CN103172367A - Preparation method of microwave dielectric ceramic material - Google Patents
Preparation method of microwave dielectric ceramic material Download PDFInfo
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- CN103172367A CN103172367A CN2011104357847A CN201110435784A CN103172367A CN 103172367 A CN103172367 A CN 103172367A CN 2011104357847 A CN2011104357847 A CN 2011104357847A CN 201110435784 A CN201110435784 A CN 201110435784A CN 103172367 A CN103172367 A CN 103172367A
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Abstract
The invention discloses a preparation method of a microwave dielectric ceramic material. The preparation method comprises the following steps of: mechanically mixing mixed powder of calcium carbonate, alumina, lanthana and titanium dioxide uniformly to form powder particles; carrying out primary high-energy ball milling on the powder particles to uniformly refine the powder particles; calcining the powder after primary high-energy ball milling at a high temperature in a closed container to form precursor powder; and carrying out secondary high-energy ball milling on the precursor powder to further refine the precursor powder uniformly to form ceramic powder. The preparation method has the beneficial effects that by appropriately increasing the mole percent of the volatile element Ca in the raw materials and combining with the ultrafine powder preparation technology and thereby sintering the microwave dielectric ceramic material with high densification, a medium dielectric constant and a high quality factor at low temperature, not only can the defect effects caused by the volatile element Ca be inhibited, the sintering temperature greatly reduced and the sintering time shortened, but also high densification of the sintered ceramic body is achieved, thus reducing the production cost and the technical difficulty.
Description
Technical field
The present invention relates to the stupalith field, particularly relate to a kind of preparation method of microwave dielectric ceramic materials.
Background technology
Microwave-medium ceramics refers to be applied to the new function electron ceramic material that has the stupalith of fabulous dielectric properties in the microwave frequency range of 300MHz～300GHz and be applied to complete as dielectric material in the microwave frequency band circuit one or more functions, is bringing into play the functions such as media isolated, Medium Wave Guide and dielectric resonance in microwave circuit.
Due to perovskite structure (1-x) CaTiO
3-xLaAlO
3(be called for short CTLA, wherein x represents molar percentage) base microwave medium ceramic material has high dielectric constant (30＜ε
r＜45), close to zero temperature coefficient of resonance frequency (τ
f～0) and quite high quality factor (Q * f＞30000), extensive concern and the research of industry have been caused.Yet, for the more cheap CaTiO of cost
3-LaAlO
3Base microwave medium ceramic material, the research of industry mainly rest on the mutual relationship of its microtexture and dielectric properties, for the research of its preparation method seldom.
At present, the preparation method that domestic and international manufacturer mostly adopts mechanically mixing to be combined with solid state sintering, solid state reaction occurs under the high-temperature calcination condition and prepare required ceramic powder after being about to the solid powder raw material and fully mixing in planetary or stirring ball mill, and then compression moulding, solid state sintering become medium ceramic material.This traditional preparation method mainly contains following defective: in high-temperature sintering process, the powder reactive behavior is relatively poor, need very high sintering temperature (1500～1650 degrees centigrade) and very long sintering time (12～24 hours), caused high production energy consumption, even adopt lqiuid phase sintering method to reduce sintering temperature, the degree that reduces is limited (1450 degrees centigrade) also, the dielectric properties of destruction finished product that also can be in various degree; The synthetic ceramic powder particle diameter of reaction is larger, and size-grade distribution is wide, is difficult to realize the sintering high compaction, and its homogeneity also only has by extending mixing time and guarantee, namely is difficult to obtain to possess the medium ceramic material of stablizing good microwave dielectric property; And ignored the detrimentally affect that " defect effect " that Volatile Elements Ca causes causes the product microwave property in sintering process.
Therefore, need to provide a kind of preparation method of microwave dielectric ceramic materials, to solve the problem that in prior art, in preparation microwave dielectric ceramic materials process, sintering temperature is too high, sintering time is long and be difficult to realize sintering densification.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of preparation method of microwave dielectric ceramic materials, can reduce sintering temperature, shorten sintering time and suppress " defect effect " that Volatile Elements Ca causes in preparation microwave dielectric ceramic materials process.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of microwave dielectric ceramic materials, comprising: the mixed powder of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide is carried out the mechanical uniform mixing, form powder granule; Powder granule is carried out high-energy ball milling for the first time, with the even refinement of powder granule; With the powder high-temperature calcination in encloses container after high-energy ball milling for the first time, form the presoma powder; The presoma powder is carried out high-energy ball milling for the second time, with the further evenly refinement of presoma powder, form ceramic powder.
Wherein, also comprise after the high-energy ball milling step for the second time: mist projection granulating, add concentration and be 5%, mass percent is 5%～10% polyvinyl alcohol water solution, ceramic powder is made the powder granule of the spherical mobility of tool in ceramic powder.
Wherein, also comprise after the mist projection granulating step: compression moulding, the powder granule of the spherical mobility of tool is made the pressed compact of desired shape.
Wherein, pressed compact carries out two-sided compression moulding by pressing machine in filler mode manually or automatically, perhaps carries out shot moulding by shot forming technique.
Wherein, also comprise after the compression moulding step: sintering, pressed compact is carried out stoking, form ceramic blank, wherein, the highest sintering temperature is 1300～1500 degrees centigrade, soaking time is 3～6 hours.
Wherein, also comprise after sintering step: mechanical workout and sample detection, ceramic blank is carried out surface treatment obtain sample, and the dielectric properties index of measure sample.
Wherein, according to chemical formula (1-x) Ca
1+yTiO
3-x[La
1-zRe
zAlO
3] make wherein molar percentage x, y and z satisfy respectively 0.1mol%≤x≤0.7mol%, 0.1mol%≤y≤0.5mol% and 0.01mol%≤z≤0.1mol%, the purity of calcium carbonate and aluminum oxide is all greater than 99.5%, and the purity of titanium dioxide and lanthanum trioxide is not less than 99.9%.
Wherein, the mixed powder of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide is carried out the step that mechanical uniform mixes to be comprised: add the zirconium dioxide abrading-ball as grinding medium in spherical tank, adding dehydrated alcohol or deionized water as organic solvent, mixed powder to be carried out mechanical uniform mixes, and after forming powder granule, remove organic solvent and carry out drying treatment, wherein, mixed powder, grinding medium, organic solvent three part by weight be 1: 3: 3 and account for 60%～80% of spherical tank volume, and mixing time is 1～3 hour.
Wherein, powder granule is carried out for the first time in the high-energy ball milling step, ratio of grinding media to material is 8: 1～10: 1, and Ball-milling Time is 1～3 hour, and rotating speed is 600～800 rev/mins.
Wherein, for the first time the size-grade distribution of the powder after high-energy ball milling in 1～2 μ m scope.
Wherein, in the high-temperature calcination step, encloses container is high-temperature crucible, and calcining temperature is 1100～1350 degrees centigrade, and soaking time is 3～5 hours.
Wherein, the presoma powder is carried out for the second time in the high-energy ball milling step, ratio of grinding media to material is 10: 1～12: 1, Ball-milling Time 1～3 hour, 800～1000 rev/mins of rotating speeds.
Wherein, for the second time the granularity of the ceramic powder after high-energy ball milling less than 1 μ m.
Wherein, the presoma powder is carried out for the second time further adding modification doping agent, property-modifying additive and sintering aid in the high-energy ball milling step.
Wherein, the modification doping agent is the oxide compound that contains rare earth element, and rare earth element is one or more in yttrium, neodymium, cerium, praseodymium, samarium, europium, gadolinium, dysprosium, erbium and ytterbium, and property-modifying additive is CaO, SrO, TiO
2, ZnO, Al
2O
3, Nb
2O
5And Ta
2O
5In one or more, sintering aid is Bi
2O
3, B
2O
3, CuO, V
2O
5And one or more in BaO.
Wherein, the formula of dielectric material is according to chemical formula (1-x) Ca
1+yTiO
3-x[La
1-zRe
zAlO
3] make wherein molar percentage x, y and z satisfy respectively 0.1mol%≤x≤0.7mol%, 0.1mol%≤y≤0.5mol% and 0.01mol%≤z≤0.1mol%.Wherein, the mass percent of property-modifying additive is 1%～4% of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide total amount, and the mass percent of sintering aid is 0.1%～1% of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide total amount.
The invention has the beneficial effects as follows: the situation that is different from prior art, thereby the preparation method of microwave dielectric ceramic materials of the present invention adopts the medium dielectric constant microwave medium of the molar percentage easy fired high compaction of appropriate increase Volatile Elements Ca in raw material and the microwave dielectric ceramic materials of high quality factor, " defect effect " that not only can suppress the volatile generation of Ca element, reduce to a great extent sintering temperature and shorten sintering time, and realize burning till the high compaction of porcelain body, thereby reduced production cost and technical difficulty.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, during the below will describe embodiment, the accompanying drawing of required use is done to introduce simply, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings, wherein:
Fig. 1 is preparation method's the schematic flow sheet of the microwave dielectric ceramic materials of the embodiment of the present invention;
Fig. 2 is in the preparation method of microwave dielectric ceramic materials according to an embodiment of the invention, pass through respectively traditional mechanically mixing (12 hours) (a) and for the first time high-energy ball milling (2 hours) (b) prepare respectively the particle size distribution figure of powder;
Fig. 3 is in the preparation method of microwave dielectric ceramic materials according to an embodiment of the invention, adopts respectively traditional mechanically mixing+solid reaction process (a) and mechanically mixing of the present invention to make respectively scanning electron microscope (SEM) image of CTLA base microwave dielectric ceramics sample in conjunction with high-energy ball milling method (b).
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiment.Based on the embodiment in the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
Embodiment one
A kind of preparation method of microwave dielectric ceramic materials, its schematic flow sheet comprises as shown in Figure 1:
Step S101 carries out mechanical uniform with the mixed powder of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide and mixes, and forms powder granule.
Step S101 is included in further to add the zirconium dioxide abrading-ball in spherical tank as grinding medium and add dehydrated alcohol or deionized water as organic solvent, mixed powder to be carried out mechanical uniform and mixes, and after forming powder granule, remove organic solvent and carry out drying treatment, wherein, mixed powder, grinding medium, organic solvent three part by weight be 1: 3: 3 and account for 60%～80% of spherical tank volume, and mixing time is 1～3 hour.Wherein, the formula of microwave dielectric ceramic materials is according to chemical formula (1-x) Ca
1+yTiO
3-x[La
1-zRe
zAlO
3] make wherein molar percentage x, y and z satisfy respectively 0.1mol%≤x≤0.7mol%, 0.1mol%≤y≤0.5mol% and 0.01mol%≤z≤0.1mol%, the purity of calcium carbonate and aluminum oxide is all greater than 99.5%, and the purity of titanium dioxide and lanthanum trioxide is not less than 99.9%.By improving the molar percentage of calcium carbonate, can suppress " defect effect " that Volatile Elements Ca causes.
Step S102 carries out high-energy ball milling for the first time with powder granule, with the even refinement of powder granule.
In the present embodiment, carry out high-energy ball milling for the first time with the zirconium dioxide abrading-ball as the grinding medium of high-energy ball milling, with the size-grade distribution of the powder after high-energy ball milling for the first time in 1～2 μ m scope, reactive behavior and the contact area of powder granule have effectively been improved, and then reach the purpose that reduces the calcination reaction synthesis temperature, wherein, ratio of grinding media to material is 8: 1～10: 1, Ball-milling Time is 1～3 hour, and rotating speed is 600～800 rev/mins.
Step S103 with the powder high-temperature calcination in encloses container after high-energy ball milling for the first time, forms the presoma powder.
In the present embodiment, the powder after high-energy ball milling for the first time is placed in airtight high-temperature crucible, through the presoma powder of pyroreaction synthesis of high purity principal crystalline phase.The processing parameter of high-temperature calcination process is: encloses container is high-temperature crucible, and calcining temperature is 1100～1350 degrees centigrade, and soaking time is 3～5 hours.
Step S104 carries out high-energy ball milling for the second time with the presoma powder, with the further evenly refinement of presoma powder, forms ceramic powder.
In the present embodiment, with the grinding medium of zirconium dioxide abrading-ball as high-energy ball milling, and further add modification doping agent, property-modifying additive and sintering aid and carry out high-energy ball milling for the second time.Control the granularity of the ceramic powder that forms less than 1 μ m, the modification doping agent is the oxide compound that contains rare earth element, and rare earth element is one or more in yttrium, neodymium, cerium, praseodymium, samarium, europium, gadolinium, dysprosium, erbium and ytterbium, and property-modifying additive is CaO, SrO, TiO
2, ZnO, Al
2O
3, Nb
2O
5And Ta
2O
5In one or more, sintering aid is Bi
2O
3, B
2O
3, CuO, V
2O
5And one or more in BaO, the formula of this microwave dielectric ceramic materials is according to chemical formula (1-x) Ca
1+yTiO
3-x[La
1-zRe
zAlO
3] make wherein molar percentage x, y and z satisfy respectively 0.1mol%≤x≤0.7mol%, 0.1mol%≤y≤0.5mol% and 0.01mol%≤z≤0.1mol%, wherein, the mass percent of property-modifying additive is 1%～4% of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide total amount, and the mass percent of sintering aid is 0.1%～1% of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide total amount.By adding modification doping agent, property-modifying additive and sintering aid, can reach the purpose that reduces sintering temperature and microwave-medium ceramics sintering densification.Wherein, ratio of grinding media to material is 10: 1～12: 1, Ball-milling Time 1～3 hour, 800～1000 rev/mins of rotating speeds.
In addition, in the present embodiment, after ceramic powder is formed, can also be further comprising the steps as required:
Mist projection granulating adds concentration and is 5%, mass percent is 5%～10% polyvinyl alcohol water solution, ceramic powder is made the powder granule of the spherical mobility of tool, so that this powder granule has good mobility in ceramic powder.
The pressed compact of desired shape is made the powder granule of the spherical mobility of tool in compression moulding.
In the present embodiment, pressed compact carries out two-sided compression moulding by pressing machine in filler mode manually or automatically, perhaps carries out shot moulding by shot forming technique.
Sintering carries out stoking with pressed compact, forms ceramic blank, and wherein, the highest sintering temperature is 1300～1500 degrees centigrade, and soaking time is 3～6 hours.
In the present embodiment, pressed compact is put into airtight high-temperature resistant aluminium oxide crucible carry out stoking, in the high temperature period, solid state reaction occurs and generate fine and close ceramic blank.
Mechanical workout and sample detection are carried out surface treatment with ceramic blank and are obtained sample, and the dielectric properties index of measure sample.
In the present embodiment, surface treatment can be adopted the mechanical workout modes such as grinding, polishing, obtains the specimen of desired size, and measures the dielectric properties index with network analyzer: DIELECTRIC CONSTANT ε
r, temperature coefficient of resonance frequency τ
fAnd quality factor q.
Embodiment two
A kind of preparation method of microwave dielectric ceramic materials comprises:
Step 1, before batching with the former powder of lanthanum trioxide 800 degrees centigrade of lower pre-burnings 2 hours, and with the former powder of titanium dioxide 1280 degrees centigrade of lower pre-burnings 3 hours, to carry out drying; According to chemical formula 0.88Ca
1+0.15mol%TiO
3-0.12LaAlO
3Calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide mixed powder are placed on carry out the mechanical uniform mixing in spherical tank; Add the zirconium dioxide abrading-ball as grinding medium, add dehydrated alcohol or deionized water as organic solvent, and after forming powder granule, remove organic solvent and carry out drying treatment, mixed powder, abrading-ball, solvent (weight) ratio are that 1: 3: 3 and its account for 80% of spherical tank volume, and the raw material mixing time is 1 hour.
In the present embodiment, the stoichiometric ratio of calcium carbonate and titanium dioxide is 0.88mol%, and the stoichiometric ratio of aluminum oxide and lanthanum trioxide is 0.12mol%.Need to prove, the purity of calcium carbonate and alumina powder is all greater than 99.5%, and the purity of titanium dioxide and lanthanum trioxide powder is not less than 99.9%.
Step 2, take the zirconium dioxide abrading-ball as grinding medium, will carry out high-energy ball milling for the first time after the powder drying of step 1 and obtain the mixing raw material of even refinement.Wherein, High Energy Ball Milling Time is 1 hour, and ratio of grinding media to material is 10: 1, and rotating speed is 800 rev/mins.
Step 3, the mixing raw material of step 2 is placed in airtight high-temperature crucible, through the synthetic presoma powder with high purity principal crystalline phase of high-temperature calcination reaction; Calcining temperature is 1200 degrees centigrade, and soaking time is 3 hours.
Step 4, take the zirconium dioxide abrading-ball as grinding medium, powder after calcining is carried out high-energy ball milling for the second time obtains further the evenly ceramic powder of refinement.Wherein, High Energy Ball Milling Time is 1 hour, and ratio of grinding media to material is 10: 1, and rotating speed is 1000 rev/mins.
Step 5, to obtain in powder adding the mass percent example in step 4 be 10% polyvinyl alcohol (PVA) aqueous solution (concentration is 5%), utilizes drying tower or tablets press to make the powder granule of spherical and good fluidity.
Step 6, with pressing machine (filler manually or automatically), powder granule is made the pressed compact of desired shape, adopted two-sided compacting, its pressing pressure is 120MPa; Perhaps, adopt shot forming technique also can obtain the pressed compact of desired shape.
Step 7, pressed compact is put into the high-temperature resistant aluminium oxide crucible of sealing, carried out stoking.Wherein, the highest sintering temperature is 1500 degrees centigrade, and soaking time is 4 hours.
The porcelain body blank is burnt till in step 8, taking-up, obtains required specimen size after the surface treatments such as grinding, polishing.Then, utilizing network analyzer to record its dielectric properties index is respectively: ε
r=45..4; τ
f=7.2ppm/ ℃; Q * f=47800 (test frequency is 1.1GHz).
Embodiment three
A kind of preparation method of microwave dielectric ceramic materials comprises:
Step 1, before batching with the former powder of lanthanum trioxide 800 degrees centigrade of lower pre-burnings 2 hours, and with the former powder of titanium dioxide 1280 degrees centigrade of lower pre-burnings 3 hours, to carry out drying; According to chemical formula 0.52Ca
1+0.2mol%TiO
3-0.48LaAlO
3Calcium carbonate, aluminum oxide, lanthanum trioxide, titanium dioxide mixed powder are placed on carry out the mechanical uniform mixing in spherical tank; Add the zirconium dioxide abrading-ball as grinding medium, add dehydrated alcohol or deionized water as organic solvent, mixed powder, abrading-ball, solvent (weight) ratio are that 1: 3: 3 and its account for 60% of spherical tank volume, and the raw material mixing time is 2 hours.
In the present embodiment, the stoichiometric ratio of calcium carbonate and titanium dioxide is 0.72mol%, and the stoichiometric ratio of aluminum oxide and lanthanum trioxide is 0.28mol%.Need to prove, the purity of calcium carbonate and alumina powder is all greater than 99.5%, and the purity of titanium dioxide and lanthanum trioxide powder is not less than 99.9%.
Step 2, take the zirconium dioxide abrading-ball as grinding medium, the dried powder of step 1 is carried out for the first time high-energy ball milling to obtain the mixing raw material of even refinement.Wherein, High Energy Ball Milling Time is 1 hour, and ratio of grinding media to material is 12: 1, and rotating speed is 1000 rev/mins.
Step 3, the mixing raw material of step 2 is placed in airtight high-temperature crucible, through the synthetic presoma powder with high purity principal crystalline phase of pyroreaction.Wherein, calcining temperature is 1280 degrees centigrade, and soaking time is 4 hours.
Step 4, take the zirconium dioxide abrading-ball as grinding medium, powder after calcining is carried out high-energy ball milling for the second time obtains further the evenly ceramic powder of refinement.Wherein, High Energy Ball Milling Time is 1 hour, and ratio of grinding media to material is 10: 1, and rotating speed is 800 rev/mins.
Step 5, the mass percent example of adding in the powder that step 4 obtains are 8% polyvinyl alcohol (PVA) aqueous solution (concentration is 5%), utilize drying tower or tablets press to make the powder granule of spherical and good fluidity.
Step 6, with pressing machine (filler manually or automatically), powder granule is made the pressed compact of desired shape, adopted two-sided compacting, its pressing pressure is 120MPa; Perhaps, adopt shot forming technique also can obtain the pressed compact of desired shape.
Step 7, pressed compact is put into the high-temperature resistant aluminium oxide crucible of sealing, carried out stoking.Wherein, the highest sintering temperature is 1450 degrees centigrade, and soaking time is 4 hours.
The porcelain body blank is burnt till in step 8, taking-up, obtains required specimen size after the surface treatments such as grinding, polishing.Then, utilizing network analyzer to record its dielectric properties index is respectively: ε
r=34.6; τ
f=-8.5ppm/ ℃; Q * f=41300 (test frequency is 1.1GHz).
Embodiment four
A kind of preparation method of microwave dielectric ceramic materials comprises:
Step 1, before batching with the former powder of lanthanum trioxide 800 degrees centigrade of lower pre-burnings 2 hours, and with the former powder of titanium dioxide 1280 degrees centigrade of lower pre-burnings 3 hours, to carry out drying; According to chemical formula 0.36Ca
1+0.35mol%TiO
3-0.64LaAlO
3Calcium carbonate, aluminum oxide, lanthanum trioxide, titanium dioxide mixed powder are placed on carry out the mechanical uniform mixing in spherical tank; Add the zirconium dioxide abrading-ball as grinding medium, add dehydrated alcohol or deionized water as organic solvent, mixed powder, abrading-ball, solvent (weight) ratio are that 1: 3: 3 and its account for 70% of spherical tank volume, and the raw material mixing time is 8 hours.
In the present embodiment, the stoichiometric ratio of calcium carbonate and titanium dioxide is 0.36mol%, and the stoichiometric ratio of aluminum oxide and lanthanum trioxide is 0.64mol%.Need to prove, the purity of calcium carbonate and alumina powder is all greater than 99.5%, and the purity of titanium dioxide and lanthanum trioxide powder is not less than 99.9%.
Step 2, take the zirconium dioxide abrading-ball as grinding medium, the dried powder of step 1 is carried out for the first time high-energy ball milling to obtain the mixing raw material of even refinement.Wherein, High Energy Ball Milling Time is 2 hours, and ratio of grinding media to material is 10: 1, and rotating speed is 600 rev/mins.
Step 3, the mixing raw material of step 2 is placed in airtight high-temperature crucible, through the synthetic presoma powder with high purity principal crystalline phase of pyroreaction.Wherein, calcining temperature is 1250 degrees centigrade, and soaking time is 6 hours.
Step 4, take the zirconium dioxide abrading-ball as grinding medium, powder after calcining is carried out high-energy ball milling for the second time obtains further the evenly ceramic powder of refinement.Wherein, High Energy Ball Milling Time is 2 hours, and ratio of grinding media to material is 8: 1, and rotating speed is 1000 rev/mins.
Step 5, the mass percent example of adding in the powder that step 4 obtains are 5% polyvinyl alcohol (PVA) aqueous solution (concentration is 5%), utilize drying tower or tablets press to make the powder granule of spherical and good fluidity.
Step 6, with pressing machine (filler manually or automatically), powder granule is made the pressed compact of desired shape, adopted two-sided compacting, its pressing pressure is 100MPa; Perhaps, adopt shot forming technique also can obtain the pressed compact of desired shape.
Step 7, pressed compact is put into the high-temperature resistant aluminium oxide crucible of sealing, carried out stoking.Wherein, the highest sintering temperature is 1400 ℃, and soaking time is 6 hours.
The porcelain body blank is burnt till in step 8, taking-up, obtains required specimen size after the surface treatments such as grinding, polishing.Then, utilizing network analyzer to record its dielectric properties index is respectively: ε
r=35.6; τ
f=-12.9ppm/ ℃; Q * f=40000 (test frequency is 1.1GHz).
Embodiment five
The employing processing parameter identical with the preparation method of the microwave dielectric ceramic materials of embodiment three carries out trial-production and the detection of different components proportioning sample, be described in detail thereby the above embodiment of the present invention is applied in specific environment, the fundamental property index of gained sample sees table 1 for details.
Table 1 different components (x) proportioning (1-x) Ca
(1+0.2mol%)TiO
3-xLaAlO
3The dielectric properties index of sample
Embodiment six
Preparation process processing parameter with embodiment two, appropriate modification doping agent, property-modifying additive and the sintering aid of adding, the modification doping agent is the oxide compound that contains rare earth element, rare earth element is one or more in yttrium, neodymium, cerium, praseodymium, samarium, europium, gadolinium, dysprosium, erbium and ytterbium, and property-modifying additive is CaO, SrO, TiO
2, ZnO, Al
2O
3, Nb
2O
5And Ta
2O
5In one or more, sintering aid is Bi
2O
3, B
2O
3, CuO, V
2O
5And one or more in BaO, the formula of this microwave dielectric ceramic materials is according to chemical formula 0.88Ca
1+yTiO
3-0.12[La
1-zRe
zAlO
3] make wherein molar percentage y and z satisfy respectively 0.1mol%≤y≤0.5mol% and 0.01mol%≤z≤0.1mol%, wherein, the mass percent of property-modifying additive is 1%～4% of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide total amount, the mass percent of sintering aid is 0.1%～1% of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide total amount, and adopt the same process parameter to carry out trial-manufacture of sample and detection, be described in detail thereby the above embodiment of the present invention is applied in specific environment, its fundamental property index sees table 2-5 for details.
The dielectric properties of the corresponding sample of the different molar percentage calcium carbonate of table 2 refer to
The dielectric properties index of the rare-earth element modified doping sample of the different proportionings of table 3
The dielectric properties index of the corresponding sample of the different proportioning property-modifying additives of table 4
The dielectric properties index of the corresponding sample of the different proportioning sintering aids of table 5
The embodiment of the present invention is provided on the basis of traditional mechanically mixing and solid phase reaction method in conjunction with high-energy ball-milling process, impel the even refinement of ceramic powder by high-energy ball milling for the first time, not only effectively reduce the powder calcined temperature, and guaranteed the ceramic powder of reaction synthesis of high purity principal crystalline phase.Impel further evenly refinement of powder granule by high-energy ball milling for the second time, reduced sintering temperature, guaranteed to burn till the high compaction of porcelain body, and increased the molar percentage of Volatile Elements Ca in raw material, suppressed " defect effect " that in the sintering process, Volatile Elements Ca causes.
See also Fig. 2, Figure 2 shows that in the preparation method of microwave dielectric ceramic materials according to an embodiment of the invention, pass through respectively traditional mechanically mixing (12 hours) (a) and high-energy ball milling (2 hours) (b) prepares respectively powder for the first time particle size distribution figure.
In figure, X-coordinate is particle size diameter, and unit is μ m, and left side ordinate zou is powder per-cent, and unit is %, and the right ordinate zou is quality factor q, and unit is on%.Can obviously draw the powder particles high concentration that the preparation method that adopts microwave dielectric ceramic materials of the present invention makes from figure, granularity narrows obviously, and diameter is generally less than 1 μ m, and has very high quality factor q.
See also Fig. 3, Figure 3 shows that in the preparation method of microwave dielectric ceramic materials according to an embodiment of the invention, adopt respectively traditional mechanically mixing+solid reaction process (a) and mechanically mixing of the present invention to make respectively scanning electron microscope (SEM) image of CTLA base microwave dielectric ceramics sample in conjunction with high-energy ball milling method (b).
Can find out obviously that from figure the microwave dielectric ceramic materials that the preparation method that adopts microwave dielectric ceramic materials of the present invention makes does not have obvious crackle and local hole (pore), its porcelain body even particle distribution and high compaction.
By the way, thereby the preparation method of microwave dielectric ceramic materials of the present invention adopts molar percentage and the medium dielectric constant microwave medium of incorporating ultrafine powder technology of preparing easy fired high compaction and the microwave dielectric ceramic materials of high quality factor of appropriate increase Volatile Elements Ca in raw material, " defect effect " that not only can suppress the volatile generation of Ca element, reduce to a great extent sintering temperature and shorten sintering time, and realize burning till the high compaction of porcelain body, thereby reduced production cost and technical difficulty.
The above is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention and accompanying drawing content to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in scope of patent protection of the present invention.
Claims (16)
1. the preparation method of a microwave dielectric ceramic materials, is characterized in that, comprising:
The mixed powder of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide is carried out the mechanical uniform mixing, form powder granule;
Described powder granule is carried out high-energy ball milling for the first time, with the even refinement of described powder granule;
With the powder high-temperature calcination in encloses container after described high-energy ball milling for the first time, form the presoma powder;
Described presoma powder is carried out high-energy ball milling for the second time, with the further evenly refinement of described presoma powder, form ceramic powder.
2. the preparation method of microwave dielectric ceramic materials according to claim 1, is characterized in that, also comprises after the described step of high-energy ball milling for the second time:
Mist projection granulating adds concentration and is 5%, mass percent is 5%～10% polyvinyl alcohol water solution, described ceramic powder is made the powder granule of the spherical mobility of tool in described ceramic powder.
3. the preparation method of microwave dielectric ceramic materials according to claim 2, is characterized in that, also comprises after described mist projection granulating step:
The pressed compact of desired shape is made the powder granule of the spherical mobility of described tool in compression moulding.
4. the preparation method of microwave dielectric ceramic materials according to claim 3, is characterized in that, described pressed compact carries out two-sided compression moulding by pressing machine in filler mode manually or automatically, perhaps carries out shot moulding by shot forming technique.
5. the preparation method of microwave dielectric ceramic materials according to claim 3, is characterized in that, also comprises after described compression moulding step:
Sintering carries out stoking with described pressed compact, forms ceramic blank, and wherein, the highest sintering temperature is 1300～1500 degrees centigrade, and soaking time is 3～6 hours.
6. the preparation method of microwave dielectric ceramic materials according to claim 5, it is characterized in that, also comprise after described sintering step: mechanical workout and sample detection, described ceramic blank is carried out surface treatment obtain sample, and measure the dielectric properties index of described sample.
7. the preparation method of microwave dielectric ceramic materials according to claim 1, is characterized in that, the formula of microwave dielectric ceramic materials is according to chemical formula (1-x) Ca
1+yTiO
3-x[La
1-zRe
zAlO
3] make wherein molar percentage x, y and z satisfy respectively 0.1mol%≤x≤0.7mol%, 0.1mol%≤y≤0.5mol% and 0.01mol%≤z≤0.1mol%, the purity of described calcium carbonate and aluminum oxide is all greater than 99.5%, and the purity of described titanium dioxide and lanthanum trioxide is not less than 99.9%.
8. the preparation method of microwave dielectric ceramic materials according to claim 1, it is characterized in that, with calcium carbonate, aluminum oxide, the step that the mixed powder of lanthanum trioxide and titanium dioxide carries out the mechanical uniform mixing comprises: add the zirconium dioxide abrading-ball as grinding medium in spherical tank, adding dehydrated alcohol or deionized water as organic solvent, mixed powder to be carried out mechanical uniform mixes, and after forming powder granule, remove organic solvent and carry out drying treatment, wherein, mixed powder, grinding medium, organic solvent three part by weight is 1: 3: 3 and accounts for 60%～80% of spherical tank volume, mixing time is 1～3 hour.
9. the preparation method of microwave dielectric ceramic materials according to claim 1, it is characterized in that, described powder granule is carried out for the first time in the high-energy ball milling step, and ratio of grinding media to material is 8: 1～10: 1, Ball-milling Time is 1～3 hour, and rotating speed is 600～800 rev/mins.
10. the preparation method of microwave dielectric ceramic materials according to claim 9, is characterized in that, the size-grade distribution of the powder after described high-energy ball milling for the first time is in 1～2 μ m scope.
11. the preparation method of microwave dielectric ceramic materials according to claim 1 is characterized in that, in the high-temperature calcination step, encloses container is high-temperature crucible, and calcining temperature is 1100～1350 degrees centigrade, and soaking time is 3～5 hours.
12. the preparation method of microwave dielectric ceramic materials according to claim 1, it is characterized in that, described presoma powder is carried out for the second time in the high-energy ball milling step, and ratio of grinding media to material is 10: 1～12: 1, Ball-milling Time 1～3 hour, 800～1000 rev/mins of rotating speeds.
13. the preparation method of microwave dielectric ceramic materials according to claim 12 is characterized in that, the granularity of the ceramic powder after described high-energy ball milling for the second time is less than 1 μ m.
14. the preparation method of microwave dielectric ceramic materials according to claim 1 is characterized in that, described presoma powder is carried out for the second time further adding modification doping agent, property-modifying additive and sintering aid in the high-energy ball milling step.
15. the preparation method of microwave dielectric ceramic materials according to claim 14, it is characterized in that, described modification doping agent is the oxide compound that contains rare earth element, described rare earth element is one or more in yttrium, neodymium, cerium, praseodymium, samarium, europium, gadolinium, dysprosium, erbium and ytterbium, and described property-modifying additive is CaO, SrO, TiO
2, ZnO, Al
2O
3, Nb
2O
5And Ta
2O
5In one or more, described sintering aid is Bi
2O
3, B
2O
3, CuO, V
2O
5And one or more in BaO.
16. the preparation method of microwave dielectric ceramic materials according to claim 15 is characterized in that, the formula of medium ceramic material is according to chemical formula (1-x) Ca
1+yTiO
3-x[La
1-zRe
zAlO
3] make wherein molar percentage x, y and z satisfy respectively 0.1mol%≤x≤0.7mol%, 0.1mol%≤y≤0.5mol% and 0.01mol%≤z≤0.1mol%.Wherein, the mass percent of described property-modifying additive is 1%～4% of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide total amount, and the mass percent of described sintering aid is 0.1%～1% of calcium carbonate, aluminum oxide, lanthanum trioxide and titanium dioxide total amount.
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| CN2011104357847A CN103172367A (en) | 2011-12-22 | 2011-12-22 | Preparation method of microwave dielectric ceramic material |
| PCT/CN2012/085435 WO2013078993A1 (en) | 2011-11-30 | 2012-11-28 | Method for manufacturing microwave dielectric ceramic material |
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