the step (2), and sieving with a 40-mesh sieve. And mixing according to a wet ball milling method, finely milling for 24 hours according to the mass ratio of the ball to the water of 1:4.5:1.0, and drying the finely milled ceramic powder. Then adding 5 wt.% of PVA binder (molecular weight 12 ten thousand), granulating, briquetting and aging for 24 hours, sieving by a 20-mesh sieve, pressing and molding under the pressure of 1.5MPa, then heating to 650 ℃ at the heating rate of 2 ℃/min, preserving heat for 3 hours, and discharging to obtain the ceramic biscuit.
(4) And (3) putting the ceramic biscuit into an alumina crucible, heating to 1400 ℃ at the heating rate of 2 ℃/min, preserving the temperature for 3 hours, and cooling along with the furnace to obtain the ceramic chip. And grinding the sintered ceramic wafer to be 0.5mm thin, cleaning, drying, screen-printing silver paste, drying again, heating to 700 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation for 40 minutes to burn the silver to obtain the microwave dielectric ceramic material.
Example 3
The composition of the material is as follows: ca0.6Ti0.6Pr0.4Al0.4O3
(1) Heating the sludge of the electronic factory to 1500 ℃ at a heating rate of 2 ℃/min, preserving heat for 3 hours, processing to obtain a molten block, feeding related waste gas into a desulfurizing tower, crushing the molten block, sieving with a 40-mesh sieve, and processing by a wet ball milling method, wherein a ball milling medium is zirconia balls, and mixing for 24 hours according to a mass ratio of the raw materials, namely balls and water, of 1:5.2:1.5, so that the components are uniformly mixed and the particle size of powder is reduced. After drying, sieving by a 40-mesh sieve.
(2) The molar ratio of Ca to Al in the powder is 3:2 by chemical titration, a certain mass of the powder is weighed, TiO with the molar quantity equal to that of Ca is added into the powder2Equal molar amount of Pr to 0.5Al2O3The raw materials are mixed by a wet ball milling method, and the raw materials are mixed for 24 hours according to the mass ratio of ball to water of 1:4.5:1.2, so that the components are uniformly mixed. After drying, sieving with a 40-mesh sieve, pressing the blocks under 5MPa, raising the temperature to 1300 ℃ at the heating rate of 2 ℃/min, and preserving the temperature for 1 hour to synthesize the ceramic powder.
(3) Grinding the ceramic powder in the step (2), and sieving with a 40-mesh sieve. And mixing according to a wet ball milling method, finely milling for 24 hours according to the mass ratio of the ball to the water of 1:4.5:1.0, and drying the finely milled ceramic powder. Then adding 7 wt.% of PVA binder (molecular weight 12 ten thousand), granulating, briquetting and aging for 24 hours, sieving by a 20-mesh sieve, pressing and molding under the pressure of 1.5MPa, then heating to 750 ℃ at the heating rate of 2 ℃/min, preserving heat for 1 hour, and discharging to obtain the ceramic biscuit.
(4) And (3) putting the ceramic biscuit into an alumina crucible, heating to 1600 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 1 hour, and cooling along with the furnace to obtain the ceramic wafer. And grinding the sintered ceramic wafer to be 0.5mm thin, cleaning, drying, screen-printing silver paste, drying again, raising the temperature to 800 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation for 5 minutes to burn the silver to obtain the microwave dielectric ceramic material.
Test example 1
For these embodiments, the microwave dielectric ceramic material sample obtained by sintering can be tested by using a TE01D resonant cavity and a network analyzer E5071C at normal temperature, the dielectric property of the microwave at the resonant frequency of the cylinder can be tested by using the dielectric resonant cavity method of HakkiandColeman, and the temperature coefficient of the resonant frequency can be tested by using an oven, so that the test results of the dielectric property of the microwave dielectric ceramic material are shown in table 1:
TABLE 1 measurement of dielectric properties of microwave dielectric ceramic materials
As can be seen from table 1, the dielectric properties dielectric constant, center frequency, q.f and t.f (resonant frequency temperature coefficient) of the microwave dielectric ceramic material prepared in inventive example 1 are significantly better than those of comparative examples 1-4, while the q.f. high of the product prepared in inventive example 1 represents low dielectric loss of the material system; meanwhile, the Tf of the product prepared in the embodiment 1 is close to zero, and the product can be better applied to the field of microwave communication, circuit board substrates and the like. The results of the above comparative examples 1 to 4 illustrate the importance of sludge from electronic factories at high temperature treatment temperature and sintering temperature of ceramic bodies in the preparation method of the present invention.
Claims (10)
1. A method for preparing microwave dielectric ceramics based on solid wastes is characterized by comprising the following steps:
(1) processing sludge of an electronic factory at high temperature to prepare a molten block, crushing the obtained molten block, adding water, ball-milling and drying to obtain powder;
(2) chemically quantifying the powderThe ratio of Ca and Al elements is measured, the powder is weighed, and TiO is added into the powder2Mixing with rare earth oxide, ball milling for the first time, synthesizing, and ball milling for the second time to obtain ceramic powder;
(3) adding a binder into the ceramic powder for granulation, aging, pressing for molding, and then heating for plastic removal to obtain a ceramic green body;
(4) sintering the ceramic blank obtained in the step (3) to obtain the ceramic plate;
(5) and processing the ceramic chip, ultrasonically cleaning, screen-printing silver, drying and burning the silver to obtain the microwave dielectric ceramic material.
2. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the high-temperature treatment conditions in the step (1) are as follows: heating to 1500-1600 ℃ at a heating rate of not higher than 2 ℃/min, preserving the heat for 1-3 hours, and cooling to room temperature along with the furnace.
3. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the melting block of the step (1) is mainly composed of metal oxides of CaO and Al2O3And (4) forming.
4. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the water-adding ball milling in step (1) is preferably mixed by a wet ball milling method according to the following raw materials: ball: the mass ratio of water to water is 1 (2.8-5.2) to (0.6-1.5), wherein the ball milling medium is zirconia balls, and the ball milling time is 20-24 hours.
5. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the step (2) is to add TiO into the microwave dielectric ceramics2With rare earth oxide to which TiO is added in an amount equimolar to Ca2And rare earth oxide in an amount equal to one-half mole of Al.
6. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the rare earth isThe oxide is R2O3。
7. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the synthesis in the step (2) is carried out by heating to 1100-1300 ℃ at a heating rate of not higher than 2 ℃/min, keeping the temperature for 1-3 hours, and cooling to room temperature along with a furnace.
8. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the conditions of the ball milling twice in the step (2) are the same as those of the ball milling in the step (1).
9. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the binder in the step (3) is polyvinyl alcohol (PVA), and the amount of the added binder is 5-7 wt.% of the weight of the ceramic powder; and the plastic removing condition is that the temperature is raised to 650-750 ℃ at the temperature rise rate of not higher than 2 ℃/min, and the temperature is kept for 1-3 hours.
10. The method for preparing microwave dielectric ceramics based on solid wastes according to claim 1, wherein the sintering conditions in the step (4) are heating to 1400-1600 ℃ at a heating rate of not more than 2 ℃/min, keeping the temperature for 1-3 hours, and furnace cooling to room temperature.
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