CN109231977A - A kind of high-temperature stable medium ceramic material and preparation method thereof - Google Patents
A kind of high-temperature stable medium ceramic material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high-temperature stable medium ceramic material and preparation method thereof, the high-temperature stable medium ceramic material has aspidelite structure, and constitutional chemistry formula is CaTi1‑xM10.5xM20.5xSiO5, wherein M1 and M2 is metal ion, 0 < x≤10%, preferably 3≤x≤5%.
Description
Technical field
The present invention relates to a kind of high-temperature stable medium ceramic material and preparation method thereof, in particular to a kind of high-temperature stable
Aspidelite structure multilayer ceramic capacitor dielectric ceramic material and preparation method thereof, belongs to ceramic material technical field.
Background technique
Multilayer ceramic capacitor (Multilayer Ceramic Capacitor, MLCC) as blocking, coupling, bypass,
The critical elements of filtering, resonant tank etc. are widely used in consumption electronic product, wireless telecommunications, automotive electronics, weaponry etc.
Numerous areas.Especially the fields such as aerospace, oil drilling require that electronic system can be under extreme harsh environment just
Normal steady operation, this requires MLCC that can work at a high temperature of 200 DEG C or more.So it is steady to explore the high dielectric temperature of exploitation
Fixed ceramic dielectric material is of great significance.
The high temperature capacitors dielectric material of most study is multiple based on two or more ferroelectric or relaxation ferroelectric
The dielectric material of conjunction.For the ferroelectric or relaxation ferroelectric ceramics applied to 200 DEG C or more, with the high dielectric of perovskite structure
Constant material is main feature, is being more than in complex media when temperature although can satisfy 200 DEG C of temperature service condition
After a kind of Curie temperature of material, due to Curie-weiss effect, dielectric constant can have significant fluctuation with gradient of temperature,
This has a significant impact for the long-time stability of material at high temperature.
The dielectric constant of linear medium is generally free from the influence of extra electric field.So although linear dielectric usually has
Relatively low dielectric constant can obtain high-energy density due to its high dielectric breakdown strength and biggish band gap.Cause
This is expected to obtain the high storage for the function admirable that can be worked at high temperature if the high-temperature stability that linear dielectric can have
The capacitor dielectric material of energy density.
Reported in literature aspidelite structural material Ca (Ti0.85Zr0.15)SiO5(Applied Physics Letters, 108,
062902,2016) there is excellent dielectric-temperature stability and electrical insulation characteristics, the temperature range class phase between 300-780K
It is about 43 to dielectric constant, dielectric loss is higher than 10 less than 0.05, in the resistance of 523K or less material11Ω cm, but aspidelite knot
Structure material C a (Ti0.85Zr0.15)SiO5Relative dielectric constant it is lower.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide a kind of capacitor dielectric material of high-temperature stable and its preparation sides
Method.
On the one hand, the present invention provides a kind of high-temperature stable medium ceramic material, the high-temperature stable medium ceramic materials
With aspidelite structure, constitutional chemistry formula is CaTi1-xM10.5xM20.5xSiO5, wherein M1 and M2 be metal ion, 0 < x≤
10%.
The present invention has smaller by obtaining relatively high dielectric constant to the electricity prices codope such as aspidelite structural ceramics
Dielectric loss and high insulation resistance.It, being capable of effective Horizon by the doping of M1 and M2 with Ti ion different ions radius
Weigh electricity price, and lattice is made to twist.The present invention also improves crystallite dimension by modes such as sand millings, and it is strong to obtain biggish breakdown
Degree, to obtain preferable energy storage density.In addition, trivalent M1 and pentavalent M2 equivalent doping of the present invention using Ti, realize etc.
Electricity price is co-doped with, and avoids the generation of aspidelite structure antiferroelectric phase, improves Jie's temperature stability of dielectric material.
Preferably, replacing Ti ion, M1 and the average electricity of two metal ion species of M2 jointly using two metal ion species M1 and M2
The sum of valence is+4.
Preferably, M1 is at least one of Al, Ga, In three-group metal element, in M2 Nb, Ta group-v element at least
It is a kind of.The present invention can effectively balance electricity by the trivalent M1 and pentavalent M2 of equivalent doping and Ti ion different ions radius
Valence, and lattice is made to twist.In addition, doped chemical (one of M1 Al, Ga, In, M2 are one of Nb, Ta) adds
The intrinsic phase transformation for entering to inhibit aspidelite structural material makes it in room temperature to obtaining stable dielectric properties within the scope of 300 DEG C.
Preferably, dielectric constant of the high-temperature stable medium ceramic material at 25~300 DEG C is 38~57, preferably
47~53.
Preferably, the compressive resistance of the high-temperature stable medium ceramic material is greater than 900kV/cm, preferably > 1000kV/
cm。
On the other hand, the present invention also provides a kind of preparation methods of above-mentioned high-temperature stable medium ceramic material, comprising:
The source Ca, the source Si, the source Ti, the source M1, the source M2 powder are weighed simultaneously according to the constitutional chemistry formula of the high-temperature stable medium ceramic material
Mixing, obtains mixed powder；
By the pre-burning at 800~1200 DEG C of gained mixed powder, pre-burning powder is obtained；
By gained pre-burning powder and binder, then repressed molding, green body is obtained；
By gained green body after dumping, it is sintered 2~6 hours at 1250~1350 DEG C, obtains the high-temperature stable media ceramic
Material.
Preferably, the source Ca is CaCO3, the source Si be SiO2, the source Ti be TiO2, oxygen that the source M1 is M1
Compound, the oxide that the source M2 is M2.
Preferably, the system of the pre-burning includes: first at 800~1000 DEG C to keep the temperature 1~4 hour, then at 1100~
4~8 hours are kept the temperature at 1200 DEG C；Preferably, 2 hours first are kept the temperature at 900 DEG C, then is warming up at 1150 DEG C and keeps the temperature 6 hours.This
In invention by two kinds of elements etc. electricity prices be co-doped with and preparation process in two step pre-burnings, gained high-temperature stable media ceramic
Material has temperature-stable and high withstand voltage intensity.
Preferably, the heating rate of the pre-burning is 2~5 DEG C/min.
Preferably, the binder is at least one of PVAC polyvinylalcohol, polyvinyl butyral PVB；The bonding
The additional amount of agent is 6~8wt% of pre-burning powder quality.
Preferably, the mode of the compression moulding is dry-pressing formed and/isostatic pressing, it is preferably first dry-pressing formed, then etc.
Hydrostatic profile；The dry-pressing formed pressure is 0.5~2MPa, and the pressure of the isostatic pressing is 200~300MPa.
Preferably, the temperature of the dumping is 450~650 DEG C, the time is 0.5~2 hour.
Preferably, the heating rate of the dumping is 2~5 DEG C/min；The heating rate of the sintering is 3~5 DEG C/minute
Clock.
The beneficial effects of the present invention are: pure phase (M1-M2) has been made and has been co-doped with aspidelite by adjusting the ratio of Ti/ (M1-M2)
Structural ceramics obtains preferable capacitance temperature factor in 25 DEG C to 300 DEG C temperature ranges.At room temperature, biggish hit can be obtained
Intensity and energy storage density are worn, can all guarantee good energy storage efficiency in 25 DEG C to 180 DEG C temperature ranges.
Detailed description of the invention
The XRD diagram of the high-temperature stable medium ceramic material that Fig. 1 is embodiment 1-4 and prepared by comparative example 1 at room temperature
Spectrum, it can be seen that all embodiments and comparative example all form pure CaTiSiO5Phase, but as x=0 and x=0.5%, out
In existing antiferroelectric CaTiSiO5 phaseWithCharacteristic peak, remaining characteristic peak are paraelectric phase.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the present invention, by aspidelite structure C aTiSiO5The electricity prices codopes such as material Ti, in the base of balance chemical valence
It on plinth, improves its dielectric constant and keeps other performance, to obtain high energy storage density and condenser capacity density.Its
In, the constitutional chemistry formula of high-temperature stable medium ceramic material can be CaTi1-xM10.5xM20.5xSiO5, wherein M1 is in Al, Ga, In
One kind, M2 is one of Nb, Ta, 0 < x≤10%.When x value is more than 10%, the defect of resulting materials increases, dielectric
Constant is decreased obviously and compressive resistance significantly reduces.Further preferably, x is 3%~5%.
In alternative embodiments, dielectric constant of the high-temperature stable medium ceramic material at 25 DEG C~300 DEG C is 47
~57.
In an embodiment of the present invention, high-temperature stable medium ceramic material is prepared by solid phase reaction method.With shown below
Illustrate to example property the preparation method of high-temperature stable medium ceramic material.
It according to the weighing source Ca molar ratio 1:1:(1-x): 0.5x:0.5x, the source Si, the source Ti, the source Al, the source Nb and mixes, obtains
Mixed powder.Wherein, the source Ca is CaCO3.The source Si can be SiO2.The source Ti can be TiO2.The source M1 can for M1 oxide (for example,
Al2O3、Ga2O3、In2O3).The source M2 is the oxide of M2 (for example, Nb2O3、Ta2O3).Mixed mode can be mixed for ball milling
It closes.It is preferred that carrying out drying and processing, sieving after ball milling mixing, mixed powder is obtained.As an example, claim according to molar ratio
Measure CaCO3、SiO2、TiO2、Al2O3、Nb2O5Powder is that raw material is configured to mixture, and ball milling is then added into the mixture and helps
It is dried after the abundant ball milling of agent, 60 meshes is crossed after the mixture after drying is fully ground, obtain mixed powder.
By mixed powder in 900 DEG C or more (such as 900~1150 DEG C) progress preheatings.It is preferred that using pre-burning twice,
2~4 hours first are kept the temperature at 900~1000 DEG C, in order to which powder can sufficiently absorb heat and obtain the preburning powder of pure phase, then at
4~7 hours are kept the temperature at 1100~1150 DEG C, obtains the pre-burning powder with pure aspidelite structure phase.Further preferably, first 900
2 hours are kept the temperature at DEG C, then is warming up at 1150 DEG C and keeps the temperature 6 hours.Wherein, the heating rate of pre-burning can be 2~5 DEG C/min.This
Outside, by first drying sieving after pre-burning powder ball milling, then pre-burning powder is handled under conditions of 760 DEG C, removal is wherein
Extra organic matter.
By pre-burning powder and binder mixing granulation, after sieve, compression moulding obtains green body.
By green body after dumping, it is sintered 2~6 hours at 1250~1300 DEG C, obtains high-temperature stable medium ceramic material.
Wherein, the temperature of dumping can be 450~650 DEG C, and the time is 0.5~2 hour.The heating rate of dumping can be 2~5 DEG C/min.
The heating rate of sintering can be 3~5 DEG C/min.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
Selection Ti:Al:Nb molar ratio is 1:0:0, by CaCO3、SiO2、TiO2、Al2O3And Nb2O5Powder is according to CaTiSiO5Point
Minor mixes after weighing, and ball milling is dried after 6 hours, obtains mixed powder；
It is sieved after mixed powder is continued grinding, and it is small that the mixed-powder (mixed powder) after sieving is kept the temperature to 2 at 900 DEG C
When, then be warming up to 1150 DEG C and keep the temperature 6 hours；
By the powder (pre-burning powder) of pre-burning in nylon tank ball milling 6 hours again, then dry.By the powder mull after drying
Sieving, is then placed in furnace and handles 30 minutes under the conditions of 760 DEG C, to remove the organic matter in powder；
Alcohol is added in above-mentioned powder to be sanded, rate is 2000 rpms, is sanded 1 hour.By the mixing after sand milling
Solution drying, is added the binder PVA of 8wt%, and is fully ground uniformly, and be sieved.Powder, which is pressed into diameter, after sieving is
The thin slice of 13mm or so.The thin slice pressed is sealed, carries out waiting static pressure, pressure 250MPa in transformer oil；
Piece pressed is put into furnace and is warming up to 600 DEG C with 3 DEG C of rates per minute, keeps the temperature 2 hours, carries out dumping.Then
1250 DEG C are warming up to 5 DEG C of rates per minute, heat preservation is sintered for 6 hours.The XRD of gained sample is shown in Fig. 1.
Embodiment 2
Selection Ti:Al:Nb molar ratio is 0.995:0.0025:0.0025, by CaCO3、SiO2、TiO2、Al2O3And Nb2O5Powder
According to CaTi0.995Al0.0025Nb0.0025SiO5Molecular formula mixes after weighing, and ball milling is dried after 6 hours, obtains mixed powder；
It is sieved after mixed powder is continued grinding, and it is small that the mixed-powder (mixed powder) after sieving is kept the temperature to 2 at 900 DEG C
When, then be warming up to 1150 DEG C and keep the temperature 6 hours；
By the powder (pre-burning powder) of pre-burning in nylon tank ball milling 6 hours again, then dry.By the powder mull after drying
Sieving, is then placed in furnace and handles 30 minutes under the conditions of 760 DEG C, to remove the organic matter in powder；
Alcohol is added in above-mentioned powder to be sanded, rate is 2000 rpms, is sanded 1 hour.By the mixing after sand milling
Solution drying, is added the binder PVA of 8wt%, and is fully ground uniformly, and be sieved.Powder, which is pressed into diameter, after sieving is
The thin slice of 13mm or so.The thin slice pressed is sealed, carries out waiting static pressure, pressure 250MPa in transformer oil；
Piece pressed is put into furnace and is warming up to 600 DEG C with 3 DEG C of rates per minute, keeps the temperature 2 hours, carries out dumping.Then
1270 DEG C are warming up to 5 DEG C of rates per minute, heat preservation is sintered for 6 hours.The XRD of gained sample is shown in Fig. 1.
Embodiment 3
Selection Ti:Al:Nb molar ratio is 0.97:0.015:0.015, by CaCO3、SiO2、TiO2、Al2O3And Nb2O5Powder according to
CaTi0.97Al0.015Nb0.015SiO5Molecular formula mixes after weighing, and using dehydrated alcohol as medium, zirconia balls are that mill is situated between,
Ball milling is dried after 6 hours in nylon tank, obtains mixed powder；
It is sieved after mixed powder is continued grinding, and it is small that the mixed-powder (mixed powder) after sieving is kept the temperature to 2 at 900 DEG C
When, then be warming up to 1150 DEG C and keep the temperature 6 hours；
By the powder (pre-burning powder) of pre-burning in nylon tank ball milling 6 hours again, then dry.By the powder mull after drying
Sieving, is then placed in furnace and handles 30 minutes under the conditions of 760 DEG C, to remove the organic matter in powder；
Alcohol is added in above-mentioned powder to be sanded, rate is 2000 rpms, is sanded 1 hour.By the mixing after sand milling
Solution drying, is added the binder PVA of 8wt%, and is fully ground uniformly, and be sieved.Powder, which is pressed into diameter, after sieving is
The thin slice of 13mm or so.The thin slice pressed is sealed, carries out waiting static pressure, pressure 250MPa in transformer oil；
Piece pressed is put into furnace and is warming up to 600 DEG C with 3 DEG C of rates per minute, keeps the temperature 2 hours, carries out dumping.Then
1270 DEG C are warming up to 5 DEG C of rates per minute, heat preservation is sintered for 6 hours.The XRD of gained sample is shown in Fig. 1.
Embodiment 4
Selection Ti:Al:Nb molar ratio is 0.95:0.025:0.025, by CaCO3、SiO2、TiO2、Al2O3And Nb2O5Powder according to
CaTi0.95Al0.025Nb0.025SiO5Molecular formula mixes after weighing, and using dehydrated alcohol as medium, zirconia balls are that mill is situated between,
Ball milling is dried after 6 hours in nylon tank, obtains mixed powder；
It is sieved after mixed powder is continued grinding, and it is small that the mixed-powder (mixed powder) after sieving is kept the temperature to 2 at 900 DEG C
When, then be warming up to 1150 DEG C and keep the temperature 6 hours；
By the powder (pre-burning powder) of pre-burning in nylon tank ball milling 6 hours again, then dry.By the powder mull after drying
Sieving, is then placed in furnace and handles 30 minutes under the conditions of 760 DEG C, to remove the organic matter in powder；
Alcohol is added in above-mentioned powder to be sanded, rate is 2000 rpms, is sanded 1 hour.By the mixing after sand milling
Solution drying, is added the binder PVA of 8wt%, and is fully ground uniformly, and be sieved.Powder, which is pressed into diameter, after sieving is
The thin slice of 13mm or so.The thin slice pressed is sealed, carries out waiting static pressure, pressure 250MPa in transformer oil；
Piece pressed is put into furnace and is warming up to 600 DEG C with 3 DEG C of rates per minute, keeps the temperature 2 hours, carries out dumping.Then
1270 DEG C are warming up to 5 DEG C of rates per minute, heat preservation is sintered for 6 hours.The XRD of gained sample is shown in Fig. 1.
Comparative example 1
Selection Ti:Al:Nb molar ratio is 0.8:0.1:0.1, by CaCO3、SiO2、TiO2、Al2O3And Nb2O5Powder according to
CaTi0.8Al0.1Nb0.1SiO5Molecular formula mixes after weighing, and using dehydrated alcohol as medium, zirconia balls are that mill is situated between, in nylon
Ball milling is dried after 6 hours in tank, obtains mixed powder；
It is sieved after mixed powder is continued grinding, and it is small that the mixed-powder (mixed powder) after sieving is kept the temperature to 2 at 900 DEG C
When, then be warming up to 1150 DEG C and keep the temperature 6 hours；
By the powder (pre-burning powder) of pre-burning in nylon tank ball milling 6 hours again, then dry.By the powder mull after drying
Sieving, is then placed in furnace and handles 30 minutes under the conditions of 760 DEG C, to remove the organic matter in powder；
Alcohol is added in above-mentioned powder to be sanded, rate is 2000 rpms, is sanded 1 hour.By the mixing after sand milling
Solution drying, is added the binder PVA of 8wt%, and is fully ground uniformly, and be sieved.Powder, which is pressed into diameter, after sieving is
The thin slice of 13mm or so.The thin slice pressed is sealed, carries out waiting static pressure, pressure 250MPa in transformer oil；
Piece pressed is put into furnace and is warming up to 600 DEG C with 3 DEG C of rates per minute, keeps the temperature 2 hours, carries out dumping.Then
1250 DEG C are warming up to 5 DEG C of rates per minute, heat preservation is sintered for 6 hours.
Embodiment 5
Prepared high-temperature stable medium ceramic material obtains silver electrode on perfecting in embodiment 1-4, comparative example 1, after sintering
Carry out dielectric constant, compressive resistance, megger test, the data obtained such as table 1.
The electric parameters for the high-temperature stable medium ceramic material that table 1 is 1-4 of the embodiment of the present invention, prepared by comparative example 1:
Claims (8)
1. a kind of high-temperature stable medium ceramic material, which is characterized in that the high-temperature stable medium ceramic material has aspidelite knot
Structure, constitutional chemistry formula are CaTi1-xM10.5xM20.5xSiO5, wherein M1 and M2 is metal ion, 0 < x≤10%, preferably 3≤x
≤5%。
2. high-temperature stable medium ceramic material according to claim 1, which is characterized in that using two metal ion species M1 and
M2 replaces Ti ion jointly, and the sum of two metal ion species average electricity price of M1 and M2 is+4.
3. high-temperature stable medium ceramic material according to claim 2, which is characterized in that M1 Al, Ga, In three-group metal
At least one of element, at least one of M2 Nb, Ta group-v element.
4. high-temperature stable medium ceramic material according to any one of claim 1-3, which is characterized in that the high temperature is steady
Determining dielectric constant of the medium ceramic material at 25~300 DEG C is 38~57, preferably 47~53.
5. high-temperature stable medium ceramic material described in any one of -4 according to claim 1, which is characterized in that the high temperature is steady
The compressive resistance for determining medium ceramic material is greater than 900 kV/cm, preferably 1000 kV/cm of >.
6. a kind of preparation method of high-temperature stable medium ceramic material according to any one of claims 1 to 5, feature exist
In, comprising:
The source Ca, the source Si, the source Ti, the source M1, the source M2 powder are weighed simultaneously according to the constitutional chemistry formula of the high-temperature stable medium ceramic material
Mixing, obtains mixed powder；
By the pre-burning at 800~1200 DEG C of gained mixed powder, pre-burning powder is obtained；
By gained pre-burning powder and binder, then repressed molding, green body is obtained；
By gained green body after dumping, it is sintered 2~6 hours at 1250~1350 DEG C, obtains the high-temperature stable media ceramic
Material.
7. preparation method according to claim 6, which is characterized in that the source Ca is CaCO3, the source Si be SiO2, institute
Stating the source Ti is TiO2, the source M1 be M1 oxide, the source M2 be M2 oxide.
8. preparation method according to claim 6 or 7, which is characterized in that the system of the pre-burning include: first 800~
2~5 hours are kept the temperature at 1000 DEG C, keeps the temperature 4~8 hours at 1050~1200 DEG C；Preferably, first heat preservation 2 is small at 900 DEG C
When, then be warming up at 1150 DEG C and keep the temperature 6 hours.
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