CN102584212A - Low-dielectric-loss ceramic material and preparation method thereof - Google Patents
Low-dielectric-loss ceramic material and preparation method thereof Download PDFInfo
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- CN102584212A CN102584212A CN2012100220939A CN201210022093A CN102584212A CN 102584212 A CN102584212 A CN 102584212A CN 2012100220939 A CN2012100220939 A CN 2012100220939A CN 201210022093 A CN201210022093 A CN 201210022093A CN 102584212 A CN102584212 A CN 102584212A
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Abstract
The invention discloses a low-dielectric-loss ceramic material and a preparation method thereof and relates to a ceramic material. The low-dielectric-loss ceramic material consists of CaCu3Ti4O12 and V2O5 and the chemical formula is CaCu3Ti4O12+xV2O5, wherein x is equal to 0.001-0.005; or the low-dielectric-loss ceramic material consists of CaCu3Ti4O12 and Bi2O3-CuO and the chemical formula is CaCu3Ti4O12+x[yBi2O3-(1-y)CuO], wherein x is equal to 0.005-0.05 and y is equal to 0.4-0.5. In an atmosphere of air, CaCO3, CuO, TiO2 and V2O5 or Bi2O3 are used as raw materials, a solid-phase method is adopted, V2O5 or Bi2O3 is used as an additive, the press-formed ceramic material sample is heated for binder removal, the sample after binder removal is continuously heated and then the sample is cooled to room temperature together with a furnace to obtain the low-dielectric-loss ceramic material.
Description
Technical field
The present invention relates to a kind of stupalith, especially relate to a kind of low-dielectric loss stupalith and preparation method thereof.
Background technology
Stupalith CaCu
3Ti
4O
12(being abbreviated as CCTO) in 1979 by (the B.Bochu of Bochu seminar; M.N.Deschizeaux; J.C.Joubert, et al.Synthese et caract é risation d ' unes é rie de titanates p ē rowskites isotypes de [CaCu
3] (Mn
4) O
12.Journal of Solid State Chemistry, 1979,29 (2): 291-298) through the solid sintering technology preparation.People (M.A.Subramanian, Li Dong, Duan N, et al.High dielectric constant in ACu such as M.A.Subramanian in 2000
3Ti
4O
12And ACu
3Ti
3FeO
12Phases.Solid State Chem., 2000,151:323-325) find to have the CaCu of calcium titanium ore structure
3Ti
4O
12(CCTO) its specific inductivity and has very little temperature dependency more than 10000 under the frequency of 1KHz, from its value between the room temperature to 300 ℃ near constant.Along with the development of microelectronics industry, the microminiaturization of electronic devices and components is just pressing for this high dielectric-constant dielectric material, has very big application potential aspect the important electron devices such as storer, wave filter, resonator.
Though CCTO has huge specific inductivity, the loss of CCTO ceramic dielectric also bigger (Ni Weiqing, Yu Jianchang, Zheng Xinghua, Liang Ping Liang. firing process is to CaCu
3Ti
4O
12Ceramic dielectric Effect on Performance [J], electronic component and material, 2006,10 (10): 26-29).In practical application, can cause the problems such as heating, job insecurity or signal attenuation of device or circuit, bigger dielectric loss has limited the application of CCTO.Some scholars are doing a lot of trials aspect the loss of reduction CCTO ceramic dielectric; These trials or do not reach the purpose that enough degree reduces dielectric loss; Obvious damage the original high-k characteristic of CCTO pottery, cause modification after specific inductivity very low: people such as Li Jie utilize cold isostatic compaction technology in Chinese patent 200710009111.9; The loss of CCTO ceramic dielectric is dropped to 0.026 in room temperature, 1KHz condition, but specific inductivity is reduced to about 3000 also.People such as KOBAYASH (KOBAYASHI W, TERASAKI I.CaCu
3Ti
4O
12/ CaTiO
3Composite dielectrics:Ba/Pb-free dielectric ceramics with high dielectric constants [J] Appl.Phys.Lett., 2005,87:032902-032904) composition of change CCTO is prepared Ca
2Cu
2Ti
4O
12(moity is CaCu
3Ti
4O
12And CaTiO
3), its dielectric loss is 0.02 under room temperature, 100KHz condition, specific inductivity reduces to 1800.People such as PATTERSON (PATTERSON E A, KWON S, HUANG C C, et al.Effects of ZrO
2Additions on the dielectric properties of CaCu
3Ti
4O
12[J] Appl.Phys.Lett., 2005,87:182911-182913) through adding ZrO
2Method, make the loss of CCTO ceramic dielectric drop to 0.05 in room temperature, 1KHz condition, specific inductivity is also reduced to below 5000.
Summary of the invention
The purpose of this invention is to provide a kind of low-dielectric loss stupalith and preparation method thereof.
Said low-dielectric loss stupalith is by CaCu
3Ti
4O
12And V
2O
5Form, chemical formula is CaCu
3Ti
4O
12+ xV
2O
5, x=0.001～0.005 wherein.
Said low-dielectric loss stupalith is by CaCu
3Ti
4O
12And Bi
2O
3-CuO forms, and chemical formula is CaCu
3Ti
4O
12+ x [yBi
2O
3-(1-y) CuO], x=0.005～0.05 wherein, y=0.4～0.5.
Said low-dielectric loss stupalith CaCu
3Ti
4O
12+ xV
2O
5The preparation method following:
Under air atmosphere, with CaCO
3, CuO, TiO
2, V
2O
5Be raw material, adopt solid phase method technology, wherein V
2O
5As additive, with the ceramic material sample intensification of press forming, carry out binder removal and handle, the sample after binder removal is handled continues to heat up, and cools to room temperature then with the furnace, promptly obtains low-dielectric loss stupalith CaCu
3Ti
4O
12+ xV
2O
5
The temperature rise rate that the condition of said intensification can be with 3 ℃/min is incubated 2h after room temperature rises to 600 ℃; The condition that said continuation heats up is incubated 5～10h after can be and rising to 1000～1100 ℃ of sintering with 3 ℃/min temperature rise rate.
Said low-dielectric loss stupalith CaCu
3Ti
4O
12+ x [yBi
2O
3-(1-y) CuO] the preparation method following:
Under air atmosphere, with CaCO
3, CuO, TiO
2, Bi
2O
3Be raw material, adopt solid phase method technology, wherein Bi
2O
3-CuO, carries out binder removal and handles the ceramic material sample intensification of press forming as additive, and the sample after binder removal is handled continues to heat up, and cools to room temperature then with the furnace, promptly obtains low-dielectric loss stupalith CaCu
3Ti
4O
12+ x [yBi
2O
3-(1-y) CuO].
The condition of said intensification can be with 3 ℃/min temperature rise rate and after room temperature rises to 600 ℃, is incubated 2h; The condition that said continuation heats up is incubated 5～10h after can be and rising to 1000～1100 ℃ of sintering with 3 ℃/min temperature rise rate.
The present invention has the following advantages: the method for a kind of CCTO of reduction ceramic dielectric loss is provided, has adopted solid phase method technology, through adding V
2O
5Or Bi
2O
3-CuO at high temperature sinters porcelain into.(specific inductivity reaches 10 keeping the CCTO high-k
4～10
5The order of magnitude) time, reduces the CCTO dielectric loss, prepare the CCTO stupalith of high dielectric constant and low dielectric loss, improved the dielectric properties of CCTO stupalith.Fully use simple, repeatable high, the yield rate advantages of higher of solid-phase process preparation, be easy to realize large-tonnage suitability for industrialized production.
The present invention is through the change of additive and the variation of component, and (specific inductivity reaches 10 keeping CCTO stupalith high-k
4～10
5The order of magnitude) time, reduces its dielectric loss, improve the dielectric properties of this stupalith.
Embodiment
Following examples will be further described the present invention.
Embodiment 1
Use solid phase method to prepare component and mass percentage content is CaCu at 1080 ℃ of insulation 10h
3Ti
4O
12+ 0.001V
2O
5Stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is 120 ℃ of oven dry in baking oven, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.99g pre-burning powder, adding 0.01g purity is 99.0% V
2O
5Powder also mixes, and adds sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1080 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 10h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=32038, tan δ=0.026.
Embodiment 2
Use solid phase method to prepare component and mass percentage content is CaCu at 1080 ℃ of insulation 10h
3Ti
4O
12+ 0.005V
2O
5Stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is measured oven dry under 1 room temperature, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.95g pre-burning powder, adding 0.05g purity is 99.0% V
2O
5Powder also mixes, and adds sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1080 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 10h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=19990, tan δ=0.0565.
Embodiment 3
Use solid phase method to prepare component and mass percentage content is CaCu at 1080 ℃ of insulation 10h
3Ti
4O
12+ 0.005 (0.444Bi
2O
3-0.556CuO) stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is at room temperature measured oven dry, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.95g pre-burning powder, adding 0.0222g purity is 99.0% Bi
2O
3Powder, 0.0278g purity are 99.0% CuO powder and mix, and add sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1080 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 10h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=62675, tan δ=0.086.
Embodiment 4
Use solid phase method to prepare component and mass percentage content is CaCu at 1080 ℃ of insulation 10h
3Ti
4O
12+ 0.05 (0.444Bi
2O
3-0.556CuO) stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is at room temperature measured oven dry, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.5g pre-burning powder, adding 0.2222g purity is 99.0% Bi
2O
3Powder, 0.2778g purity are 99.0% CuO powder and mix, and add sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1080 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 10h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=6674.5, tan δ=0.0775.
Embodiment 5
Use solid phase method to prepare component and mass percentage content is CaCu at 1000 ℃ of insulation 10h
3Ti
4O
12+ 0.001V
2O
5Stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is 120 ℃ of oven dry in baking oven, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.99g pre-burning powder, adding 0.01g purity is 99.0% V
2O
5Powder also mixes, and adds sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1000 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 10h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=11820, tan δ=0.154.
Embodiment 6
Use solid phase method to prepare component and mass percentage content is CaCu at 1000 ℃ of insulation 10h
3Ti
4O
12+ 0.005V
2O
5Stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is measured oven dry under 1 room temperature, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.95g pre-burning powder, adding 0.05g purity is 99.0% V
2O
5Powder also mixes, and adds sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1000 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 10h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=9890.3, tan δ=0.187.
Embodiment 7
Use solid phase method to prepare component and mass percentage content is CaCu at 1000 ℃ of insulation 10h
3Ti
4O
12+ 0.005 (0.4Bi
2O
3-0.6CuO) stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is at room temperature measured oven dry, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.95g pre-burning powder, adding 0.02g purity is 99.0% Bi
2O
3Powder, 0.03g purity are 99.0% CuO powder and mix, and add sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1000 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 10h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=15328, tan δ=0.194.
Embodiment 8
Use solid phase method to prepare component and mass percentage content is CaCu at 1000 ℃ of insulation 10h
3Ti
4O
12+ 0.05 (0.4Bi
2O
3-0.6CuO) stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is at room temperature measured oven dry, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.5g pre-burning powder, adding 0.2g purity is 99.0% Bi
2O
3Powder, 0.3g purity are 99.0% CuO powder and mix, and add sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1000 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 10h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=4674.5, tan δ=0.128.
Embodiment 9
Use solid phase method to prepare component and mass percentage content is CaCu at 1100 ℃ of insulation 5h
3Ti
4O
12+ 0.001V
2O
5Stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is 120 ℃ of oven dry in baking oven, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.99g pre-burning powder, adding 0.01g purity is 99.0% V
2O
5Powder also mixes, and adds sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1100 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 5h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=21056, tan δ=0.028.
Embodiment 10
Use solid phase method to prepare component and mass percentage content is CaCu at 1100 ℃ of insulation 5h
3Ti
4O
12+ 0.005V
2O
5Stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is measured oven dry under 1 room temperature, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.95g pre-burning powder, adding 0.05g purity is 99.0% V
2O
5Powder also mixes, and adds sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1100 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 5h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=14650, tan δ=0.065.
Embodiment 11
Use solid phase method to prepare component and mass percentage content is CaCu at 1100 ℃ of insulation 5h
3Ti
4O
12+ 0.005 (0.5Bi
2O
3-0.5CuO) stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is at room temperature measured oven dry, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.95g pre-burning powder, adding 0.025g purity is 99.0% Bi
2O
3Powder, 0.025g purity are 99.0% CuO powder and mix, and add sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1100 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 5h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=55996, tan δ=0.0989.
Embodiment 12
Use solid phase method to prepare component and mass percentage content is CaCu at 1100 ℃ of insulation 5h
3Ti
4O
12+ 0.05 (0.5Bi
2O
3-0.5CuO) stupalith.With purity 99.0% CaCO
3Powder, CuO powder, TiO
2Powder mixes in molar ratio, puts into the agate jar wet ball grinding, is ball-milling medium with zero(ppm) water, by quality than raw material: agate ball: zero(ppm) water=1: 1: 1.2.Use planetary ball mill with 300r/min ball milling 4h, mixed powder after grinding is at room temperature measured oven dry, and the powder after will drying then places retort furnace, rises to 1000 ℃ of pre-burnings and is incubated 2h from room temperature with 3 ℃/min temperature rise rate.The pre-burning powder is through ball mill crushing, drying.Get 9.5g pre-burning powder, adding 0.25g purity is 99.0% Bi
2O
3Powder, 0.25g purity are 99.0% CuO powder and mix, and add sticker then, and 80 eye mesh screens are crossed in grinding, granulation in agate mortar.Prilling powder dry-pressing under 450MPa pressure is become diameter 13mm, the disk of thickness 1.2mm.Base substrate is risen to 600 ℃ of insulation 2h with 3 ℃/min temperature rise rate from room temperature carry out the binder removal processing in retort furnace under air atmosphere; After rising to 1100 ℃ with 3 ℃/min temperature rise rate, sample continuation after binder removal is handled is incubated 5h; Cool to room temperature then with the furnace, obtain ceramic body.Surface finish, last Ag electrode carries out the dielectric properties test.Measure under the room temperature, during 1kHz, ε
r=6832.6, tan δ=0.095.
Claims (8)
1. a low-dielectric loss stupalith is characterized in that by CaCu
3Ti
4O
12And V
2O
5Form, chemical formula is CaCu
3Ti
4O
12+ xV
2O
5, x=0.001～0.005 wherein.
2. the preparation method of a kind of low-dielectric loss stupalith as claimed in claim 1 is characterized in that its concrete steps are:
Under air atmosphere, with CaCO
3, CuO, TiO
2, V
2O
5Be raw material, adopt solid phase method technology, wherein V
2O
5As additive, with the ceramic material sample intensification of press forming, carry out binder removal and handle, the sample after binder removal is handled continues to heat up, and cools to room temperature then with the furnace, promptly obtains low-dielectric loss stupalith CaCu
3Ti
4O
12+ xV
2O
5
3. the preparation method of a kind of low-dielectric loss stupalith as claimed in claim 2 is characterized in that the condition of said intensification is incubated 2h for the temperature rise rate with 3 ℃/min after room temperature rises to 600 ℃.
4. the preparation method of a kind of low-dielectric loss stupalith as claimed in claim 2 is characterized in that the condition that said continuation heats up is incubated 5～10h after rising to 1000～1100 ℃ of sintering with 3 ℃/min temperature rise rate.
5. a low-dielectric loss stupalith is characterized in that by CaCu
3Ti
4O
12And Bi
2O
3-CuO forms, and chemical formula is CaCu
3Ti
4O
12+ x [yBi
2O
3-(1-y) CuO], x=0.005～0.05 wherein, y=0.4～0.5.
6. the preparation method of a kind of low-dielectric loss stupalith as claimed in claim 5 is characterized in that its concrete steps are:
Under air atmosphere, with CaCO
3, CuO, TiO
2, Bi
2O
3Be raw material, adopt solid phase method technology, wherein Bi
2O
3-CuO, carries out binder removal and handles the ceramic material sample intensification of press forming as additive, and the sample after binder removal is handled continues to heat up, and cools to room temperature then with the furnace, promptly obtains low-dielectric loss stupalith CaCu
3Ti
4O
12+ x [yBi
2O
3-(1-y) CuO].
7. the preparation method of a kind of low-dielectric loss stupalith as claimed in claim 6, the condition that it is characterized in that said intensification is for to be incubated 2h with 3 ℃/min temperature rise rate after room temperature rises to 600 ℃.
8. the preparation method of a kind of low-dielectric loss stupalith as claimed in claim 6 is characterized in that the condition that said continuation heats up is incubated 5～10h after rising to 1000～1100 ℃ of sintering with 3 ℃/min temperature rise rate.
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| CN107930825A (en) * | 2017-11-24 | 2018-04-20 | 龙岩高岭土股份有限公司 | A kind of method that separation colour developing mineral improve product quality from porcelain stone |
| CN112811897A (en) * | 2021-01-11 | 2021-05-18 | 湖南省美程陶瓷科技有限公司 | Pressure sensor ceramic material and preparation method thereof |
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